Condensate Polishing Guidelines:

Ammonium Form Operation

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Condensate Polishing Guidelines:
Ammonium Form Operation

1004322

Final Report, September 2001

EPRI Project Manager

R. Dooley

EPRI • 3412 Hillview Avenue, Palo Alto, California 94304 • PO Box 10412, Palo Alto, California 94303 • USA
800.313.3774 • 650.855.2121 • [email protected] • www.epri.com
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M. A. Sadler

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CITATIONS

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This report describes research sponsored by EPRI

The report is a corporate document that should be cited in the literature in the following manner:

Condensate Polishing Guidelines: Ammonium Form Operation, EPRI, Palo Alto, CA: 2001.
1004322.

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REPORT SUMMARY

Successful condensate polishing operation maintains control of ionic and particulate impurity
transport in the fossil plant and allows the unit to operate more reliably. This report will assist
utilities in reducing the overall cost of condensate polishing.

Background
EPRI’s fossil plant guidelines for cycle chemistry provide direction and guidance on selecting
and optimizing water and steam chemistry for fossil plants. Since the optimum condensate and
feedwater treatments are central to ensuring plant component availability and reliability, the
chemistry parameters have been and are continuing to be tightened. EPRI's Condensate Polishing
Guidelines (EPRI report TR-104422) assist utilities in achieving these limits. The operation of
polishers in the “ammonia form” is a commonly used, but still controversial, method of reducing
operating costs. A fresh look at ammonium form operation of polishers was needed.

Objective
To provide comprehensive guidelines for all aspects of ammonium form operation of condensate
polishers.

Approach
The EPRI consultant reviewed the literature on ammonium form operation (AFO) of polishers
and interviewed a number of operators around the world and assembled the experiences from
Asia, Australia, Germany, Ireland, United Kingdom, United States and South Africa. He then
assembled an initial draft, which was reviewed by members of EPRI’s Boiler and Turbine Steam
and Cycle Chemistry Target, prior to producing the final version.

Results
The guideline contains individual sections on:
• Summary of experience of AFO around the world
• Theory of AFO
• Regeneration of polishers operating in the ammonium form
• A road map to help select power plants that could benefit from AFO
• Guidance on operation in the ammonium form.

EPRI Perspective
These guidelines provide detailed information to assist those plants currently operating using
AFO and to allow other plants to decide whether they could operate in this form. The guidelines

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indicate that if properly used, ammonium form polishers can routinely and consistently provide
condensate that meets all EPRI fossil plant cycle chemistry guidelines. AFO will provide full
protection against condenser leaks or similar incidences. Clearly, however, AFO is not suitable
for all plants. It is necessary to provide a very high degree of regeneration of the resins, and the
concentration of impurities in polished water from AFO polishers will always be higher than
achieved with the same resins operating in the H-OH mode.
These guidelines are part of a concentrated effort to increase the number of fossil plants with
condensate polishers and to improve their operating costs. Thus, EPRI is currently also
investigating radial flow polishing systems (EPRI report 1001409) and the use of off-site
regeneration (EPRI report 1001502).

Keywords
Water chemistry
Condensate polishing
Feedwater
Boiler water
Resins
Regeneration

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ABSTRACT

Previous EPRI reports have shown that condensate polishing is useful to power stations of all
types and that significant benefits, both operational and economic, can be derived from its
application. These benefits are generally accepted but there is now interest in reducing capital
and operational costs involved. Deep bed polishers, whether of the mixed bed or separate bed
type, conventionally operate with their anion and cation resins in the form to which they are
normally returned by the regeneration process. This is with the cation resin in the hydrogen ion
form (H+) and the anion resin in the hydroxide form (OH-). This mode of operation, the “H-OH
form”, is simple to use and is capable of producing a very high quality of polished condensate.
Unfortunately, relatively short service runs of, typically, 3 to 7 days are achieved so that the beds
require frequent regeneration as the cation resin becomes exhausted by ammonia in condensate.
Ammonium Form Operation is an alternative mode of operating polishing plants and employs
cation resins already converted to the ammonium form. In the absence of condenser leaks, this
leads to bed service lives of several months, as beds in this form are no longer capable of
removing ammonia. Significant savings in regeneration chemicals, water and operator time are
achieved by the use of this procedure and it has been successfully applied by many stations.

Unfortunately ammonium form operation of condensate polishers has disadvantages and because
of this EPRI has always adopted a cautious approach to its use. The quality of polished
condensate produced by plants run in this form is inferior to that potentially achievable from
polishers running in the conventional H-OH mode. Given very effective regeneration of the
resins, the condensate produced is acceptable for fossil stations with some ammonium form
polishers consistently yielding water containing less than 0.5 ppb (µg/kg) of ionic impurities.
However, power stations suffering frequent condenser leaks or startups will not benefit from its
use. Polisher beds are normally allowed to ammoniate in service and this usually gives rise to an
enhanced leakage of sodium, peaking at 1 to 3 ppb sodium, during the period following ammonia
breakthrough. Also, following condenser leaks or other impurity ingress incidents, the impurities
removed can subsequently be released or “thrown”. This occurs if conditions such as the pH of
the condensate or the level of influent impurity change and demonstrates the difference between
the conventional H-OH form of operation, in which impurities are held securely, and the possible
behaviour in ammonium form polishing. These Guidelines discuss the theory of running in the
economical ammonium form and procedures to be followed so as to minimise the associated
disadvantages. They provide advice to assist stations in deciding whether they should adopt
ammonium form operation as it is not suitable for all. Finally, they offer some, as yet untried,
ideas for further development of the technique.

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ACKNOWLEDGMENTS

In preparing this report the author has drawn from the many earlier papers on ammonium form
operation of condensate polishing plants. He gratefully acknowledges the help given by Albert
Bursik, Frances Cutler, Bruce Larkin, Frank McCarthy, Fred Pocock and John O’Sullivan. He
wishes to thank Professor Gary Foutch and Dr Denis Hussey of Oklahoma State University for
the computer simulations that they kindly provided. The help and encouragement given by
Dr. Barry Dooley is also gratefully acknowledged

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CONTENTS

1 INTRODUCTION ................................................................................................................. 1-1

1.1 Background ................................................................................................................. 1-1
1.2 General Benefits of Condensate Polishing .................................................................. 1-1
1.3 Steam Generator and Boiler Designs and their Condensate Quality Demands............ 1-1
1.3.1 Fossil Fired Power Stations With Drum Boilers ..................................................... 1-1
1.3.2 Fossil Power Stations With Once-through Boilers ................................................ 1-2
1.3.3 Once-through and Drum Boilers Employing Oxygenated Treatment ................... 1-2
1.3.4 Heat Recovery Steam Generators ....................................................................... 1-3
1.3.5 Nuclear Power Stations........................................................................................ 1-3
1.4 Types of Condensate Polishing Plants ....................................................................... 1-4
1.4.1 Filter Demineralisers (“Powdex”).......................................................................... 1-4
1.4.2 Deep Bed Condensate Polishing Plant Designs................................................... 1-4
1.5 Cost Implications of Condensate Polishing .................................................................. 1-5
1.6 By-pass Operation....................................................................................................... 1-6
1.7 Ammonium Form Operation ........................................................................................ 1-6
1.8 References .................................................................................................................. 1-7

2 AMMONIUM FORM OPERATION OF CONDENSATE POLISHING BEDS ........................ 2-1

2.1 Advantages ................................................................................................................. 2-1
2.2 Disadvantages............................................................................................................. 2-2
2.3 Other High pH Condensate Polishing Processes......................................................... 2-6
2.4 The Use of Ammonium Form Operation in Various Countries...................................... 2-8
2.4.1 Asia...................................................................................................................... 2-8
2.4.2 Australia............................................................................................................... 2-8
2.4.3 Germany.............................................................................................................. 2-8
2.4.4 Ireland.................................................................................................................. 2-8
2.4.5 United Kingdom ................................................................................................... 2-9
2.4.6 United States ....................................................................................................... 2-9

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2.4.7 South Africa ........................................................................................................2-10

2.5 References .................................................................................................................2-10

3 THEORY OF AMMONIUM FORM OPERATION ................................................................. 3-1

3.1 Background ................................................................................................................. 3-1
3.2 Ion Exchange Capacities in Ammonium Form Operation............................................. 3-5
3.3 Equilibrium Leakages in Ammonium Form Operation .................................................. 3-7
3.4 Ammonium Displacement Effects ................................................................................ 3-9
3.5 The Behaviour of the Common Impurities in Ammonium Form Condensate
Polishing............................................................................................................................. 3-9
3.5.1 Sodium ................................................................................................................ 3-9
Sodium Leakage Behaviour in Under Ammonium Form Conditions –Without
Condenser Leakage.................................................................................................. 3-9
Sodium Leakage Behaviour in Under Ammonium Form Conditions – With
Condenser Leakage.................................................................................................3-13
3.5.2 Chloride ...............................................................................................................3-14
3.5.3 Sulphate ..............................................................................................................3-19
3.5.4 Carbonate ............................................................................................................3-20
3.5.5 Acetic and Formic Acids.......................................................................................3-21
3.5.6 Silica ....................................................................................................................3-22
3.5.7 Iron ......................................................................................................................3-23
3.5 Regeneration..............................................................................................................3-25
3.6 Computer Models of Ammonium Form Condensate Polishing ....................................3-25
3.7 References .................................................................................................................3-27

4 REGENERATION ................................................................................................................ 4-1

4.1 Requirements .............................................................................................................. 4-1
4.2 Separation ................................................................................................................... 4-2
4.3 Resin Cleaning ............................................................................................................ 4-8
4.4 Conditions for Regeneration .......................................................................................4-12
4.4.1 Cation Resin Regeneration .................................................................................4-12
Sulphuric Acid ..........................................................................................................4-12
Hydrochloric Acid .....................................................................................................4-16
4.4.2 Other Cation Resin Regenerants .........................................................................4-18
4.4.3 Anion Resin Regeneration ..................................................................................4-19
Form of Anion Resin Supplied by Manufacturer. ......................................................4-19

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Removal of Chloride.................................................................................................4-21
Routine Regeneration of Anion Resins for Ammonium Form Polishers ....................4-23
4.4.4 Other Anion Regenerants. ...................................................................................4-23
4.5 Post Regeneration Resin Purification Techniques ......................................................4-24
4.5.1 Requirement for Post Regeneration Purification..................................................4-24
4.5.2 Ammonia Rinse Process......................................................................................4-25
4.5.3 Caustic Flotation Process ....................................................................................4-25
4.5.4 Resin on Resin ....................................................................................................4-27
4.6 Other Techniques .......................................................................................................4-28
4.6.1 Soaking Resins in Regenerants ..........................................................................4-28
4.6.2 Soaking Regenerated Resins in High Purity Water .............................................4-28
4.7 Regenerant Quality.....................................................................................................4-30
4.7.1 Need for High Purity Regenerants ......................................................................4-30
4.7.2 Quality of Sulphuric Acid .....................................................................................4-31
4.7.3 Quality of Sodium Hydroxide...............................................................................4-31
4.8 Regeneration of Resins From Other Designs of Condensate Polishing Plants ..........4-33
4.8.1 Cation-Mixed Bed Plants......................................................................................4-33
4.8.2 Separate Bed Plants ...........................................................................................4-33
4.9 Off-Site Contractor Regeneration ...............................................................................4-34
4.10 References ...............................................................................................................4-34

5 THE SELECTION OF POWER STATIONS FOR AMMONIUM FORM OPERATION

OF THEIR CONDENSATE POLISHING PLANTS.................................................................. 5-1
5.1 Objective ..................................................................................................................... 5-1
5.2 Roadmap to Assist Decision Whether to Operate Polishers in the Ammonium
Form................................................................................................................................... 5-1
5.3 The pH of Condensate and Feedwater ........................................................................ 5-2
5.4 Frequency of Condenser Leaks and Other Impurity Ingress Incidents ......................... 5-4
5.5 The Frequency of Unit Start Ups ................................................................................. 5-6
5.6 Chemical Instrumentation and Testing of Condensate Polisher Systems .................... 5-6
5.7 Operation of Ammonium Form Condensate Polishing Plants......................................5-10
5.8 Differences Between Conventional H-OH Mode Condensate Polishing and
Ammonium Form Operation ..............................................................................................5-10
5.9 The Suitability of Different Types of Condensate Polishing Plant for Operation in
the Ammonium Form .........................................................................................................5-12
5.9.1 Separate Bed Plants. ...........................................................................................5-12

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5.9.2 Mixed Bed Condensate Polishers ........................................................................5-13

5.9.3 Cation Mixed Bed Polishing Plants......................................................................5-15
5.10 Up-Grading Condensate Polishing Resin Regeneration Processes for
Ammonium Form Operation. .............................................................................................5-16
5.11 References ...............................................................................................................5-16

6 GUIDANCE ON OPERATION OF POLISHING PLANTS IN THE AMMONIUM FORM ....... 6-1

6.1 Return to Service of Regenerated Resins.................................................................... 6-1
6.1.1 Condition of Cation and Anion Resins.................................................................. 6-1
6.1.2 Pre-ammoniation of Cation Resin ......................................................................... 6-1
6.1.3 In-service Ammoniation of Cation Resins............................................................. 6-3
6.2 Operation of Polishing Plants in The Ammonium Form in the Absence of
Condenser Leaks or Other Upsets ..................................................................................... 6-5
6.2.1 Polished Water Quality.......................................................................................... 6-5
6.2.2 Crud Filtration Behaviour ...................................................................................... 6-6
Iron Corrosion Product Filtration................................................................................ 6-6
Copper Filtration........................................................................................................ 6-7
6.2.3 Possible Problems During Service Runs of Ammonium Form Beds ...................... 6-8
Increase Of Differential Pressures Across Service Beds ........................................... 6-8
Exhaustion of Anion Resin with Carbon Dioxide........................................................ 6-8
Exhaustion of Anion Resin with Weak Organic Acids ................................................ 6-8
6.3 Operation of Polishing Plants in the Ammonium Form in The Presence of
Condenser Leaks or Other Upsets ..................................................................................... 6-9
6.3.1 Predicted Behaviour of Ammonium Form Beds..................................................... 6-9
6.3.2 Ion Exchange Capacity for Influent Impurities .....................................................6-11
6.3.3 Behaviour of Sodium, Chloride and Sulphate During Condenser Leakage
Conditions on Actual Polishing Plants...........................................................................6-13
6.3.4 Regeneration of Ammonium Form Resins after a Condenser Leak Incident. .......6-18
Regeneration of Contaminated Cation Resins..........................................................6-18
Regeneration of Contaminated Anion Resins...........................................................6-19
6.4 References .................................................................................................................6-20

7 CONCLUSIONS .................................................................................................................. 7-1

7.1 Use of Condensate Polishing ...................................................................................... 7-1
7.2 Methods of Reducing Condensate Polishing Costs ..................................................... 7-1
7.3 Ammonium Form Operation of Deep Bed Condensate Polishers ................................ 7-2

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7.4 Advantages of Ammonium Form Condensate Polishing .............................................. 7-2

7.5 Disadvantages of Ammonium Form Condensate Polishing ......................................... 7-3
7.6 Possible Developments ............................................................................................... 7-3

8 POSSIBLE DEVELOPMENTS IN THE USE AND MONITORING OF AMMONIUM

FORM CONDENSATE POLISHERS ...................................................................................... 8-1
8.1 The Evolution of Ammonium Form Operation .............................................................. 8-1
8.2 On-Site Regeneration Control Techniques .................................................................. 8-2
8.2.1 Requirement for On-Site Regeneration Controls ................................................... 8-2
8.2.2 A Simple Procedure for Checking the Sodium Content of Cation Resins ............. 8-2
8.3 On-Stream Monitoring of the Sodium Inventory of Ammonium Form Mixed Beds........ 8-3
8.4 Early Detection of Sodium Throw Following a Condenser Leak................................... 8-3
8.5 Ammonium Form Bed Run Length Extension .............................................................. 8-5
8.5.1 Constraints on Extending the Service Runs of Ammonium Form Polishers.......... 8-5
8.5.2 Anion Resin Exhaustion ....................................................................................... 8-5
8.5.3 Crud Removal and Resin Fouling ......................................................................... 8-6
8.6 Avoidance of Sodium Throw by Using Pre-ammoniated Cation Resins ....................... 8-7
8.7 The Reduction of Sodium Throw During On-line Ammoniation .................................... 8-8
8.8 Possible Methods of Reducing Chloride Leakage from Ammonium Form Mixed
Bed Polishers using Cation Resin Regenerated with Hydrochloric Acid ............................. 8-9
8.9 The “Ideal” Design of Service Vessel for Ammonium Form Operation ........................8-10
8.10 References ...............................................................................................................8-10

A ION EXCHANGE RESIN SELECTIVITY COEFFICIENTS .................................................. A-1

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LIST OF FIGURES

Figure 2-1 Sodium in polished condensate during on-line ammoniation at pH 9.6 of a

mixed bed at Aghada G.S. .............................................................................................. 2-3
Figure 2-2 Sodium in polished condensate during on-line ammoniation at pH 9.3 of a
mixed bed at Wateree P.S............................................................................................... 2-4
Figure 2-3 Variation of anion exchange kinetics with influent pH. New macroporous
strongly basic anion exchanger. ...................................................................................... 2-5
Figure 2-4 Variation of anion exchange kinetics with influent pH. Used macroporous
strongly basic anion exchanger. ...................................................................................... 2-6
Figure 3-1 Na/H exchange equilibria. Macroporous cation resin.............................................. 3-2
Figure 3-2 Na/NH4 exchange equilibria. Extreme dilution. ....................................................... 3-4
Figure 3-3 Ammonium form condensate polishing, calculated equilibrium capacities of
strongly acidic cation resin for sodium at a range of pH values. (Assuming volume
capacity = 2 eq/L and selectivity coefficient = 0.8) ........................................................... 3-6
Figure 3-4 Ammonium form condensate polishing, calculated equilibrium capacities of
strongly basic anion resin for chloride at a range of pH values. (Assuming volume
capacity = 1 eq/L and selectivity coefficient = 22) ............................................................ 3-7
Figure 3-5 Ammonium form condensate polishing, equilibrium leakage of sodium from
strongly acidic cation resin at a range of pH values @ 25°C. (Assuming volume
capacity = 2 eq/L and selectivity coefficient = 0.8) ........................................................... 3-8
Figure 3-6 Ammonium form condensate polishing, equilibrium leakage of chloride from
strongly basic anion resin at a range of pH values @ 25°C. (Assuming volume
capacity = 1 eq/L and selectivity coefficient = 22) ............................................................ 3-9
Figure 3-7 Ammonium form operation on a gas fired 270 MW boiler with seawater
cooling, on-line ammoniation. .........................................................................................3-10
Figure 3-8 Ammonium form operation—impurity levels at condensate polisher outlet,
Moneypoint Generating Station. pH 9.6. .........................................................................3-11
Figure 3-9 Ammonium form operation—impurity levels at condensate polisher outlet,
Mohave Power Station. Polisher 2S. pH 9.6. ..................................................................3-12
Figure 3-10 Predicted sodium breakthrough with constant sodium inputs at pH 9.6...............3-14
Figure 3-11 Cl/OH exchange equilibrium at extreme dilution with strongly basic anion
exchange resin. ..............................................................................................................3-16
Figure 3-12 Equilibrium chloride leakage at high pH and 25°C...............................................3-17
Figure 3-13 Ammonium form operation—chloride, cation conductivity and sulphate levels
at condensate polisher outlet, Moneypoint Generating Station. pH 9.6...........................3-18
Figure 3-14 Ammonium form operation—chloride, cation conductivity and sulphate levels
at condensate polisher outlet, Aghada Generating Station. pH 9.6. ................................3-19

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Figure 3-15 Variation of equilibrium capacity for acetate with pH and acetate input level
AC
(assuming K OH = 3.2 and anion resin volume capacity = 1 eq/L)...................................3-21
Figure 3-16 Acetate breakthrough in morpholine form operation of a condensate
polishing plant at pH 9.5. Composite of a number of runs with inlet concentration
approx. 20 ppb. ..............................................................................................................3-22
Figure 3-17 Ammonium form operation—iron levels at condensate polisher inlet and
outlet, Moneypoint generating station. pH 9.6.................................................................3-24
Figure 3-18 The effect of pH on iron filtration by anion and cation resin, laboratory test
using a synthetic crud based on haematite.....................................................................3-25
Figure 3-19 Computer simulation of throw of sodium loaded for a short period of time at
different pH levels...........................................................................................................3-26
Figure 3-20 Computer simulation of ammonium cycle operation past the ammonia break
for pH 9.6 and a cation:anion ratio of 1.5:1. The sodium feed concentration is 23
ppb. ................................................................................................................................3-27
Figure 4-1 Bottom transfer separation/regeneration system. .................................................. 4-4
Figure 4-2 Interface isolation separation/regeneration system. .............................................. 4-5
Figure 4-3 SCE design of mixed bed separation system. ....................................................... 4-6
Figure 4-4 Ammonium sulphate mixed bed separation system based on resin density
differences....................................................................................................................... 4-7
Figure 4-5 Ammonium form operation—impurity levels at condensate polisher outlet,
Mohave Power Station. Polisher 2S. pH 9.6. ................................................................... 4-8
Figure 4-6 Cleaning of exhausted ammonium form mixed bed by air scouring and drain-
down. Iron in drain-down water shown by filter stains. ....................................................4-10
Figure 4-7 Schematic of Japanese process for resin cleaning...............................................4-11
Figure 4-8 Elution of sodium from cation resin. .....................................................................4-14
Figure 4-9 Impurities on cation resin used in ammonium form condensate polishing,
before and after regeneration. ........................................................................................4-15
Figure 4-10 Percentage of ion exchange sites on anion resin in chloride, hydroxide,
sulphate and bicarbonate form before and after use in ammonium form polishing..........4-18
Figure 4-11 Percentage of ion exchange sites on anion resin in chloride, hydroxide,
sulphate and bicarbonate form after use being sulphated and regenerated....................4-21
Figure 4-12 Effect of sodium hydroxide regenerant level on regeneration efficiency of
chloride and sulfate from duolite A161 resin. ..................................................................4-22
Figure 4-13 Ammonia rinse (Ammonex®) regeneration process. ............................................4-26
®
Figure 4-14 Seprex regeneration process. ............................................................................4-27
Figure 4-15 Resin-on-resin regeneration procedure. ..............................................................4-29
Figure 4-16 Sulphate washout during return to service of regenerated mixed beds—
comparing behavior of beds used without standing and beds allowed to rest for 5
days. ..............................................................................................................................4-30
Figure 5-1 Road Map for Deciding Whether Ammonium Form Operation is Suitable for
Stations and Steps in its Adoption ................................................................................... 5-3
Figure 5-2 Cycle chemistry diagram for a drum unit on all-volatile treatment (plants with
reheat)—core parameters only. ....................................................................................... 5-8

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Figure 5-3 Moneypoint Generating Station: ammonium form operation annual cost
savings. ..........................................................................................................................5-10
Figure 5-4 Tripol service vessel diagrammatic internal arrangement......................................5-12
Figure 5-5 Equilibrium capacities of cation and anion resins for sodium and chloride at
Na
pH 9.2, ( K NH = 0.8, K Cl
OH = 22)....................................................................................5-14

Figure 5-6 Equilibrium capacities of cation and anion resins for sodium and chloride at
Na
pH 9.6, ( K NH = 0.8, K Cl
OH = 22)....................................................................................5-15

Figure 6-1 Pre-ammoniation and on-line ammoniation of resins containing 0.03% sodium
at Aghada Generating Station, 1981................................................................................ 6-2
Figure 6-2 Impurity levels in polished water at Moneypoint Generating Station showing
operation in the ammonium form at pH 9.4-9.5................................................................ 6-4
Figure 6-3 Sodium in water from ammonium form condensate polishers, Tarong Power
Station, Australia, 1986 ................................................................................................... 6-6
Figure 6-4 Simulated sea water leakage test into condensate to an ammonium form
condensate polishing plant at Moneypoint Generating Station, pH 9.6. ..........................6-10
Figure 6-5 Sodium concentration profiles, in ppb (µg/kg), during displacement from an
ammonium form bed operating at pH 9.6—following sodium contamination of the
bed. ................................................................................................................................6-11
Figure 6-6 Ammonium form condensate polisher performance in face of a condenser
leak of variable size on a 500 MW unit without optimum regeneration facilities,
1979. ..............................................................................................................................6-12
Figure 6-7 Aghada Generating Station polishing plant trials, simulated sea water leak
test, chloride in condensate. ...........................................................................................6-15
Figure 6-8 Aghada Generating Station polishing plant trials, simulated sea water leak
test, sodium in condensate. ............................................................................................6-16
Figure 6-9 Results of a simulated condenser leak test on polishing plant operated in the
morpholine form at pH 9.5. .............................................................................................6-17
Figure 8-1 Adverse effects of fluidizing resin........................................................................... 8-4

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LIST OF TABLES

Table 4-1 Impurity Levels on Cation and Anion Resins to Give 1 ppb Equilibrium
o o
Leakage at 25 C (77 F).................................................................................................... 4-2
Table 4-2 Cation Bead Resin Specification ...........................................................................4-13
Table 4-3 Cation Ion Exchange Resin Regeneration..............................................................4-16
Table 4-4 Regeneration of Resins with Ammonium Sulphate................................................4-19
Table 4-5 Anion Bead Resin Specification .............................................................................4-20
Table 4-6 Anion Ion Exchange Resin Regeneration..............................................................4-23
Table 4-7 Sulphuric Acid Regenerant Specifications .............................................................4-31
Table 4-8 Guide to the Relationship Between Chloride in Bulk Sodium Hydroxide and the
Resultant Anion Resin Levels.........................................................................................4-32
Table 5-1 Run Length of Cation Resin in a Typical Condensate Polisher to Ammonium
Breakthrough................................................................................................................... 5-4
Table 5-2 Indication of Run Lengths of Condensate Polishers in the H-OH Mode and in
the Ammonium Form, pH 9.6........................................................................................... 5-5
Table 5-3 Frequency of Condenser Leaks and Acceptability for Ammonium Form
Operation ........................................................................................................................ 5-6
Table 6-1 Impurity Levels in Water from Ammonium Form Polishers (Under Steady
State, No In-leakage, Conditions) .................................................................................... 6-5
Table A-1 Effect of Degree of Crosslinking on Selectivity Coefficients of Various Cations
for Polystyrene Cation Exchange Resin at 25°C.............................................................. A-1
Table A-2 Selectivity Coefficients of Various Anions for Polystyrene-Based Strong-Base
Anion-Exchange Resins at 25°C ..................................................................................... A-2
Table A-3 Selectivity Coefficients of Various Amines on Common Cation Resins at 25°C ..... A-2

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1
INTRODUCTION

1.1 Background

The operation of condensate polishing plants with the resin fully in the ammonium form, as
opposed to the conventional hydrogen ion-hydroxide (H-OH) mode, is a well-established but
frequently misunderstood procedure. It offers most of the advantages of full flow polishing and
at the same time makes significant economies in the use of ammonia, regeneration chemicals and
water and also in operator time. An additional benefit, in view of the increasing environmental
constraints being placed upon power stations, is that the volume of liquid waste requiring
discharge is consequently also significantly reduced. There are, however, disadvantages and
constraints associated with operating in this economical mode and these must be understood both
by plant designers and by operators. This report is intended to be a review of the technique and a
discussion of its advantages and disadvantages.

1.2 General Benefits of Condensate Polishing

The benefits of condensate polishing extend well beyond simply offering protection in the event
of a condenser leak. Its use minimises corrosion and deposition within the circuit and reduces the
need to chemically clean units. It also assists at start-up by eliminating, or at least reducing,
delays caused for reasons associated with condensate and feedwater purity. These benefits have
been shown to give an overall saving of about $600,000/year on a typical 360 MWe fossil-fired
boiler1. Further studies, based on the results obtained from 95 units taking part in the EPRI
Cycle Chemistry Improvement Program, provided evidence that even these predicted benefits are
in fact an under estimate 2.

1.3 Steam Generator and Boiler Designs and their Condensate Quality
Demands

Condensate polishing has evolved so that the various classes of power station tend to use it
differently and the attempt, given below, to categorise these uses must be accepted as a very
broad generalisation

1.3.1 Fossil Fired Power Stations With Drum Boilers

This general type of boiler is widely used throughout the world for power production, out
numbering any other design. Operators of fossil drum boilers are particularly interested in
protecting against the effects of condenser leaks and in using polishers to enable them to start up

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Introduction

more quickly. Stations of this type do not need the very high water qualities sought by nuclear
power stations but the ability, given by the use of condensate polishing, to continue operating in
the face of a significant condenser leak is valuable. With the benefit of polishers, and depending
on the size of the leak, stations can continue generating until a time is reached when coming off
load for repairs is both convenient and economically acceptable to the utility. This may be the
next weekend or much later if the leak is small.

These advantages are well understood by operators and appreciated by accountants. What
frequently escapes attention is the fact that the use of full flow polishing allows operators of
drum boilers to safely use simple, yet effective, boiler water conditioning regimes such as All
Volatile Treatment (AVT) and, as discussed below, Oxygenated Treatment (OT). Dooley has
pointed out that 90% of the drum boilers in the USA using congruent phosphate treatment
suffered “hideout” and that 70% of these were experiencing corrosion3. The major obstacle
preventing many stations changing to the far less troublesome AVT is the lack of condensate
polishing. In contrast 95% of boilers using AVT, both once-through and drum boilers, have
condensate polishing.

Hence, over the course of time there has been a shift in the reasons why fossil stations use or
retrofit condensate polishing. The early objectives of protecting against condenser leaks have
evolved to the view, currently held by EPRI, that polishing is also important in that it aids fossil
stations to use easier to control water treatment regimes. These simple yet effective water
treatment regimes lead, in turn, to a reduction of corrosion within the circuit, a reduced need to
chemically clean units and, overall, an improved availability.

The condensate and feedwater quality requirements of drum boilers varies with their pressure
and treatment regime but typically call for sodium levels of less than 3 ppb and cation
conductivity values of less than 0.15 µS/cm @ 25 C .
o 4

1.3.2 Fossil Power Stations With Once-through Boilers

Most stations of this type already use some form of condensate polishing with many employing
filter demineralisers in order to minimise feedwater corrosion product transport around the
steam/water circuit. Many operators of fossil-fired once-through boilers have now adopted OT
and are reporting significantly lower levels of crud transport and deposition.

The condensate and feedwater quality requirements of once-through fossil fired boilers typically
call for sodium levels of less than 3 ppb (µg/kg) and cation conductivity values of less than 0.15
µS/cm . Some utilities such as Eskom, South Africa, place more stringent limits on impurities in
4

polished condensate for boilers of this type5.

1.3.3 Once-through and Drum Boilers Employing Oxygenated Treatment

All power stations employing OT use, or are strongly advised by EPRI to use, full flow H-OH
form condensate polishing6. EPRI also advises these stations to maintain low cation conductivity
levels with a normal operation level of 0.15 µS/cm @ 25oC and a target of less than 0.1 µS/cm
being preferred. Without full flow, H-OH form, condensate polishing it is often difficult, to

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Introduction

achieve these levels. With condensate polishing, the 0.1 µS/cm cation conductivity target is
easily met and levels of around 0.06 µS/cm can be achieved without difficulty by the proper use
of appropriately designed plant. The use of OT on drum boilers is still developing and a
particular need to maintain waterside, and especially boiler water, purity and cleanliness at a very
high level on these plants is stressed.

1.3.4 Heat Recovery Steam Generators

EPRI advice on cycle chemistry conditions has now been extended to cover the rapidly growing
Heat Recovery Steam Generator class of boilers within combined cycle plants. The earlier
designs of HRSGs operated at relatively low pressures but the new designs now evolving are
operating at temperatures and pressures approaching those used on conventional fossil fired
boilers and even incorporating once-through sections. Again, the use of condensate polishing is
advocated7.

1.3.5 Nuclear Power Stations

The majority of nuclear power stations throughout the world are equipped with, and use,
condensate polishing. Pressurised Water Reactors (PWRs) have become the most common types
of power reactor with those employing “recirculating” steam generators being the design
normally used. Owing to the fact that impurities in condensate and feedwater can, and do,
concentrate within the steam generator the specifications governing condensate and feedwater
8
quality demand a very high purity . Sawochka has calculated that a PWR with a Recirculating
Steam Generator could require sodium levels in polished condensate as low as 7 ppt which is,
arguably, only just above the current limit of analytical detectability9. Very low levels of chloride
and sulphate are also demanded and these water qualities can only be achieved when using a
polishing plant by operating in the conventional H-OH mode and then only with very effectively
regenerated resins.

BWR Nuclear Power Stations are the second most commonly used type of power reactor and
also demand the lowest possible impurity levels in condensate and feedwater with H-OH form
condensate polishing being used to attain the desired water quality8.

Gas (CO2) Cooled Reactors are used in the UK with all but the very early designs employing
once-through boilers. The condensate and feedwater specifications are less stringent than those
demanded by PWRs and BWRs and, in fact, are similar to the specifications adopted for fossil
plants. All use full flow deep bed condensate polishers operating in the H-OH form with the
exception of Oldbury on Severn that operates in the morpholine form to allow use of very high
levels of the amine, 60 ppm, so as to minimise two phase flow assisted corrosion (FAC). Some
CANDU reactors also use condensate polishing with the plants at Point Lepreau operating in the
morpholine form for the same reasons as Oldbury.

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Introduction

1.4 Types of Condensate Polishing Plants

The various designs of condensate polishing plants are detailed in EPRI TR-104422, Condensate
Polishing Guidelines, September 1996 and EPRI TR-101942, Condensate Polishing Guidelines
for PWR and BWR Plants-1997 Revision, September 19971,8. Briefly, there are two main types
and these are described below.

1.4.1 Filter Demineralisers (“Powdex”)

Filter demineralisers employ a thin coating of powdered mixed anion and cation resins upon
septa contained in a service vessel. The system acts as a very effective filter for particulate
impurities, with a crud removal efficiency of over 95%, but has a low ion exchange capacity.
When used on a system conditioned with ammonia, or other volatile amine, the cation resin in
the ion exchange resin coating is rapidly converted to the ammonium or amine form. For the
remainder of the time the vessel is in service the resins then operate in the ammonium (or amine
form). Although this does not noticeably affect its filtration properties the quality of the polished
water is adversely affected. The reasons for this deterioration in treated water quality will be
subsequently discussed. Powdered resin pre-coats are often applied with the cation resin already
fully converted to the ammonium or morpholine form. Filter demineralisers continue to be used
under neutral water conditions on BWRs, are often installed on other designs of nuclear once-
through boilers, such as PWR-OTSGs, and are also found on some drum boilers.

1.4.2 Deep Bed Condensate Polishing Plant Designs

The naked mixed bed is the most common type of deep bed condensate polishing plant. In this
design a mixture of anion and cation resins act both as a filter for particulate matter and to
remove ionic impurities. As EPRI TR-104422 shows, it is the least costly of all the deep bed
designs as it employs the minimum number of service vessels and their associated equipment.
Naked mixed beds are suitable for use in the H-OH form and, with suitably regenerated resins, in
the ammonium form. Two nuclear power stations successfully employ them in the morpholine
form.

The cation-mixed bed approach is frequently used in Europe and has been adopted elsewhere. It
has both theoretical and practical advantages as the lead cation bed acts as a filter preventing iron
fouling of the mixed bed and at the same time allowing a much greater cation exchange
capability to be built into the system. This larger cation exchange capacity facilitates the plant
being used in the H-OH form on stations operating at relatively high ammonia levels in their
steam/water circuits. On exhaustion of the lead cation bed it is possible to regenerate this charge
without the need to regenerate the following mixed bed – a facility that offers savings and can
improve the quality of the final polished water. When running in the H-OH form, and this is
normal with cation-mixed bed plants, the anion resin in the mixed bed is operating under either
neutral or slightly acidic conditions. These conditions favour anion exchange kinetics. Despite
the theoretical advantages, both cation-mixed bed plants and naked mixed bed plants have been
shown, when well operated, to yield approximately the same quality of polished water. Cation-
mixed bed plants are probably more convenient, robust and forgiving to operate. However, they

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Introduction

cost approximately 50% more to install than naked mixed bed plants and have higher
maintenance requirements.

There are no reasons why a cation-mixed bed plant cannot be successfully operated in the
ammonium form and in fact several advantages can be suggested. However, as already stated,
polishing plants of this design are invariably operated in the conventional H-OH form taking
advantage of their higher cation exchange capacity to obtain longer service runs than achievable
with naked mixed bed plants.

The separate bed design is also widely used in Europe, mainly in Germany although it use is
being adopted by other European countries. Some of the German designs employ in-situ counter-
current regeneration which, after some early problems, is now being used successful although it
continues to be viewed with mistrust elsewhere. Eskom, South Africa, has adopted the use of
separate bed polishers for some of its stations. A proprietary separate bed design, in which
shallow layers of cation-anion-cation resin are contained in the same vessel, was investigated by
EPRI and is being successfully used on stations in Australia and Singapore10,11. Separate beds
represent a robust design of condensate polishers with the anion resin again, in H-OH form
operation, running under conditions that give optimum anion exchange kinetics. Polished water
qualities from separate bed plants are inferior to those from well operated naked mixed bed and
cation-mixed bed plants that, at their best, can yield impurity levels of well below 10 ppt of the
common impurities. The best that can usually be expected from a separate bed plant operating in
the H-OH form are impurity levels in polished water of 0.1-0.2 ppb. However, this quality of
polished water is totally acceptable for virtually all types of fossil power station although not
acceptable for PWR and BWRs. The separate bed design easily lends itself to ammonium form
operation as the cross contamination problems arising from mixed bed separation and
regeneration are avoided. EPRI figures show that they cost about 50% more to install than a
comparable naked mixed bed plant although this is disputed by one of the users of separate bed
plants11.

1.5 Cost Implications of Condensate Polishing

There is little doubt that all forms of power generation are being subjected to increasing
pressures to reduce the cost of the electricity that they produce. With the emergence of the new
combined cycle designs of power plants, and the role now being played by co-producers, the
economic pressures on the more conventional power plants have increased disproportionately.
As EPRI studies have shown, condensate polishing has a value and benefit beyond being an aid
at start-up and in protecting from condenser leaks. It includes improved availability, often
stemming from the ability to use more effective forms of conditioning the steam/water circuit,
cleaner circuits leading to a reduced need to chemically clean, reduced blowdown on drum
boilers and improved turbine efficiency. These matters are discussed in detail in EPRI TR-
1
104422 . Whilst the claims made are fully justified, and probably understated as Larkin has
pointed out, the savings and benefits are not always readily apparent whilst the capital and
operating costs of a condensate polishing plant can act as an obstacle and deterrent to stations
interested in adopting the technique.

Ways in which the capital cost of deep bed condensate polishing plants for fossil power stations
could possibly be reduced are currently being studied in a pilot EPRI project. The handling of

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Introduction

such large flows of water imposes many constraints such as the safety and hence designs of
pressure vessels. However, innovative vessel designs are being considered together with the
adoption of off-site regeneration so obviating the need for regeneration facilities for polisher
resins on the power stations using such services. Off-site regeneration could also have benefits in
that it reduces the quantity of effluent to be disposed by the station. In the more distant future the
development of membrane techniques may offer other options.

Thus, at this early stage, some savings do seem possible and it is hoped that that current EPRI
sponsored studies may result in less costly designs for some future polishing plants. For the
present time, however, only two methods of reducing the costs of deep bed condensate polishing
are known. They are the use of partial or full by-pass so extending the service life of any
polishing bed and the use of cation resins in the fully ammoniated (or amine) form. Ammonium
form resins do not remove ammonia (or amine) from the condensate to be treated and can remain
in service for many months rather than a few days.

1.6 By-pass Operation

By-pass operation is used successfully by some fossil stations and increasingly by PWRs as most
are now using higher levels of volatile amines so as to minimise circuit corrosion and iron
transport/deposition. The advantages are obvious in that the polishing beds are only used when
considered necessary such as at start-up or when plant instrumentation indicates a deterioration
in the chemical quality of condensate or feedwater. The disadvantage is that it takes a finite time
to restore to full flow service a polishing bed that has been out of service with some estimates
putting this time at about 30 minutes providing prompt action is taken. In instances of major and
multiple condenser tube failures, or similar catastrophic events, this is not fast enough to prevent
contamination of the steam/water circuit. In some cases, in the past, human error has allowed
poor quality condensate conditions to persist without polisher beds being put into service. Given
modern instrumentation and expert computer monitoring systems there seems little need to now
accept these disadvantages with the main problem becoming that of rapidly restoring a by-passed
polisher to full flow. This has been addressed by Eskom at its Koeberg Nuclear Power Station in
12
a design in which the beds are maintained on partial flow on a separate, cooled, by-pass circuit .
It is claimed that they can be restored to full flow polishing of the main circuit in 45 seconds on
receipt of instrumentally generated instructions.

1.7 Ammonium Form Operation

Ammonium form operation has been known and used for over 30 years with the important
aspects of its theory and practice discussed at an early stage by authors such as Abrams, Pocock
and his co-workers and Salem.13, 14, 15. It involves operating mixed or separate beds with the cation
resin fully in the ammonium form so that the polishing plant ceases to remove ammonia. Thus,
ammonium form beds can remain in service for several months, in the absence of a condenser
leak or other impurity ingress incident with run times usually being determined by increasing
pressure drop, the cation conductivity of the polished water or by operational convenience.
Depending on the pH of operation and the design and cation resin inventory of the actual beds,
regeneration costs can be reduced by over 90% relative to operating the same bed in the
conventional H-OH form. Polisher regenerant effluent volumes are obviously reduced by the

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Introduction

same percentage. Full condensate protection is maintained with the ammonium form plant being
capable of removing influent impurities should a condenser leak arise and continuing to act as a
useful filter to remove particulate impurities. This mode of operation is attractive for the
significant cost savings that it can achieve and the convenience it offers.

Unfortunately there are disadvantages. As the ammonia added as a conditioning agent is no

longer removed, the water phase throughout the polisher bed(s) remains at a high pH level,
generally that of the influent condensate. It is this high pH (high OH ion concentration) together
with the presence of ammonium ions, which controls the behaviour of ammonium form beds. It
leads to:
• A significant decrease in the quality of the polished water, even under no in-leakage
conditions, relative to that that would be produced if the same resins were operated in the
conventional H-OH form. (Nevertheless, given an appropriate level of regeneration,
ammonium form beds can and do yield polished water perfectly suitable for use on fossil
power plants).
• A tendency to “throw” even higher levels of impurities in some circumstances.
• Lower capacities for removing impurities.
• The subsequent leakage, under some conditions and after a few days, of impurities removed
from condensate.

This behaviour is unlike that shown by beds operated in the H-OH form and, in the past, has
caused difficulties to those operators not well versed in the characteristics of ammonium form
beds. Ammonium form beds have become viewed by some as being unstable. Stations suffering
from frequent condenser leaks or experiencing frequent startups should not consider adopting
this mode of operation nor should those stations unable to regenerate resins to the much higher
quality required for successful ammonium form operation. These aspects are considered in
greater detail in the following Sections of these Guidelines.

1.8 References

1. EPRI Condensate Polishing Guidelines, EPRI TR-104422, September, 1996.

th
2. B. A. Larkin and D. E. Shallberg, “Condensate Polishing Cost Benefit Analysis”, 5 EPRI
International Conference on Cycle Chemistry in Fossil Plants, June 1997, Charlotte, NC,
USA.

3. R. B. Dooley and J. A. Matthews, “The Current State of Cycle Chemistry for Fossil Plants”,
5th EPRI International Conference on Cycle Chemistry in Fossil Plants, June 1997, Charlotte,
NC, USA.

4. EPRI TR-105040, Selection and Optimisation of Boiler Water and Feedwater Treatments for
Fossil Plants, March 1997.

5. ESKOM Chemistry Standard For Coal Fired Units With Drum Boilers Operating at 17 MPA
and Above. GGS 0210, August 1996.

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Introduction

6. EPRI TR- 102285, Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment,
December 1994.

7. EPRI TR-110051 Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery
Steam Generators (HRSGs), November1998.

8. EPRI TR-101942-R1, Condensate Polishing Guidelines for PWR and BWR Plants-1997
Revision, September 1997.

9. S. G. Sawochka, “Condensate Polishing Issues and Evolution”, Proceedings of the EPRI

Condensate Polishing Workshop, New Orleans, USA, September 1997.

10. D. C. Auerswald, F. M. Cutler and S. S. Simmons, “Parts per Trillion Without Mixed Beds”,
Proceedings of the 50th International Water Conference, Engineers’ Society of Western
Pennsylvania,1989.

11. R. N. R. Robinson and L. A. Chapple, “Operation of the World’s Largest Tripol Condensate
Polishing Vessels at Stanwell Power Station (Queensland) Australia”, Ion Exchange
Developments and Applications, Royal Society of Chemistry, Cambridge, United Kingdom,
1996.

12. K. J. Galt, M. W. Adendorff and A. Welsh, “Flexible Condensate Polishing Operation at

th
Koeberg Nuclear Power Station”, Proceedings of 7 BNES Conference on the Water
Chemistry of Nuclear Reactor Systems, Bournemouth, United Kingdom,1996.

13. I. Abrams, “New Requirements for Ion Exchange in Condensate Polishing”, Proceedings of
the 37th International Water Conference, Engineers’ Society of Western Pennsylvania, 1976.

14. T. McLaughlin, F. J. Pocock and J. F. Stewart, Four Years Operating Experience with a
High Flow-Rate Condensate Polishing System at the Middletown Station of The Hartford
Electric Light Company. Proceedings of the American Power Conference, 1969.

15. E. Salem, “A Study of the Chemical and Physical Characteristics of Ion Exchange Media
st
Used in Trace Contaminant Removal”, Proceedings of the 31 American Power Conference,
Engineers’ Society of Western Pennsylvania, 1969

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2
AMMONIUM FORM OPERATION OF CONDENSATE
POLISHING BEDS

2.1 Advantages

Ammonium form operation has the advantage that condensate polishing beds, when running in
this mode, can operate for long periods provided condenser leaks are absent. One station has
reported bed service lives of up to 200 days although it must be pointed out that such long runs
are not usual1. More typically ammonium form beds remain in service for 30-60 days (1 – 2
months) and are normally regenerated at an operationally convenient time. This must be
contrasted with the service run lengths achieved on mixed bed polishers, operated in the
conventional H-OH mode on drum boilers. Units with boilers of this type work within an advised
condensate pH range of pH 8.8-9.6, depending on their circuit metallurgy. Their actual polisher
run lengths depend on design and condensate pH, but are usually in the range of 3 to 7 days.
Once-through boilers normally now use OT, with a circuit pH of 8.0 – 8.5, and as a consequence
can operate polishers in the ammonium form for 30-60 days. Obviously, for these once-through
units, and drum units operating at the bottom range of their pH range, ammonium form operation
offers little real advantage. For some other units, significant savings in terms of ammonia
replacement costs, resin regeneration costs and operator time can be made by adopting
ammonium form operation. The fact that the volume of spent regenerants being discharged is
also reduced, as it is obviously proportional to the number of regenerations, is possibly of greater
interest to power stations situated in areas imposing severe restriction on effluents.

Ammonium form beds still act as effective filters for particulate matter such as iron oxide and
other corrosion debris (crud) and it can be the increase in pressure drop caused by this which
dictates the useful service life of a bed. They also offer a useful capacity for the removal of
impurities such as sodium, chloride and sulphate. This allows the beds to effectively combat a
condenser leak. It must be pointed out that their behaviour in the removal and retention of
influent impurities is complex and this behaviour is discussed in detail in the following Sections.

Thus, the main advantage of ammonium form operation is that it allows resin beds to be operated
for very long periods of time. This, of course, assumes the absence of condenser leaks and
disturbances such as start-ups and shutdowns. The consequence of this is that when the
procedure is used on suitable stations the number of regenerations carried out can be
significantly reduced. At the same time full protection against the unexpected condenser leak is
given as well as the bed acting as filters. Savings on annual condensate polisher operating costs
of up to a 90% are claimed.

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Ammonium Form Operation of Condensate Polishing Beds

2.2 Disadvantages

The disadvantages of operating in the ammonium form compared to the conventional H-OH
mode must be clearly understood by any user. They include the facts that: -

(a) The levels of ionic impurities, such as sodium and chloride, in polished condensate from ion
exchange beds operated in the ammonium form will always be higher than the levels of these
impurities that could be obtained from the same resins if they were operated in the
conventional H-OH mode. There is a factor of x100 to x1000 between the leakage levels seen
when operating in the neutral H-OH mode and the high pH ammonium forms. The exact
level of leakage in the ammonium form depends, amongst other things, on the pH of
operation.

(b) The consequence of this higher level of equilibrium leakage is that, inorder to compensate,
resins intended for use in the ammonium form must be regenerated to a far higher quality
than resins intended for use in the conventional H-OH mode of operation. Ideally this
requires the use of very effective separation procedures for the mixed beds together with
additional, post regeneration, techniques for further purifying the resins.The percentage of
the active cation exchange sites in the sodium formshould be reduced to less than 0.08% and
the chloride content of the anion resin to less than 1%. (These figures relate to resins being
prepared for operation at pH 9.6. Some relaxation is possible for thoseintended for use under
lower pH conditions. This issue is discussed in more detail in Section 3)

(c) Resin beds intended for operation in the ammonium form are usually returned from
regeneration and placed into service with cation resin in the H+ form. The cation resin is
allowed to ammoniate in-service as this is the simplest way of achieving this state.
Following the breakthrough of ammonia from the mixed bed there is, invariably, an increase
in the level of sodium in the final polished water. These sodium levels can reach peak values
of several ppb depending on the efficiency of regeneration of the resin and whether the bed
has picked up sodium in service. The “sodium throw” following ammoniation generally
peaks over a period of about five days with the polished water sodium levels then gradually
falling over the next five to ten, or even more, days to a steady state value. As discussed
above, the steady state level of sodium leakage under ammonium form conditions is two to
three orders of magnitude higher than that seen in the earlier part of the service run when the
bed would normally be operating in the H-OH mode. This behaviour is illustrated by plant
data obtained on a 270 MWe once through unit when operating its polishers in the
ammonium mode2, Figure 2-1.

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Ammonium Form Operation of Condensate Polishing Beds

Figure 2-1
Sodium in polished condensate during on-line ammoniation at pH 9.6 of a mixed bed at
Aghada G.S.

Unless care is taken over regeneration, the sodium peaks experienced during the sodium
throw can cause sodium levels in the circuit to exceed the limits recommended by EPRI and
other advisory bodies. Figure 2-2 shows results, obtained some years ago, in which sodium
levels in polished water peak at 3 ppb. A sodium throw such as this, although acceptable at
3,4
the time, would not be regarded as desirable today despite being within EPRI action limits .
Beds subjected to condenser leaks during the H-OH part of the cycle will also show an
enhanced sodium throw following ammonia breakthrough if they are not removed from
service.

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Ammonium Form Operation of Condensate Polishing Beds

Figure 2-2
Sodium in polished condensate during on-line ammoniation at pH 9.3 of a mixed bed at
Wateree P.S.

(d) Beds operated in the ammonium form retain a useful capacity for removing sodium and
chloride. This capacity is generally lower than that shown by resins operating in the H-OH
form and is both input concentration and pH related. The capacity for weak organic acids,
such as acetic and formic acids, and silica is also lower than that shown by resins operating in
the H-OH mode. Impurities such as the weak organic acids and silica normally enter
steam/water circuits as contaminants of make-up water. Thus, the low capacity shown to
them need not be a problem given effective procedures for the deionisation of make-up
water.

(e) When operating in the ammonium form the ability to monitor the overall quality of polished
water by the use of direct conductivity is lost as ammonia levels are the same as those
entering the polishing plant. Surveillance of polished water quality must, as a minimum, be
carried out using cation conductivity for anion impurities and sodium monitors for sodium.
Direct conductivity, or pH measurements, will allow ammonia levels to be estimated.
Obviously, the use of on-stream instruments such as ion chromatographs will provide more
detailed information. Influent sodium and conductivity levels should also be monitored

(f) In ammonium form operation, whether conducted using mixed beds or separate beds, the
anion resins operate in a high pH environment, typically between pH 9.0 and 9.6. The
kinetics of anion exchange are lower under these conditions compared to the kinetics
displayed under the neutral or slightly acid conditions experienced by the resin when being
used in plants operating in the H-OH mode. Anion resins usually suffer deterioration of their

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Ammonium Form Operation of Condensate Polishing Beds

exchange kinetics as they age in service and/or become slightly fouled. These effects are far
more evident on resins operating under high pH conditions as evidenced by determinations of
mass transfer coefficients under different pH conditions5, Figures 2-3 & 2-4.

(g) The anion resins used in ammonium form operation must be regenerated to a very high
degree so that chloride impurity levels are reduced to less than 1% for use at pH 9.6. This
demands the use of very high purity sodium hydroxide with that produced by the mercury
cell process normally being employed. Supplies of a suitable grade are not easily available in
all countries or regions of countries.

Figure 2-3
Variation of anion exchange kinetics with influent pH. New macroporous strongly basic
anion exchanger.

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Figure 2-4
Variation of anion exchange kinetics with influent pH. Used macroporous strongly basic
anion exchanger.

2.3 Other High pH Condensate Polishing Processes

The use of volatile alkalis to condition steam/water circuits of boilers and steam generators is
well established and the benefits proven by experience. Ammonia is by far the most commonly
used volatile alkali and is employed by most fossil power stations with a very few exceptions. It
is inexpensive, readily available, compatible with ion exchange resins and, when properly
handled, poses few problems. Furthermore, amongst the volatile amines currently in use, it is the
only one that does not decompose thermally under the temperature and pressure conditions used
in modern fossil fired power station boilers. From the corrosion prevention point of view,
however, it is not the ideal amine. It is a relatively weak base and, when in a two phase
water/steam situation, its partition behaviour favours the steam phase.

Steam/water circuits on the major designs of nuclear power plants, in contrast to those on most
designs of fossil power plants, operate under pressure and temperature conditions that subject
large sections of the circuits to wet steam. This often gives rise to two phase Flow Accelerated
Corrosion (FAC). It is known that this form of corrosion can be countered by increasing the pH
of the water phase. Thus, under these conditions, it is desirable to use a volatile amine that
shows a better steam/water partition behaviour than the commonly used ammonia. Many PWRs
and a few gas cooled reactors have now successfully adopted the use of volatile amines in place
of ammonia. The question of whether polishing plants could be used in the amine form,

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analogous to the ammonium form, was raised following the introduction of volatile amines. The
motivation for this was primarily to minimise the dosing costs of these more expensive
chemicals but also to allow the use of higher concentrations and hence achieve higher circuit pH
levels. It was quickly realised that PWRs with recirculating steam generators could not operate
their polishers in the amine form as the quality of the polished water yielded by polishers
operated in the amine form was inadequate for their needs.

Operation of deep bed polishers with the cation resins in the morpholine form was however
introduced at Oldbury on Severn Nuclear Power Station in 19826. Oldbury, a gas cooled station
of the earlier Magnox type, is situated on a river estuary and uses once-through boilers.
Although the pressure and temperature conditions in its steam/water circuits are very similar to a
PWR the acceptable impurity levels in its condensate and feed water are not as stringent. The
polished water specifications are almost the same as currently advised for fossil power stations.
Experience shows that the ion exchange behaviour of the polisher when treating morpholine
dosed condensate is almost exactly the same as seen in ammonium form operation with an added
benefit that sodium leakage effects are less pronounced. This is because the sodium/morpholine
exchange equilibria is more favourable to sodium retention on the resins, i.e. the
sodium/morpholine selectivity is higher. Morpholine form operation has allowed Oldbury to
operate with about 60 ppm of morpholine in its steam water circuit since 1982. The result has
been that the FAC, that was threatening the life of the plant life, has been controlled and massive
savings have been achieved.

The CANDU nuclear power station at Point Lepreau has also successfully adopted morpholine
form operation of its deep mixed beds. A limited number of PWRs with once-through steam
generators are reported to be using morpholine form powdered resin filter demineraliser systems.

The ion exchange chemistry of amines is relatively easy to predict given knowledge of the
relevant basicities of the amines concerned, temperature effects and above all sodium/amine
selectivities. The physically destructive effect that some amines have on cation exchange resins
is, however, unexpected. Even now, there are no certain ways of predicting whether an amine
will attack a cation bead and new combinations have to be tested. Experience is still being gained
with recent information suggesting that ethanolamine, now commonly used on PWR-RSGs with
H-OH form condensate polishing and considered to be benign, is subtly attacking cation resins.
Fortunately, morpholine has been shown to have an acceptable behaviour with resin bed at
Oldbury giving normal lives although, even with this amine, some evidence of physical attack
has been noted.

At this point in time there do not appear to be any proposals to extend the use of amine form
condensate polishing to fossil power stations. They will not, therefore, be considered further.
However, the guidance given in this document could serve as a basis for assessing the
possibilities of operating with other amines but it will be necessary to establish the relevant
amine/sodium selectivity behaviour and the compatibility of the amine with the chosen cation
resin.

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2.4 The Use of Ammonium Form Operation in Various Countries

The use of ammonium form operation varies from country to country with utilities in some, such
as Germany, deciding against the use of the technique although others, such as in Australia,
apply it widely and successfully. There is little doubt that the economies that it apparently offers
are also attractive to operators of power stations in developing countries. This is understandable
but can lead to difficulties if they do not have access to regenerants of the appropriate quality,
particularly sodium hydroxide, or have staff with the knowledge that trouble-free operation in the
ammonium form demands. A brief review of the reported use of ammonium form operation
world-wide is given below.

2.4.1 Asia

The situation in Asia is not clear but it is known that stations in large countries such as China and
India have showed interest in ammonium form operation. However, the problem of obtaining
7
sodium hydroxide regenerant of adequate purity is reported to be an obstacle . The problems
reported by Indian power stations in connection with the use of hydrochloric acid for
regeneration of cation resins used in ammonium form polishing plants are discussed in Section 3
and 8.

2.4.2 Australia

Several Australian power stations have reported successful and continued operation of
condensate polishers in the ammonium form. They range from stations such as the 4x350 MWe
Tarong Power Station, which employs a Conesep high efficiency mixed bed separation system,
to stations such as Stanwell (4x350 MWe) which uses the proprietary Tripol separate bed
polisher. This experience is discussed later.

2.4.3 Germany

Separate bed condensate polishing plants are being increasingly used on fossil power stations in
Germany. This design of plant would be very convenient for ammonium form operation but it is
reported that German power stations only operate their polishing plants in the H-OH mode.

2.4.4 Ireland

The Electricity Supply Board of Ireland (ESB) is a relatively small utility with a total capacity of
about 4300 MWe. In 1980 a successful series of ammonium form operation trials were
conducted in collaboration with the Central Electricity Generating Board of the UK on a 270
MWe once-through boiler at Aghada Generating Station. The ESB subsequently developed its
own procedures at the 3x 300 MWe coal fired drum station at Moneypoint and has successfully
applied them on other stations. The information derived from Aghada and Moneypoint is
particularly useful and instructive and is considered in further detail elsewhere in these
Guidelines.

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2.4.5 United Kingdom

The UK did not include condensate polishing in the design of any of its drum boiler fossil
stations. Three seawater cooled fossil stations were later retrofitted with polishing to alleviate
problems caused by condenser leakage but these were operated in the H-OH form. There was,
in fact, one fossil power station equipped with once-through boilers and this was fitted with
condensate polishing that, again, was operated in the H-OH form.

To gather information on ammonium form operation, in support of its possible use on gas cooled
nuclear plant, a series of trials were carried out in the late 1970’s on the oil fired drum power
station at Fawley, UK. The results obtained supported the belief that effective separation and
regeneration of mixed beds is essential to allow successful operation in this mode. The work
was pursued in the joint investigations with the ESB (Ireland) referred to above. These studies
as well as providing useful information on ammonium form operation subsequently formed a
basis for the development of the morpholine mode of operation.

Morpholine form condensate polishing, which is essentially the same as ammonium form
operation, has very successfully been used at the gas cooled nuclear power station at Oldbury on
Severn since 1984 allowing it to use 60 ppm of the amine and to overcome circuit corrosion
problems. The mixed bed regeneration system was upgraded by the replacement of the
conventional top sluicing design of separation vessel by a bottom transfer separation system.

2.4.6 United States

The use of ammonium form operation on fossil stations in the United States is common, with the
survey of polishing plants on US power stations reported in EPRI TR-104422 supporting this
belief. There are many early papers dealing with the use of ammonium form operation on US
fossil power stations but fewer in recent years. Of the more recent publications that by Meyers
dealing with the application of the Amsep separation process on the 2x800 MWe coal fired
supercritical unit at Mohave is of most interest and is discussed in Section 4.3. Resins prepared
by this high efficiency separation/regeneration process yielded a polished water containing 0.1-
0.2 ppb of sodium and chloride when operating in the ammonium form at pH 9.55.

US power stations are, of course, influenced by the advice given by EPRI. It is well aware of
difficulties experienced by some stations in the past when using ammonium form operation and
has therefore taken a very guarded position, neither condemning nor endorsing the procedure.
As discussed elsewhere in this document, the conventional H-OH approach is certainly the more
robust and easier mode of operation. Thus, in its Cycle Chemistry Guidelines for Fossil Plants :
Oxygenated Treatment (TR-102285), EPRI recommends the use of deep bed condensate
polishing which “should be conducted in the hydrogen form. Ammonium form operation is not
justified except under unusual circumstances”8. The main users of OT Guidelines are once-
through boilers employing very low levels of ammonia. Hence the economic benefits to be
derived from operation of their polishers in the ammonium form are small so this is not a
condemnation of ammonium form operation. In the more recent TR-110051, Interim Cycle
Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators (HRSGs) those
boiler units operating on AVT at pH 9.2-9.6 are advised that “for economic and regenerant
waste disposal reasons” they could operate in the ammonium form9.

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2.4.7 South Africa

ESKOM, the South African national power utility, has several large, 6x600 MWe, dry cooled
power stations. All employ condensate polishing with some using plants of a cation-anion
separate bed design. A paper dealing with the very early experience of ammonium form
operation of the polishing plant at Matimba indicates sodium in polished water levels of 0.9-1.7
ppb with inlet temperatures normally well above 55oC (131oF), and sometimes above 80oC
(176oF), and a pH of approximately 9.510. Nine years later Matimba was still operating in the
ammonium form but at a very much higher pH of 9.8 and by this time had also adopted Oxygen
11
Treatment .

2.5 References
1. F. McCarthy and G. O’Connor, “Ammonium Form Operation of Condensate Polishing Plant
rd
for Long Periods in High pH Systems at Moneypoint Power Station”, Proceedings of the 53
International Water Conference, Engineers’ Society of Western Pennsylvania,1992.
2. D. J. O’Sullivan and E. F. McCarthy, “A Review of Condensate Polishing Plant Operation in
the Electricity Supply Board of Ireland”, Proceedings of the EPRI Fifth International Cycle
Chemistry in Fossil Plants, Charlotte, NC, 1997
3. B. A. Derrick and K L Atwood, “Condensate Polishing Experience at Wateree Power
th
Station”, Proceedings of the 37 International Water Conference, Engineers Society of
Western Pennsylvania, 1976.
4. EPRI TR-105040, Selection and Optimisation of Boiler Water and Feedwater Treatments for
Fossil Plants. R R Harries, “The Role of pH in Ion Exchange Kinetics”, Ion Exchange for
Industry, Ellis Horwood, Chichester, United Kingdom, 1988.
5. M. A. Sadler, J. C. Bates, M. R. Darvill and G. W. Ellis, “Morpholine Form Condensate
Polishing at Oldbury on Severn Nuclear Power Station”, Ion Exchange for Industry, Ellis
Horwood, Chichester, United Kingdom, 1988.
6. Zhang Chenxin and Chen Long, “The Special Problems Might BeEncountered with the
st
Operation of Condensate Polishing Systems in China”, Proceedings of the 61 International
Water Conference, Engineers’ Society of Western Pennsylvania,1998.
7. EPRI TR-102285, Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment.
8. EPRI TR-110051, Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery
Steam Generators (HRSGs).
9. W. A. Marchewka, J D Asden and J B Conlin, “Condensate Polishing atElevated
st
Temperatures”, Proceedings of the 51 International Water Conference, Engineers’ Society
of Western Pennsylvania,1988.
10. O. Sadie, “ Experience with the Effects of AVT and OT on the Condensate System at
Matimba Power Station and Condensate Polisher Performanceat Elevated Temperatures”,
Proceedings of the Eskom International Conference on Process Water Treatment and Power
Plant Chemistry, Midrand, South Africa,1997.

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3
THEORY OF AMMONIUM FORM OPERATION

3.1 Background

In all ion exchange processes, given sufficient time, equilibrium is established between the
concentration of an impurity in the water phase and that in the resin phase. This is simply
expressed, for sodium exchange on an H+ cation resin, by the well known equation:-

Na + RH ⇔ RNa + H
+ +

Where : Na+ = Sodium ion concentration in the aqueous phase

H+ = Hydrogen ion concentration in the aqueous phase
RH = Proportion of the ion exchange sites on the cation resin occupied by
hydrogen ions
RNa = Proportion of the ion exchange sites on the cation resin occupied
by sodium ions

In the simple two ion component system being described, RH + RNa = 1, i.e. ion exchange sites
+ +
on the cation resin are occupied by either Na or H ions.

Using an equilibrium constant, K, this equation can also be shown as:-

+
K = [RNa][H ]
[Na+][RH]

In condensate polishing applications employing mixed beds of cation resin in the H+ form and
anion resins in the OH- form (H-OH form beds), the H+ ion concentration is, ideally, reduced by
the ion exchange process to that of pure water, 1x 10-7 equivalents/litre @ 25oC (77oF). Provided
that low values of sodium on resin [RNa] are achieved through effective regeneration procedures
then concentrations of sodium in the water phase [Na+] will also be very low. It has been shown,
experimentally that water containing sodium at levels of less than 2 ppt (ng/kg) can be prepared
by H-OH form polishing plants. Even lower levels of sodium in water, below the current limits
1
of analytical detection, are predicted by theory and possibly attained in practice . In real life, the
situation is more complicated because other ions will be present but the simple approach outlined
above serves as a useful guide.

In the case of sodium exchange on H+ form cation resin, the effective equilibrium constant is the
selectivity coefficient, K HNa . In reality, K HNa and other selectivity coefficients are not true
constants but vary with temperature, resin type and with the concentration of the ion on the resin
phase2, Figure 3-1. For most calculations concerned with condensate polishing it is, however, a

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convenient approximation to regard these selectivities as constants and Appendix 1 gives a list of
the commonly used values. Selectivities are also influenced by the presence of other ionic
impurities in the system being considered. Nevertheless, they provide a very useful, but simple,
approach to understanding ion exchange equilibria and to gaining an insight into the possible
leakage of ionic impurities..

Figure 3-1
Na/H exchange equilibria. Macroporous cation resin.

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Anion exchange reactions can be similarly described by :

Cl- + ROH ⇔ RCL + OH-

-
This reaction, in H-OH form mixed beds, is driven almost to completion as the OH concentration
is moved towards that of pure water, 1x 10-7 equivalents/litre. Some condensate polishing plants
operating in the H-OH form consistently yield water containing less than the current limit of
detection of chloride, about 5 ppt.

Similar equilibrium equations control the behaviour of ammonium form condensate polishing
beds, i.e.

Na + RNH4 ⇔ RNa + NH4

+ +

Cl- + ROH ⇔ RCL + OH-

There are, however, two major changes that affect the behaviour of ammonium form mixed bed
making them significantly different to conventional H-OH form beds. In cation exchange the
very low H term ( ⇒ 1x 10 eq/l) is replaced by an ammonium ion concentration which, at pH
+ -7

9.6 is over two orders of magnitude higher (40x10-6 eq/l) than the H+ term in H-OH form
operation. Similarly, in anion exchange, the OH- term in the equilibrium equation increases to
40x10-6 eq/l. The effect of this is that the water phase values of sodium and chloride have to
increase to balance the equations. In brief, the impurity levels in polished water increase by
several orders of magnitude and this change is discussed below.

The second change affects sodium exchange and the leakage behaviour of this impurity from
resins operating in the ammonium form. The selectivity of a typical strongly basic H+ cation
resin for sodium is about 2, i.e. the resin prefers sodium rather than the hydrogen ion. In contrast,
the selectivity of an ammonium form cation resin for sodium is lower at about 0.75-0.9 so that
the resin prefers the ammonium ion rather than the sodium ion, Figure 3-2. In any calculations
given in these Guidelines a sodium/ammonium selectivity of 0.8, representing a rounded value,
will be assumed. At equilibrium, this low selectivity contributes to a higher sodium
concentration in the water phase and hence higher levels of leakage of sodium.

These two factors, the water phase ammonium concentration and the ammonium/sodium
selectivity of the cation resin, control the behaviour of sodium in beds operated in ammonium
form operation. It is this leakage behaviour of sodium that dominates any consideration of
ammonium form operation and so it will be considered in detail. However, chloride leakage is
also increased as is that of other anionic impurities.

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Figure 3-2
Na/NH4 exchange equilibria. Extreme dilution.

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3.2 Ion Exchange Capacities in Ammonium Form Operation

The capacity of ion exchange resins for usefully removing ions of interest can be described in
different ways. The total capacity is a measure of the number of active ion exchange sites on a
resin and can be expressed on a dry weight basis (equivalents per dried weight of resin) or on a
wet volume basis, (equivalents per volume of wet, fully swollen, resin). It is the latter
measurement that is more usually employed by those engaged in condensate polishing as it can
be easily related to plant design and conditions.

Of even more practical use is the operating capacity, again quoted on a wet volume basis, as it is
an indication of the capacity available for use under defined conditions. The end point to which a
bed is run when in service is an important factor to be taken into account together with the level
of regeneration of the resin concerned. Thus, in conventional H-OH form operation of polishing
beds, a cation resin operating capacity of about 50-60% of the total capacity can be expected.
This assumes operation to conductivity breakthrough of 0.1 µS/cm caused by the increasing
leakage of ammonia. The operational capacity of anion resins under H-OH conditions is defined
in the same way, i.e. the capacity shown under defined conditions to a set conductivity endpoint
or anion leakage. Thus, operational capacities under defined conditions, and to a defined
breakpoint, serve as an approximate but important guide to what will happen in service to an H-
OH form bed.

In ammonium form operation it is the equilibrium capacity, not the total capacity, which
represents the highest achievable capacity with the operating capacity being, again, a fraction of
this. In this mode, the operator will not be concerned with the ion exchange behaviour of
ammonia, as it will pass through the bed unhindered, but only in the behaviour of other cationic
impurities such as sodium. Equilibrium capacity can therefore be defined as that shown by a
resin, under specified ammonium form plant operating conditions of pH and temperature,
towards a specific input concentration of an impurity, sodium for example. It is the capacity
exhibited up to the point when the outlet concentration of the impurity becomes equal to the inlet
concentration, i.e. when the bed reaches a state of equilibrium. Now, in practice, an ammonium
form polishing bed treating, for example, a sodium concentration in influent condensate of 500
ppb, would be taken out of service as soon as the sodium in polished water increased to a few
ppb. The bed would not be operated to equilibrium conditions with 500 ppb sodium both
entering and leaving the bed. The application of knowledge of equilibrium capacities in
predicting the more practically useful operating capacities is discussed in Section 3.5.

Equilibrium capacities can be calculated for the range of pH values now of interest to the fossil
power industry using the selectivity values given in Appendix 1 and assuming simple two
component systems. The general equation given above is used is assumed with a range of
sodium input concentrations, a pH (and hence [NH+4]) and a selectivity coefficient of 0.8.

Chloride equilibrium capacities can be calculated using a similar formula and assuming a K Cl
OH
selectivity of 22.

Figures 3-3 and 3-4 show the relationship between input levels, pH and equilibrium capacities
3
for sodium and chloride and follow earlier work by Darji and McGilbra . They show how the
equilibrium capacities vary with both pH and the impurity input level, with the variation shown

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by sodium being particularly pronounced. This, as discussed below, controls the behaviour of
ammonium form beds in the presence of an impurity ingress incident such as a condenser leak.

Figure 3-3
Ammonium form condensate polishing, calculated equilibrium capacities of strongly
acidic cation resin for sodium at a range of pH values. (Assuming volume capacity =
2 eq/L and selectivity coefficient = 0.8)

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Figure 3-4
Ammonium form condensate polishing, calculated equilibrium capacities of strongly basic
anion resin for chloride at a range of pH values. (Assuming volume capacity = 1 eq/L and
selectivity coefficient = 22)

3.3 Equilibrium Leakages in Ammonium Form Operation

The same general approach as adopted for calculating equilibrium capacities under various
ammonium form operating conditions can be used to predict equilibrium leakage from
ammonium form resins in the absence of impurity inputs. Equilibrium leakage can be described
as the steady state leakage of impurities held by ion exchange forces on the resins into the water
phase so that a resin/water equilibrium is achieved. These impurities on the resins usually arise
from incomplete regeneration. However, it must be noted that although perfect regeneration is,
in practical terms, almost impossible to attain it is possible to reduce the level of impurities on
resins to very low levels and various approaches have been devised to help achieve this end.
Impurities can, of course, also be picked up during service.

When levels of ionic impurities in the water phase impurity are very low the equilibrium leakage
mechanism causes impurities to move from the resins to the water phase. In the presence of
higher impurity levels in the water phase, when impurities move from solution on to the resins,
the concentration of impurities on the resins controls the lowest levels to which water phase
impurity concentrations can be reduced. In other words, the resin either contributes impurities to
the water or takes it from the water phase in order to achieve equilibrium conditions. Either way
resin impurity levels, and hence regeneration effectiveness, control the quality of the final
polished water.

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The calculated equilibrium leakage value shown in Figures 3-5 and 3-6 must be viewed as
simply very approximate guides to the leakage of sodium and chloride under ammonium form
condensate polishing conditions. The conditions encountered on real life polishing plants
introduce variables such as the impurity levels in the influent condensate and the temperature of
operation. The actual leakage behviour of chloride, and particularly sodium, is more complex as
plant experience and computer models show. Nevertheless, the calculated values shown in
Figures 3-5 and 3-6 are still useful in providing an indication of possible leakage levels. They
must be compared with the very much lower leakages expected from resins operated in the H-
OH form and demonstrate the need, when operating in the ammonia form, for resins to be
regenerated to a very high degree.

Figure 3-5
Ammonium form condensate polishing, equilibrium leakage of sodium from strongly
acidic cation resin at a range of pH values @ 25°C. (Assuming volume capacity = 2 eq/L
and selectivity coefficient = 0.8)

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Figure 3-6
Ammonium form condensate polishing, equilibrium leakage of chloride from strongly
basic anion resin at a range of pH values @ 25°C. (Assuming volume capacity = 1 eq/L and
selectivity coefficient = 22)

3.4 Ammonium Displacement Effects

When a mixed bed operated in the H-OH form is used to remove cationic impurities, such as
sodium, the H+ ions released by the exchange combine with OH- ions to form water.
Theoretically there is not, overall, any disturbance to the pH of the condensate being treated. In
ammonium form operation, every sodium ion exchanged results in the release of an ammonium
ion. This ammonia displacement effect and the consequent small increase in pH and sodium
leakage is discussed below.

3.5 The Behaviour of the Common Impurities in Ammonium Form

Condensate Polishing

3.5.1 Sodium

Sodium Leakage Behaviour in Under Ammonium Form Conditions –Without Condenser

Leakage

It is certainly possible to pre-ammoniate cation resins so that mixed beds and separate beds enter
service already in the NH4-OH form and this approach has some advantages. Pre-ammoniation,

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which is discussed in Sections 6 and 8, is not efficient in the use of ammonia and introduces
another step in the regeneration process. Because of this, it is not generally favoured by
operators and beds are normally returned to service in the H-OH form and allowed to ammoniate
in service.

Figures 3-7, 3-8 and 3-9 show the sodium leakage behaviour from mixed beds, at three different
power stations, from the time they enter service, through the ammoniation phase and their
subsequent steady state operation in the ammonium form. Figure 2-2 was derived from a figure
published in an early paper by Derrick and Atwood and records the performance of a mixed bed
at pH 9.2-9.4 at Wateree Power Station, South Carolina Electric and Gas Company4. Although
the leakage levels are significantly higher than currently achieved the figure shows the typical
sodium leakage behaviour of a mixed bed ammoniating in service.

With the improved separation and regeneration procedures currently available very much lower
leakage levels than shown in the Wateree graph are being consistently achieved on fossil stations
operating under even higher pH conditions. Those reported from Aghada Power Station in 1980,
Figure 3-7, and Moneypoint Power Station in 1992, Figure 3-8, are indicative of what can be
achieved. Both of these stations show sodium leakage under H-OH form conditions of <<0.1
ppb peaking to about 1 ppb during the on-line ammoniation phase and settling down to a steady
1,5
state leakage under ammonium form conditions at pH 9.6 of about 0.2-0.3 ppb . Significantly
better performances are reported by Mohave Power Station and these are discussed in Section 4
and shown in Figure 3-96.

Figure 3-7
Ammonium form operation on a gas fired 270 MW boiler with seawater cooling, on-line
ammoniation.

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Figure 3-8
Ammonium form operation—impurity levels at condensate polisher outlet, Moneypoint
Generating Station. pH 9.6.

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Figure 3-9
Ammonium form operation—impurity levels at condensate polisher outlet, Mohave Power
Station. Polisher 2S. pH 9.6.

The three phases of sodium leakage are simply explained. The first phase is controlled mainly
by H-OH equilibrium. As already discussed, in this mode of operation the sodium leakage is
related mainly to the sodium content of the resin and as long as this is low the leakage will be
low. At both Aghada and Moneypoint the resin sodium levels were less than 0.1% (i.e. <0.1% of
the cation exchange sites were in the sodium form). However as the bed gradually exhausts to
the ammonium form the capacity of the cation resin, in the exhausted zone, to hold sodium falls -
as discussed and shown in Section 3-2. The new capacity will be determined both by the pH and
the sodium level of the influent condensate so that if this is low, as it will be under no in-leakage
conditions, the ammonium form capacity will be low. A proportion of the sodium already held
by the resin will usually be displaced and be pushed along with the ammonia exhaustion front
through the bed. Ammonia breakthrough from the bed will be quickly followed by increased
leakage of sodium leading to a sodium throw peak that over the course of the next 5-10 days
gradually decays to a new steady state sodium leakage value as shown in phase 3. The
magnitude of the sodium leakage under the fully ammoniated steady state conditions will depend
upon the pH of operation, the temperature and the residual sodium content of the resin – all
assuming that no further sodium ingress occurs.

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Sodium Leakage Behaviour in Under Ammonium Form Conditions – With Condenser

Leakage

When the condensate entering an ammonium form polishing plant is contaminated by a

condenser leak the influent sodium levels will obviously increase. This influent sodium will be
exchanged by the ammonium form cation resins leading to the release of an equivalent quantity
of ammonium ions and a consequent increase in the pH of the water leaving the polishing plant.
The effect of this rise in pH is to increase the equilibrium leakage of sodium with the extent of
the increase being determined by concentration of sodium in the influent and the original pH of
the condensate.

Assuming that prior to a condenser leak the influent condensate was at pH 9.2 (approximately
520 ppb NH4) then a 500 ppb input of sodium will displace ammonia leading to a pH increase to
about 9.39 – assuming 25oC (77oF) conditions. If the cation resin had originally contained 0.1%
of its active exchange sites in the sodium form it would have been leaking about 0.46 ppb
sodium. This leakage would increase to about 0.7 ppb as a result of the ammonia displacement
caused by the condenser leak. If the original pH had been much higher, say pH 9.6, the
equilibrium leakage of sodium would have been considerably higher at 1.15 ppb. However, at
this higher pH, the effect of the ammonia displacement following the condenser leak would be
slightly less pronounced. The pH would increase to about 9.64 causing sodium leakage to
increase to about 1.3 ppb. Thus, the effect of ammonia displacement is more noticeable at low
pH than at high and is, of course, dependent on the existing sodium contamination of the resin.
However, over the course of the next 2-4 days other leakage effects begin to dominate the minor
effects of ammonia displacement.

It has already been pointed out that, under the high pH conditions of ammonium form operation,
the ion exchange capacity of cation resin for sodium varies with both pH and the concentration
of the impurity in the influent. It must also be noted that the capacity varies with temperature.
o o
For simplicity, a 25 C (77 F) steady temperature situation is assumed in all the examples given.
Ammonium form cation resin running under steady state conditions at pH 9.2 with an influent
sodium concentration of 1 ppb would have a very low equilibrium capacity of 0.004 eq/l. If the
inlet concentration increases to 500 ppb, the pH would increase slightly owing to the
displacement effects discussed above but, more importantly, there would be a large increase in
the equilibrium capacity. Thus, the cation resin would be able to retain more sodium at the
higher input level. The pH would increase, by ammonia displacement to about pH 9.39 and the
new equilibrium capacity would be about 0.83 eq/l. If the leak persisted then the resin bed
would gradually exhaust with the sodium exhaustion front descending through the bed until it
breaks through. Under these conditions the run length will be determined by the inlet impurity
concentration as indicated by computer simulations7 (Figure 3-10).

Condensate polishing beds are always taken out of service when the leakage of influent ionic
impurities exceeds a chosen level. This is often about 1 to 2 ppb or a conductivity value
approximating to a concentration of interest. Operators are more interested in the capacity to a
selected endpoint, the “operating capacity”, than in total capacities or theoretical “equilibrium
capacities”. Experience shows that under conventional H-OH form conditions the operating
capacity to, say, a 0.1 µS/cm ammonia leakage endpoint (approximately 5 ppb ammonia) is
approximately 50-60% of the total capacity although this depends on variables such as the
efficiency of regeneration. Under ammonium form operating conditions the operating capacities

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are less well identified and obviously the ammonia end point is of no interest. However,
experience again shows that to a leakage of 2 ppb sodium the cation operating capacity again
approximates to 50% of the equilibrium capacity. More accurate assessments of likely operating
capacities can be made using the predicted conditions of operation and one of the computer
models referred to earlier.

Figure 3-10
Predicted sodium breakthrough with constant sodium inputs at pH 9.6.

3.5.2 Chloride

As already mentioned, it is the leakage behaviour of sodium from ammonium form condensate
polishers that usually attracts the most attention. The leakage of this undesirable impurity is
normally higher than any other ion but the behaviour of potentially corrosive ions such as
chloride is also important although less frequently discussed. Its behaviour under the high pH
conditions of ammonium form operation is again controlled by the equilibrium equation:

Cl- + ROH ⇔ RCL + OH-

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This can be rearranged:

K Cl -
OH = [RCl][OH ]
[ROH][Cl-]

A range of values for the selectivity coefficient are shown in the literature with K Cl
OH =22 being
used in recent EPRI publications for strongly basic resins under condensate polishing conditions.
The chloride/hydroxide selectivity of strongly basic anion resins may vary with the type of resin
and has been shown to vary with concentration of chloride in the resin phase. It is highest at
very low chloride on resin levels, Figure 3-11. What is important is that this selectivity is an
order of magnitude higher that shown by ammonium form cation resins for sodium. Thus,
chloride leakage and equilibrium capacities, and hence operating capacities, are usually far less
of a problem than experienced in sodium exchange on ammonium form resins under high pH
condition. However, they are still controlled by similar mechanisms and thus dependent on resin
chloride levels, and hence on effectiveness of regeneration, and the pH of operation.

An anion resin with 1% of its exchange sites in the chloride form can be expected to leak, under
equilibrium conditions at pH 7, about 0.002 ppb of chloride but at pH 9.6 this leakage is
predicted to increase to about 0.65 ppb. For ammonium form operation the level of <1% chloride
has been suggested as the target for regeneration of anion resins and the reasons behind this
suggestions are discussed in Section 4. Figures 3-6 and 3-12, show the effect of pH and resin
chloride content on chloride leakage. However, experience with anion resins containing 1%
chloride at Moneypoint Power Station, operating under ammonium form conditions at pH 9.6
show actual leakage levels increasing to only about 0.3 ppb, Figure 3-13. Plant data from the
earlier Aghada trials show similar leakage levels. Figure 3-14. These results suggest that at low
concentrations of chloride on the resin the selectivity may be higher than assumed.

The levels of leakage of chloride seen at stations employing effective regeneration techniques are
well below any existing fossil power station condensate and feedwater specification. This shows
that generally, and under condenser leak free conditions, chloride leakage need not be a problem.
However, it should be noted that all of the station experience so far discussed was obtained on
plants using sulphuric acid as the cation resin regenerant. Some countries, such as India, use
hydrochloric acid and there suggestions, so far unsupported, that the use of this acid has led to
unacceptably high levels of chloride leakage when polishing plants are operated in the
ammonium form. This topic is considered in more detail in Sections 4 and 8.

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Figure 3-11
Cl/OH exchange equilibrium at extreme dilution with strongly basic anion exchange resin.

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Figure 3-12
Equilibrium chloride leakage at high pH and 25°C.

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Figure 3-13
Ammonium form operation—chloride, cation conductivity and sulphate levels at
condensate polisher outlet, Moneypoint Generating Station. pH 9.6.

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Figure 3-14
Ammonium form operation—chloride, cation conductivity and sulphate levels at
condensate polisher outlet, Aghada Generating Station. pH 9.6.

3.5.3 Sulphate

The equilibrium leakage behaviour of sulphate has always been difficult to predict and model.
Sulphate is, of course, a divalent ion so that the selectivity shown to it by a strongly basic anion
resin is extremely high. Even now doubt exists over the exact selectivity coefficient to be used
for sulphate exchange on to an OH form resin. Studies, published by EPRI, indicate that, at pH 7,
the equilibrium leakage of sulphate from an anion resin containing 1-10% of its active exchange
sites in the sulphate form should be 10-9 to 10-10 of a ppb8. Now at pH 9.6 the leakage should be
several orders of magnitude higher but obviously will still be very low in practical terms. These
estimates assumed a selectivity coefficient for the divalent sulphate ion of 60 and there has been
debate over whether this is the correct value to use as other workers have suggested different
values. What is not in question is that sulphate equilibrium leakage is extremely low. Under
plant conditions, using mixed beds or separate beds, the study of sulphate leakage is further
complicated by the fact that the strongly acidic cation resin itself releases trace quantities of both
sulphate and organic sulphonates. They are derived from the sulphonic acid groups that are used
as the functional cation exchange sites on strongly acidic cation resins form. The small amount
of cation resin that becomes completely sulphated owing to less than perfect separation of mixed
beds prior to regeneration is another source of sulphate leakage. It is, however, understood and
procedures for reducing this effect are known.

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Thus, the topic of sulphate leakage and the way the overall sulphate leakage is influenced by pH
is complex. Experience of ammonium form operation shows, however, that it is not a problem.
At Mohave Power Station sulphate levels of 0.1-0.2 ppb are reported when operating in the
ammonium form at pH 9.55 despite condensate temperatures of up to 60oC (140oF). Moneypoint
operates with extremely high levels of sulphate on the anion resin, between 20-25% and, despite
this, finds that the leakage under H-OH conditions is only about 0.1 ppb increasing to about 0.3
ppb when the resins run through into the ammonium form at pH 9.6. It is difficult to attribute the
increase to a pH driven increase in equilibrium leakage but it is a consistent effect also seen on
the earlier Aghada trial where, again, high levels of sulphate on the anion resin were present.
Stanwell Power Station reports sulphates of <0.1 ppb when in the H-OH mode increasing to 0.2
ppb in the ammonium form at pH 9.359. Sulphate leakage ranging from 0.1-0.3% has been
reported from Oldbury on Severn Nuclear Power Station. This plant operates its polishers in the
morpholine form at pH 9.5 so that similar behaviour to polishers operated in the ammonium form
is to be expected.

All the sulphate leakage mechanisms are not, as yet, fully understood. However, there is no
evidence or expectation that sulphate leakage when operating in the ammonium form will be a
problem unless the kinetic response of the anion resin becomes impaired owing to fouling or
simply old age. The kinetics of the ion exchange of sulphate under the high pH conditions of
ammonium form operation are known to be extremely sensitive to even slight fouling. If there is
a source of sulphate within the mixed bed itself, such as from the cation resin, then any fouling
of the anion resin could lead to a higher leakage of the impurity.

3.5.4 Carbonate

Information on carbonate removal performance by ammonium form beds is not often reported.
It is known that, at Moneypoint, resins entered service, following regeneration, containing about
3% of carbonate and after several months ammonium form service this had increased to 23.5%.
The increase can be approximated to the continuous pick-up of a few ppb of carbonate over a
service run of about 2 months but still does not yield information about the efficiency of
removal. Ammonium form bed service runs at this station were terminated on rising cation
conductivities attributed to CO2 leakage. In the development work on the Tripol process, Renouf
and Smith reported that an air leak caused condensate being fed to a large pilot plant to be
10
contaminated with a CO2 leak of about 9-31 ppb . Some CO2 slippage was suspected but despite
the high levels of carbonate on the resins a subsequent condenser leak was successfully treated
without leakage of chloride. Studies carried out on the morpholine form polishers at Oldbury on
Severn showed that carbon dioxide level in condensate ranged from 15-25 ppb rising to 50 ppb
when clean drains were being recovered to the condenser11. The results from an on-line carbon
dioxide monitor indicated almost complete removal of the impurity with levels in polished
condensate being normally less than 1 ppb. Within a bed run of thirty days, no anion exhaustion
(by carbonate) was observed. Thus, more information on the ion exchange behaviour of CO2 is
desirable but, as yet, no plant problems have been reported.

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3.5.5 Acetic and Formic Acids

The commonly occurring weak organic acids, such as acetic and formic acids, both have very
low selectivity coefficients with EPRI TR-101942 reporting values of 3.2 and 4.6 respectively
which must be compared with the value of 22 for chloride ( K Cl OH =22). All these values are
relative to a hydroxide selectivity of unity and relate to a strongly basic resin. They give a guide
to the behaviour of acetic and formic acids under ammonium form conditions and indicate that
strongly basic anion resins will have a small, but useful capacity for these anions. However, this
capacity will be, as with other ions, strongly influenced by pH, the higher the pH the lower the
capacity. Figures 3-15 shows the, theoretical, effect of pH and acetate influent concentration on
equilibrium capacities assuming a simple two component situation i.e. hydroxide and acetate.

Figure 3-15
Variation of equilibrium capacity for acetate with pH and acetate input level (assuming
AC
K OH = 3.2 and anion resin volume capacity = 1 eq/L)

The source of these acids is generally considered to be organic impurities in make-up water and
their subsequent decomposition in the steam/water circuit. Concentrations in steam water
circuits without condensate polishing are typically about 10-20 ppb of acetic acid and about 5-10
ppb of formic acid. The levels actually seen on any power station obviously depend on the
station and the quality of its make-up water. Few, if any, organic acid problems have been
reported by stations using ammonium form operation although these impurities are not often
monitored or reported by fossil power stations. Moneypoint, for instance, reports service runs of
150-200 days terminated “by an increase in bicarbonate leakage”. On this power station acetate
levels in polished condensate were about 1 ppb with even lower formate levels when the cation

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conductivity was about 0.07 µS/cm. Even when polished water conductivity values started to
rise, after 150-200 days in service, and reached 0.12 µS/cm, attributed to bicarbonate leakage,
the levels of acetate and formate remained consistently low.

On this evidence, and given make-up water of adequate quality, there seems to be little cause for
concern. However, the experience reported by Oldbury on Severn Power Station is of interest.
As already discussed, this nuclear power station uses 60 ppm of morpholine to condition its
steam/water circuit and some thermal breakdown occurs with decomposition mechanisms and
end products being well known. Acetate break-though from the morpholine form polishers
under these condition is clearly seen, Figure 3-16. The fact that few fossil power stations use
organic conditioning agents has already been mentioned in Section 2.4

Figure 3-16
Acetate breakthrough in morpholine form operation of a condensate polishing plant at pH
9.5. Composite of a number of runs with inlet concentration approx. 20 ppb.

3.5.6 Silica

Generally, silica problems have been eliminated by the introduction of modern techniques of
make-up water preparation and silica now rarely poses the problem that it once did. It is a very
weak acid and a selectivity of 5 has been proposed by Venderbosch and his co-workers12.
However, silica is a very difficult ion to study in view of the many forms in which it can be
present. Problems are encountered in its detection and analysis at the very low levels found in

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condensate. Evidence, such as that reported by the ammonium form separate bed plant at
Matimba, Eskom (South Africa) indicates that even at silica input levels as low as 4 ppb, and at
pH 9.5, some removal is still taking place with levels in polished water being about 3 ppb13.
Crits has reported experience on a station that extended its ammonium form service runs to 90
days despite having a colloidal silica slippage problem on its make-up plant. On this station
silica level in the circuit rose to over 40 ppb with silica breakthrough from its polishers occurring
in about 30 days at 27oC (80oF)14. This behaviour generally agrees with that expected from an
impurity to which the resins show a low selectivity and is similar to that seen for the weak
organic acids.

3.5.7 Iron

One of the arguments in favour of employing conventional, H-OH form, full flow condensate
polishing is that iron corrosion products are continuously removed. At high input levels the
efficiency can be as high as 90% falling to about 50% at very low input levels. Filtration
efficiencies when operating in the ammonium form appear to be about the same. Thus, when
operating at pH 9.6, iron values during a typical ammonium form run at Moneypoint varied
“from 4-10 ppb at the polisher inlet to 2-4 ppb at the polisher outlet”, Figure 3-17. On this
station, pressure drops are not a problem with beds entering service at about 1.3 bar (19 psi)
going up to about 2.1 bar (30 psi) after 200 days. Even after this time in service the resins
cleaned satisfactorily.

The separate bed plant at Stanwell, operating at pH 9.35 claimed, that at start-up, crud levels
were reduced from 80-90 ppb to less than 5 ppb and that when operating at steady state inlet
levels of 10-20 ppb were again reduced to less than 5pp. Matimba Power Station, using cation–
anion separate deep beds, found during commissioning that levels of 180-427 ppb were reduced
to 12-16 ppb across the lead cation bed and that at steady state an inlet value of 34 ppb was
reduced to 3 ppb. However, Cutler points out that there is evidence that polishers operating in
the H-OH mode are better at removing the amorphous forms of iron oxide that are usually
15
encountered during plant commissioning and at start-ups . The crystalline forms of crud are
clearly removed by both H-OH form and ammonium form polishers. Japanese experimental
work, using specially prepared haematite (α−Fe2O3) particles, indicates that at high pH these
particles were captured more easily by anion resins rather than cation resins indicating that
filtration efficiency of resin beds could be pH dependent, Figure 3-1816.

The issue of iron removal by bead resins has been intensively studied in view of its importance
to BWR operation. It is clearly a very complex topic with iron removal efficiency being linked
to the form of the oxide, the degree of cross linkage of the cation resins and the age of the resin.
The mechanisms controlling crud filtration efficiency have been discussed in a number of EPRI
and other conference papers and reports. On the whole there is not any clear evidence from
plants that the iron filtration behaviour of ammonium form polishers is inferior to that of
polishers operated in the H-OH mode except when dealing with amorphous forms of the
impurity. This topic is further discussed in Section 6.

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Figure 3-17
Ammonium form operation—iron levels at condensate polisher inlet and outlet,
Moneypoint generating station. pH 9.6.

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Figure 3-18
The effect of pH on iron filtration by anion and cation resin, laboratory test using a
synthetic crud based on haematite.

3.5 Regeneration

Successful operation in the ammonium form depends critically upon the use of very highly
regenerated resins. This important topic is discussed in Section 4.

3.6 Computer Models of Ammonium Form Condensate Polishing

The behaviour of ammonium form condensate polishers has been computer modelled by several
groups of workers. An early model was developed by J C Bates and T Johnson. It shows,
amongst other things, the effect of pH on the elution of sodium that had been loaded on to a resin
column, i.e. a simulation of the behaviour of a short term condenser leak, Figure 3-19. The
programme was written in Fortran and other workers have now written similar programmes for
PCs using a simple spreadsheet approach.

Foutch and his co-workers at Oklahoma State University have developed the computer
modelling of ion exchange reactions and in particular have evolved a widely applicable mixed
bed programme, OSU MBIE, that can be applied to simulate ammonium form and amine form
condensate polishing situations. It can simulate multi-component interactions and one
interesting finding is that, in ammonium form or amine form polishing, the high concentration of

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the amine relative to the other impurities of interest has a much greater influence on the
equilibrium than the earlier programmes allow. This finding and others allow the OSU
programme to more closely replicate the results obtained on actual plants and give confidence in
its predictive capabilities. Figure 3-20 is an example of the work of the OSU group that was
published in 199117. It is a simulation of the sodium behaviour of a mixed bed over the period of
on-line ammoniation and shows the leakage during the preliminary H-OH form period and the
typical sodium throw following ammonia breakthrough.

Figure 3-19
Computer simulation of throw of sodium loaded for a short period of time at different pH
levels.

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Figure 3-20
Computer simulation of ammonium cycle operation past the ammonia break for pH 9.6 and
a cation:anion ratio of 1.5:1. The sodium feed concentration is 23 ppb.

3.7 References

1. D. J. O’Sullivan, P. Powell, H. R. Bolton, E. K. Bullas and M. A. Sadler, “Regeneration of

Condensate Polishing Plant Resins by the Use of the Resin on Resin Technique at Aghada
Generating Station”, Ion Exchange Developments and Applications, Royal Society of
Chemistry, Cambridge, United Kingdom,1996.

2. J. R. Emmett and P. M. Grainger, “Ion Exchange Mechanisms in Condensate Polishing”,

Proceedings of the 40th International Water Conference, Engineers’ Society of Western
Pennsylvania, 1979

3. J. D. Dargi and A. F. McGilbra, “Ion Exchange Equilibrium-A Key to Condensate Polisher

Performance”, Proceedings of The American Power Conference Chicago, 1980.

4. B. A. Derrick and K. L. Atwood, “Condensate Polishing Experience at Wateree Power

th
Station”, Proceedings of the 37 International Water Conference, Engineers’ Society of
Western Pennsylvania, 1983.

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5. F. McCarthy and G. O’Connor, “ Ammonium Form Operation of Condensate Polishing Plant

for Long Periods of Time in High pH Systems at Moneypoint Power Station”, Proceedings
of the EPRI Workshop on Condensate Polishing, June 1981.

6. P. Meyers, “The Amsep Process at Mohave Generating Station”, Proceedings of the EPRI
Condensate Polishing Workshop, New Orleans, Louisiana, USA, September 1993.

7. J. C. Bates and T. D. Johnson, “ The Development of a Computer Model Amm-Leak for

Sodium Leakage from NH4+-OH- Form Beds”. Ion Exchange Technology, Ellis Horwood,
Chichester, UK, 1984.

8. EPRI TR-101942-R1, Condensate Polishing Guidelines for PWR and BWR Plants-1997
Revision.

9. R. N. R. Robinson and L. A. Chapple, “ Operation of the World’s Largest Tripol Condensate

Polishing Vessel at Stanwell Power Station, Queensland, Australia, Ion Exchange
Developments and Applications, Royal Society of Chemistry, Cambridge, United Kingdom,
1996.

10. P. W. Renouf and J. Smith, “Operating Experience with a Tripol Ammonia Cycle
st
Condensate Polisher”, Proceedings of the 41 International Water Conference, Engineers’
Society of Western Pennsylvania,1981.

11. M. A. Sadler, J. C. Bates, M R Darvill and G W Ellis, “ Morpholine Form Condensate

Polishing at Oldbury on Severn Nuclear Power Station”, Ion Exchange for Industry, Ellis
Horwood, Chichester, UK, 1988.

12. H. W. Venderbosch, A. Snel and L. J. Overman, “Concerning the Capacity of Ion Exchange
Resins When Removing Trace Impurities From Water”, VGB Feedwater Conference, 1971.

13. W. A. Marchewka, J. D. Aspden and J. B. Conlin, “Condensate Polishing at Elevated

st
Temperatures”, Proceedings of the 51 International Water Conference, Engineers’ Society
of Western Pennsylvania,1990.

14. G. J. Crits, Condensate Polishing with the Ammonex Procedure-1984, Ion Exchange
Technology, Ellis Horwood, Chichester, UK, 1984.

15. F. M. Cutler, “Effectiveness of Iron Removal by Deep Bed Polishers”, Proceedings of the
EPRI Condensate Polishing Workshop, Scottsdale, Arizona, 1991.

16. K. Ishigure et al, “Adsorption of Model Crud on Ion Exchange Resin Beads, Proceedings of
British Nuclear Energy Society Conference on Water for Nuclear Reactors, 1983.

17. G. Foutch and E. Zecchini, “Sodium Throw in Mixed-Bed Ion Exchange”, Ultrapure Water,
November 1991.

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4
REGENERATION

4.1 Requirements

On a modern well-maintained power station, condenser leaks and other impurity ingress
incidents are infrequent. Nevertheless, they are a hazard from which condensate polishing offers
protection. However, for the majority of time that a polisher is in service it is treating an influent
condensate containing very low levels of impurities other than those, such as ammonia,
deliberately added for corrosion protection of the steam/water circuit. Under these
circumstances the common ionic impurities in the final polished water are largely derived from
the resins by one of two general mechanisms. The most important of these is equilibrium
leakage. This involves the leakage of impurities, held by ion exchange forces on the resins, into
the water being treated. Absolutely pure water will take up impurities from the resins until
equilibrium is reached between the water phase and the resin phase. Less pure water will give up
impurities to the resin until, again, equilibrium is reached. This equilibrium is controlled by the
concentration of these impurities on the resins and factors such as pH, the resin selectivity
coefficients for the ions of interest and also temperature. Under power plant conditions factors
such as selectivity coefficients and temperature can not be easily changed so that to reduce
equilibrium leakage it is necessary to reduce the levels of impurities on the resins. Thus, the key
to successful operation of condensate polishing plant in the ammonium form lies in the effective
regeneration of the resins being used.

Equilibrium leakage is discussed in more detail in Section 3 in which it is pointed out that, under
+ - -7 o
H-OH operating conditions, the concentrations of both [H ] and [OH ] tend to 1x10 at 25 C
o
(77 F). These low concentrations provide little driving force for equilibrium leakage so that
levels of sodium in water of less than 2 ppt (ng/kg) have been achieved. In ammonium form
operation, the [OH-] and [NH4+] concentrations are relatively high and at pH 9.6 are about 40x10-6
o o
at 25 C (77 F). This represents an increase of over two orders of magnitude. There is also a
decrease in the selectivity of the ammonium form resin for sodium so that it becomes lower than
+
shown by H form resin. Therefore, to achieve acceptable equilibrium leakage values when
operating in the ammonium form, the level of impurities on the resins must be reduced as far as
reasonably achievable. A guide to the maximum tolerable levels of impurities on resins is given
in Table 4-1. This table, which is based upon at 25oC (77oF) data, is aimed at ensuring that the
in-service equilibrium leakage of sodium or chloride is less than 1 ppb. It also indicates the pH
dependence of these equilibrium leakage estimates.

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Table 4-1
o
Impurity Levels on Cation and Anion Resins to Give 1 ppb Equilibrium Leakage at 25 C
o
(77 F)

pH %Sodium in Cation %Chloride on Anion

Resin Resin

7 (H-OH Form) 42.5 86.1

+
7 (NH Form) 25.8 86.1
+
8 (NH Form) 3.4 38.1
+
9 (NH4 Form) 0.34 5.83
+
9.6 (NH4 Form) 0.087 1.52

Note. Impurity levels on ion exchange resins are conventionally reported in percentage terms.
This refers to the percentage of the ion exchange sites on the resin in the form being discussed,
e.g. sodium or chloride, and not the weight percentage of the impurity on the resin.

The EPRI advised target level for sodium in polished condensate is < 3 ppb. With full flow
condensate polishing significantly lower levels can easily be achieved so that operators often set
their own target at, say, 1 ppb. So, on the assumption that the maximum desirable concentration
of sodium and chloride in polished condensate is 1 ppb and the pH of operation is pH 9.6, resin
purity targets have been suggested. They are less than 0.08% for sodium on cation resins and
less than 1% for chloride on anion resin. These are slightly lower than the 0.087% sodium and
1.52% chloride indicated in Table 4-1 for pH 9.6. At lower pHs they could obviously be relaxed
and the target polished water quality still obtained. However, even the stringent resin qualities
suggested for pH 9.6 are achievable and are conservatively set for guidance and security. For
simplicity, all the following discussions in these Guidelines are, therefore, based upon pH 9.6.
The informed operator may choose to select regeneration targets more pertinent to his own plant
conditions

4.2 Separation

The first problem to be addressed when considering the regeneration of mixed beds is that of
resin separation. Naked mixed beds employ various ratios of cation to anion resin with the most
commonly used ratios being either a 1:1 or a 2:1 cation:anion resin ratio based on
volume:volume ratios but for simplicity the case of a 1:1 mixed bed will be considered. A well
maintained and operated conventional mixed bed separation system using a top sluicing
arrangement to move separated anion resin in to a dedicated regeneration vessel will, without
special care, typically yield separated resins containing between 2-5% of cross contaminating
anion or cation resin. If problems such as the presence of a high percentage of resin fines, or
incorrect volumes of resins in the charges, exist then very serious cross contamination can occur
with over 20% cross contamination being seen in extreme cases. With care, however, cross
contamination as low as 0.3% has been achieved using conventional separation equipment and
very much lower levels by the use of high efficiency separation/regeneration plants.

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Assuming that the separated anion resin contains 2% cation resin then this will be completely
converted to the sodium form during the regeneration of the anion resin. On recombination of
the regenerated anion and cation resins the total sodium content of the cation resin will therefore
consist of this 2% of resin fully in the sodium form, plus sodium originating from other sources.
These other sources include the traces of sodium hydroxide regenerant remaining on the anion
resin itself and traces of sodium not removed from the separated, main charge of cation resin
during its regeneration with sulphuric or hydrochloric acid. The sodium content of the cation
resin will then be 2% plus the contribution from minor sources whilst the target for ammonium
form operation is as low as 0.08%. Clearly if it is a 2:1 mixed bed the cross contamination
contribution is halved but the total sodium contamination is still well above the target for
ammonium operation at pH 9.6. The first obstacle to be overcome is therefore that of separation.

Several designs of high efficiency separation/regeneration plants are on the market and are
discussed in EPRI Condensate Polishing Guidelines, TR-104422 and TR-101942-R1. They
include the effective bottom transfer process that is capable of yielding cation in anion resin
cross contamination below 0.07% but higher anion in cation levels. The process has been in use
on power stations since the early 1980’s and is employed on over 40 plants throughout the world.
It also has the advantage that, unlike the conventional top sluicing separator design, its efficiency
is independent of resin volumes and ratios1, Figure 4-1. Another proprietary design is based on
separation achieved by feeding the mixed resins into an up-flow of water. This process is in use
on one US power station and effective separation is claimed2. A system widely used in Japan is
that of interface isolation employing a conventional separation vessel in which the resins from
the interface zone are isolated as they contain most of the troublesome cross contamination 3,
Figure 4-2. The use of both interface isolation and bottom transfer, together in one process, has
also been successfully used on a nuclear power station4 and the concept is now reported to be
gaining wider use, Figure 4-3.

A very effective, proprietary, density separation procedure using concentrated ammonium

sulphate is in use on one US coal fired station. Auerswald and Cutler5, Figure 4-4 first described
this interesting mixed bed separation process in 1991. It uses concentrated (32%) high-density
solutions of the salt to very efficiently separate resins. Unlike most other separation processes, it
does not depend on terminal falling velocities of the beads, and hence the particle sizes, but
solely on the density of the particles. This enables fines to be separated as well as whole beads.
It also offers a way in which the nominally “non-separating” mixtures of anion and cation resins,
now used for some polishing applications, can be parted. Resin cross contamination levels as
low as 0.05% cation in anion resin and less than 0.02% anion in cation resin have been reported
from a full scale plant using this approach on the 2x800 MWe Mohave Generating Station6. The
resins on this station are, after full regeneration, then operated through into the ammonium form
at pH 9.55 with sodium leakage of 0.1-0.2 ppb and chloride leakage of less than 0.2 ppb being
achieved, Figure 4-5. This is despite the fact that condensate temperatures are as high as 60oC
(140oF). The Mohave polisher regeneration plant is the only installation employing this different
approach to resin separation and has been in service since 1991. The process is obviously
successful, and very effective, but costs of installing and operating the system have not yet been
disclosed.

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Figure 4-1
Bottom transfer separation/regeneration system.

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Figure 4-2
Interface isolation separation/regeneration system.

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Figure 4-3
SCE design of mixed bed separation system.

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Figure 4-4
Ammonium sulphate mixed bed separation system based on resin density differences.

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Figure 4-5
Ammonium form operation—impurity levels at condensate polisher outlet, Mohave Power
Station. Polisher 2S. pH 9.6.

4.3 Resin Cleaning

Ammonium form beds are in service for a considerable period of time normally ranging from 1
to 2 months but which may be as long as 6 months. After a prolonged service run they obviously
need to be thoroughly cleaned of all the particulate corrosion products that has accumulated on
the resin bead surfaces. This material (crud) is primarily iron oxide in one of its many forms or a
mixture of these forms.

Cleaning of condensate polishing resins is normally carried out, on fossil stations, by air
scrubbing and back-washing. EPRI TR-101942 recommends: “the cation vessel should be
drained to a minimum water level of 2 to 3 inches (5 to 7.5 cm) above the resin, and the resin
scrubbed with an air flow of 6.5 to 11.5 scfm/ft2 (2 to 3.5 standard m3 /m2-min) of vessel cross
section area”. Corrosion products are flushed out of the resin during the separation backwash
with water that flows from the bottom to the top of the vessel. Crane Cochrane introduced, many
years ago, a procedure termed the Air Bump Rinse Operation or ABRO as it has become known.

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In this, short bursts of air of approximately 1minute duration, followed by a forced drain down
are repeated until the water leaving the bed is judged to be acceptably clean. Figure 4-6 shows
the results of such a procedure on a resin that had been in ammonium form service for 200 days7.
The iron concentration in water being rinsed from the resins after each cleaning stage is shown as
a stain on the test filter being used.

Other resin cleaning procedures exist such as the ultrasonic cleaner used primarily on BWRs
and, whilst effective, are unlikely on cost grounds to be widely adopted by fossil power stations.
The proprietary Japanese Organo Backwash system is widely used in Japan and employs a side
8
blow and down flow to clean resins . It is claimed to be equal or superior to ultrasonic resin
cleaning systems and is also described in EPRI TR-101942-R1, Figure 4-7.

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Figure 4-6
Cleaning of exhausted ammonium form mixed bed by air scouring and drain-down. Iron in
drain-down water shown by filter stains.

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Figure 4-7
Schematic of Japanese process for resin cleaning.

Fossil stations usually employ the simpler resin cleaning techniques and, largely, appear satisfied
with the results. The problem of iron fouling does, however, occur bringing with it kinetic
response problems. Crud filtration has been intensively studied in relation to BWRs. These
nuclear stations operate their steam water circuits under oxidising conditions thus affecting the
type of iron oxide to be filtered. It has been shown that crud can be held in three ways, loosely
held on the resin surface, tightly adsorbed crud that is difficult to dislodge and crud that has
diffused into the matrix of the bead 9.

The possibility of iron fouling occurring and not being resolved by simple cleaning techniques
must be borne in mind when considering prolonged operation in the ammonium form. Oxide
types will vary depending on whether the fossil station is using conventional reducing conditions
in its steam/water circuit or whether it is using oxygenated treatments. Tarong Power Station,
Australia, reported using repeated air scouring and backwashing operations to clean its resins
after use in the ammonium form on an AVT conditioned system. Despite this “certain resin
charges would actually release crud when placed in service causing short term fouling of
10
downstream valves” . It was found that soaking the resins in 17% hydrochloric acid removed

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60-70% of the crud held by the resin but that the problem soon re-occurred. It is difficult to
generalise about the problem of iron fouling of resins. It appears to be site specific and advice
should be sought if problems do occur.

4.4 Conditions for Regeneration

The next stage of the regeneration process is the elution of impurities from the cation and anion
resins by the use of sulphuric acid and sodium hydroxide. When dealing with mixed beds, this
obviously requires the exhausted ammonium form cation resin to be separated from the anion
resin as effectively as possible and this has already been discussed.

4.4.1 Cation Resin Regeneration

The cation bead resin specification is shown in Table 4-2 (taken from EPRI TR-104422).

Sulphuric Acid

Sulphuric acid is normally employed for the regeneration of cation resin. EPRI Condensate
Polishing Guidelines gives guidance on the conditions of use of sulphuric acid and this is
summarised in Table 4-311. The difficulty of reducing the sodium content of a cation resin to
less than 0.08% increases with its cross linkage as Figure 4-8 shows12. Resins containing 12%
DVB, both gel and macroporous, are the most commonly used in condensate polishing
applications. To reduce sodium levels on resin of these types, down to the 0.08% target given in
Section 4.1, it has been shown necessary to use 800-900 kg sulphuric acid/m3 (50-57 lb/ft3).
Table 4-3 assumes that the resin was fully in the sodium form prior to regeneration and
obviously represents an extreme regeneration situation that will probably only be encountered if,
say, new resins are supplied in the sodium form. In the absence of condenser leaks or other
impurity ingress incidents, resins from ammonium form plants are returned for regeneration
containing only very low levels of sodium7. Figure 4-9 shows the cation resin analysis obtained
on a coal fired drum boiler station before and after a prolonged service run in the ammonium
form at pH 9.6 indicating that the sodium level actually reduced in service. This will not always
be the case but, nevertheless, sodium contamination levels on cation resins after a leak free
service run will not normally be high. Therefore, it is suggested that Table 4-3 is useful as
general guidance for the application of sulphuric acid as a cation resin regenerant. Other workers
have advised different regeneration levels with Salem, in a 1969 paper, advising that 400kg/ m3
(25 lbs/ft3) of sulphuric acid should be used for the regeneration of cation resins for use in
ammonium form beds 13.

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Table 4-2
Cation Bead Resin Specification

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Figure 4-8
Elution of sodium from cation resin.

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Figure 4-9
Impurities on cation resin used in ammonium form condensate polishing, before and after
regeneration.

One of the prime reasons for employing a condensate polishing plant is to provide protection
against condenser leaks. Despite care and good maintenance, leaks occasionally occur and
cation resin will become sodium contaminated. When this happens it is prudent to increase the
sulphuric acid regeneration levels. It is difficult to give more precise advice regarding the action
to be taken. This must depend on the extent of the sodium contamination of the resin and local
conditions. Ideally, resin samples should be taken before and after regeneration and checked for
sodium content by direct analysis or by simplified go-no go tests as discussed in Section 8. The
very least that should be done, after contaminated resins are regenerated and returned to service,
is to closely monitor their behaviour. This allows them to be removed from service should there
be any doubts about their performance.

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Table 4-3
Cation Ion Exchange Resin Regeneration

3
Operation Flowrate, gpm/ft Comment
(BV/h)
3
Application of 4-10% 0.5 to 0.7 Dose: 160 to 190 kg/m
3)
sulphuric acid (4.0 to 5.6) (10 to 12 lb/ft

Acid displacement 0.5 to 0.7 1 bed volume

Fast rinse 2 to 4 Time: 10 min

(16 to 32)

Drain to resin level - -

Air scrub and backwash - Time: 20 min

Fast rinse 2 to 4 Endpoint; 10 to 20 µS/cm

Source: Derived from EPRI Condensate Polishing Guidelines, TR-104422-R1

Hydrochloric Acid

The use of hydrochloric acid for the regeneration of cation resins used in water treatment is well
known. It has advantages in that its use eliminates the risk of calcium sulphate precipitation on
those resins treating water containing this impurity and it is claimed to be useful in maintaining
them free of iron deposits that could affect their kinetic response. It is generally considered to be
a more effective regenerant than sulphuric acid but it suffers disadvantages:-
• it is significantly more expensive in many countries,
• bulk stocks of the 35% acid obviously demand more storage space than the 96- 98%
sulphuric acid commonly used
• storage vessels for hydrochloric acid must be lined to prevent them being attacked although a
variety of linings are now available.

Hydrochloric acid often finds use in smaller water treatment plants with the larger ones, in
industrialised countries, generally opting to use the less costly sulphuric acid. Because of this,
most of the experience reported in the literature relating to condensate polishing refers to the use
of sulphuric acid with power stations using the same acid for the regeneration of cation resins
from make-up demineralisation plants. There are some notable exceptions as hydrochloric acid
is used in Germany, and some of its neighbouring states, although it must be pointed out that
they do not operate polishers in the ammonium form. Power stations in India, and some other
countries in the Asian region, use hydrochloric acid primarily because supplies are more readily
accessible than sulphuric acid. However, it has emerged that when they operating their
condensate polishing plants through into the ammonium form relatively high levels of chloride in
14
polished water are often seen . As a result chloride levels in boiler water are exceeding those
considered safe and acceptable and, within India, advice has been given that condensate

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polishers should not be operated through into the ammonium form when the cation resins have
been regenerated with hydrochloric acid.

Critics of this decision point out that convincing proof that the cause of the problem is the use of
hydrochloric acid has not been established and that other factors, such as the quality of the
sodium hydroxide used for regeneration of the anion resins may be to blame. This may well be a
factor contributing to the high chloride leakage and clearly more information would be
welcomed. However, it can be argued that if, during separation of a typical 2:1 cation:anion
resin ratio mixed bed, 1% of the anion resin remains entrained in the separated cation resin then
this will be fully converted into the chloride form. From this source alone, 2 % of the anion resin
inventory will therefore be placed in the chloride form. When chloride contributions from other
sources are added then the target figure of 1% for chloride on anion resin for operation in the
ammonium form at pH 9.6 is obviously exceeded. Relatively high leakage of chloride will
result, Figures 3-6 and 3-12. This example assumes a reasonably good separation and polishing
plant using the less effective conventional separation systems can expect to see higher levels of
anion in cation cross contamination. Traces of hydrochloric acid also become chemisorbed on to
the cation resin and are difficult to dislodge merely by rinsing. Thus, traces of the hydrochloric
acid used for regeneration of the cation resin are transferred to the anion resin by two routes and
subsequently leak into the final polished water with this leakage being controlled by pH as
described in Section 3.

Anion resins from mixed beds, with the cation resins being regenerated with sulphuric acid,
suffer contamination by the same mechanism. However, the divalent sulphate ion is far more
strongly held by the anion resin than is chloride so that the consequent leakage of sulphate is
acceptably low. Moneypoint Power Station, as already discussed, operates its polishers in the
ammonium form at pH 9.5-9.6. Approximately 20 to 25% of the anion exchange sites of the
resin used in their polishers remained in the sulphate form. Despite this, the concentration of
sulphate in polished water was as low as 0.3 ppb, Figures 3-13 and 4-10. Similar levels of
chloride on the resin would give a chloride leakage of about 16 ppb, at pH 9.6. High levels of
sulphate contamination of the anion resin, although not desirable, can therefore be tolerated but
high levels of chloride cannot.

As already discussed, some power stations use hydrochloric acid, not out of choice but more out
of necessity. Although the Indian experience has not yet been fully investigated or explained, it
does seem likely that the high chloride leakage seen under ammonium form operating conditions
is linked to the use of hydrochloric acid. It would be useful if a way could be found to allow the
continued use of this acid and to be able to satisfactorily operate in the ammonium form and a
possible approach is discussed in Section 8.

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Figure 4-10
Percentage of ion exchange sites on anion resin in chloride, hydroxide, sulphate and
bicarbonate form before and after use in ammonium form polishing.

4.4.2 Other Cation Resin Regenerants

Other reagents for stripping sodium from strongly acidic cation resins have been explored. In
their 1981 paper, Ray, Ball and Parry showed the effectiveness of ammonium sulphate15. Their
results are given in Table 4-4. Using the same experimental conditions as given in this table, the
authors regenerated a macroporous resin containing only 2% of its exchange sites in the sodium
form with 265 kg/m3 (16.5 lbs/ft3) of ammonium sulphate reducing the sodium content to 0.08%.

Ammonium sulphate, as well as effectively stripping sodium, converts the cation resin to the
ammonium form. It could, therefore, be directly used in this state. Obviously, it could also be
converted to the H+ form before return to service and this is what Mohave Generating Station

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chose to do6. The use of pre-ammoniated cation resins has advantages, the main being the
avoidance of the sodium throw that always follows on-line ammoniation. The control of the pH
of the steam/water circuit is simplified. Under normal conditions, the dosage rate of ammonia
will be almost constant, and extremely low, as it will be aimed at simply replacing the minor
losses from the circuit. However, if a condenser leak arises, it is advised that ammonium form
beds be replaced, within a day or two, by resins in the conventional H-OH form. It is therefore
desirable for stations to hold reserves of regenerated cation resin in the H+ form or to have the
+
facilities to convert any ammonium form resins that it has in reserve to the H form. In-service
ammoniation is a simpler approach and is used by the majority of the stations operating their
polishers in the ammonium form. It has been shown to be successful but the use of pre-
ammoniated resins remains an alternative.

During EPRI sponsored work on the use of volatile amines Miller observed that diaminoethane
had an extremely high selectivity for cation resin so that the great majority of any sodium
16
contained by the resin was displaced . This offers another possible approach to stripping sodium
from cation resins with preliminary small scale tests indicating that sodium levels as low as
0.003% could be achieved17.
Table 4-4
Regeneration of Resins with Ammonium Sulphate

Regeneration level Gel Resin Gel resin Macroporous resin

Regeneration level 800 200 265
3
NH4SO4, kg/m (600) (150) (200)
(H2SO4 equivalent
3
kg/m )
Regenerant 5.7 5.7 5.7
concentration, %
(mol/L) (0.5) (0.5) (0.5)
Sites in sodium form 100 100 100
before, %
Sites in sodium form <0.05 2.6 1.3
after, %
Sites in sodium form 0.1 > 10 10
after equivalent
H2SO4 regeneration,
%
Source: N J Ray, M Ball and D J Parry, “Ion Exchange Purification Plant for the Treatment of High pH
Condensate”, Power Industry Research, 1981, 1, pp70-86

4.4.3 Anion Resin Regeneration

Form of Anion Resin Supplied by Manufacturer.

To attain the very low chloride levels demanded for ammonium form operation the strongly
basic anion resins used should be supplied in a low chloride form as shown in Table 4-5 taken

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from EPRI TR-104422. In some countries, or regions, it may be difficult to obtain supplies of
resins in this form. In this situation it is advised that any high chloride content resins should be
treated by converting them completely to either the sulphate or carbonate form. This action
displaces chloride and allows regeneration with sodium hydroxide to be successfully completed.
These procedures are used by resin manufacturers and have been adopted by some power
stations with the results achieved by one station being shown in Figure 4-11. They are further
discussed below.
Table 4-5
Anion Bead Resin Specification

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Figure 4-11
Percentage of ion exchange sites on anion resin in chloride, hydroxide, sulphate and
bicarbonate form after use being sulphated and regenerated.

Removal of Chloride

It is difficult to reduce chloride contamination of anion resins to very low levels, and even more
difficult to remove sulphate, by the use of sodium hydroxide as shown by Figure 4-12. A paper
by Fisher and Otten discusses this problem and points out that the elution efficiency decreases
sharply as the cross linkage increases18. They also note that with sodium hydroxide “the
regeneration of the chloride form of resins used in condensate polishing would be incomplete at
the best”. They added that it “is questionable whether the use of large volumes of caustic in

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plant operation is justified in the light of the volume of waste generated”. Because of this
difficulty, manufacturers have for many years prepared low chloride resins by displacing the
impurity using highly selectivity divalent ions, usually sulphate or carbonate, then removing the
divalent ion by regeneration with sodium hydroxide. Using this approach very low chloride
levels can be obtained with < 0.5% being guaranteed by most manufacturers with levels as low
as 0.1% being achievable.

Figure 4-12
Effect of sodium hydroxide regenerant level on regeneration efficiency of chloride and
sulfate from duolite A161 resin.

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Routine Regeneration of Anion Resins for Ammonium Form Polishers

Anion resin, of a grade suitable for use in regeneration plants associated with condensate
polishers, can therefore be obtained with chloride levels below the target set for ammonium form
operation. In routine ammonium form use, and given the absence of condenser leaks or other
contamination, anion resins do not pick up significant amounts of chloride. Figure 4-10 shows
chloride levels on anion resins before and after a prolonged service run in the ammonium form at
pH 9.6 indicating the low pick-up. The figures also show that a regenerant dosing level of 128
kg/m3 (8 lbs/ft3) of sodium hydroxide on anion resin can still reduce chloride levels as low as
1.5% to about 1%. This apparent effectiveness is interesting and apparently contradicts the
findings of Fisher and Otten18. This experience prompts the conjecture that the presence of
23.5% carbonate on the exhausted resin was a contributory factor to the effective removal of
traces of chloride - even at the low levels involved.

Anion resin regeneration conditions detailed in EPRI TR 101942-R1 are considered suitable for
the regeneration of resins used in ammonium form service provided that they have not been
subjected to a condenser leak. These conditions are given in Table 4-6.
Table 4-6
Anion Ion Exchange Resin Regeneration

Flowrate,
1 3
Operation mh /gpm/ft Comment
(BV/h)
3
Application of 4-8% 0.74 to 1.2/0.3 to 0.5 Dose: 10 to 15 lb/ft
sodium hydroxide
(2.4 to 4.0) (160 to 240 g/l)

Caustic displacement 0.74 to 1.2 /0.3 to 0.5 1 bed volume

Fast rinse 4.9 to 9.8 / 2 to 4 Time: 10 min

(16 to 32)

Drain to resin level - -

Air scrub and backwash - Time: 20 min

Fast rinse 4.9 to 9.8/2 to 4 Endpoint; 5 to 10 µS/cm

4.4.4 Other Anion Regenerants.

As already mentioned other regenerants are employed to displace chloride from strongly basic
anion resins because of the difficulty in removing the final, but important, few percent of this
impurity from the resin. The use of divalent ions such as carbonate and sulphate are well
established being employed by manufacturers and also by power stations seeking to reduce anion
resin chloride levels. As a preliminary to condensate polisher investigations at Aghada
Generating Station, chloride levels on anion resins were successfully reduced to 0.2% by treating
the resin with 5% sodium bicarbonate solution at 500 kg NaHCO3/m3 resin (31 lbs/ft3) followed

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by regeneration with sodium hydroxide19. Resins at Mohave Generating Station are routinely
sulphated during the course of the ammonium sulphate density separation process with the
subsequent chloride leakage levels during ammonium form operation at pH 9.55 indicating the
resin chloride content was about 0.3 %. The residual sulphate content of the resin has not been
reported but is likely to be high with a level of about 20% being guessed on the basis of power
station experience.

One power station wished to convert to ammonium form operation but was troubled by high
chloride levels on its anion resins. This was due to these resins being supplied in the chloride
form and not being adequately regenerated so that high levels of chloride remained. To
overcome this problem the station sulphated the resins by soaking in 5% sulphuric acid overnight
and then, after rinsing down, regenerating with 384 kg of sodium hydroxide/m3 (24 lbs/ft3) of
resin employing a 6% solution. It is claimed that chloride levels on the anion resins of
7
approximately 1% resulted . Figure 4-11. However, anion resins at this station still contained
about 20% sulphate after routine regeneration, presumably as the result of them having been
earlier put completely into the sulphate form. Obviously, sulphating anion resins for chloride
removal does lead to higher than normal sulphate levels persisting on the anion resins. Sulphate
levels could be reduced by the prolonged regeneration with sodium hydroxide. This would, of
course, increase regeneration time and costs and, as there is no evidence that a high level of
sulphate on anion resin leads to seriously increased levels of sulphate leakage, this seems rarely
to be done. The residual sulphate on the anion resin does, however, clearly represent a loss of
available anion exchange capacity.

4.5 Post Regeneration Resin Purification Techniques

4.5.1 Requirement for Post Regeneration Purification

Despite all efforts at achieving the best possible separations of mixed beds some resin cross
contamination still occurs. Anion resin on a 1:1 cation:anion mixed bed may contain about 0.05-
0.07% of cation resin even after a typical separation using a high efficiency separation plant.
This will become completely converted to the sodium form putting the total sodium content of
the resin reasonably close to the target limits even before sodium from other sources is taken into
account. The ammonium sulphate density separation process, as already discussed, produces a
better separation performance yielding as low as 0.02 to 0.05% cross contamination. On the
other hand, with the most carefully operated conventional separators, it is only possible to
achieve about 0.3-1% cation in anion cross contamination with less carefully
maintained/operated plants yielding far worse separations. Thus, in most cases, cross
contamination still represents an unacceptable source of sodium.

The opposite effect arising from anion contamination of cation resin is not of such a great
concern provided sulphuric acid is used as the cation resin regenerant. As already discussed, an
anion in cation resin cross contamination of 2% will, assuming a 1:1 mixed bed, put 2% of the
total anion resin inventory into the sulphate form. High efficiency separation/regeneration plant
should achieve lower cross contamination levels, say, 0.5% anion in cation resin. If the mixed
beds are allowed to stand for about 24 hours before use then these levels of cross contamination
should not yield significantly high levels of sulphate leakage even when operating at the high pH

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levels experienced in ammonium form operation. When hydrochloric acid is used as the cation
resin regenerant this degree of cross contamination could become of concern and, as already
discussed, give rise to an unacceptable leakage of chloride.

Other sources of sodium and sulphate (chloride) arise from the traces of regenerant held by the
separated anion and cation resins despite thorough rinsing. Various ways of dealing with these
last traces of impurities have been devised and these are discussed in detail in EPRI Condensate
Polishing Guidelines11. They include several proprietary processes and some of these are
described below

4.5.2 Ammonia Rinse Process.

This process was originally developed by Crane Cochrane and termed the Ammonex process.
The separated anion resin containing traces of cation resin is treated with a dilute (approximately
0.5%) solution of ammonia for 3 to 10 hours to convert any sodium form resin to the ammonium
form. The ammonia solution is continuously recycled in a loop containing the anion resin being
treated and then through the separated cation resin so as to reduce the sodium it has picked up
and passed through the anion resin again, Figure 4-13. A similar process involves the use of a
calcium hydroxide solution to displace sodium from cation resin entrained in anion resin.

4.5.3 Caustic Flotation Process

This approach was originally developed by the Graver Company and termed the Seprex process.
The separated anion resin is transferred to an anion regeneration vessel in which it is regenerated
with concentrated sodium hydroxide (16 to 20% by weight). This solution has a density such
that the small volume of entrained cation resin sinks to the bottom of the vessel from where it is
removed whilst the anion resin floats to the top of the vessel to be removed and rinsed. The
removal of most of the cross contaminating cation resin leads to a useful reduction in the overall
sodium levels in the final mixed bed. Figure 4-14

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Figure 4-13
®
Ammonia rinse (Ammonex ) regeneration process.

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Figure 4-14
®
Seprex regeneration process.

4.5.4 Resin on Resin

The procedure originated in South Africa in the mid-1970’s. It was originally designed to reduce
the problem of enhanced sodium leakage arising from the level of cross contamination from
conventional mixed bed separation systems, i.e. the top anion resin sluicing design. Resins are
first separated as effectively as possible and the cation or anion resins transferred to its own
regeneration vessel. The anion resin, containing the inevitable traces of cation resin, is

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regenerated and rinsed in the normal way. Any entrained cation resin will, of course, be fully
converted to the sodium form in this process. The regenerated anion resin (including the
entrained cation resin) is transferred back to the cation regeneration vessel and air mixed with the
cation resin that is still awaiting regeneration. After standing the remixed resin for several hours,
with periodic air mixing, they are separated. The cation resin is then regenerated and rinsed in
the normal way before being recombined with the anion resin for a final rinse before service.

This non-proprietary procedure significantly reduces the sodium contamination of the final
mixed bed. Its use requires that the regeneration plant should have the necessary connections to
allow the separated and regenerated anion resin to be re-mixed with the cation resin. Estimates of
its effectiveness obviously vary depending on the conditions under which it was employed. One
fossil power station estimates that it reduces the sodium originating from cross contamination by
a factor of 10 thus correcting for less than perfect separation7. The procedure has been adopted
by many PWRs to allow then to achieve very low sodium leakage when operating in the H-OH
form. Reports from these stations are positive with a typical comment being that it has allowed
them to reduce their “sodium values to an acceptable level with essentially zero cost with the
exception of a bit of time”. The mechanisms by which it works are broadly understood but
20
require further study so as to optimise the procedure , Figure 4-15.

4.6 Other Techniques

4.6.1 Soaking Resins in Regenerants

It has been claimed that improved regeneration of resins, without increasing the level or
concentration of regenerants used, can be achieved by simply soaking cation or anion resins in
regenerant solutions overnight7, 21.

4.6.2 Soaking Regenerated Resins in High Purity Water

The traces of anion resin present in separated cation resin, owing to cross contamination, will
become fully sulphated. The functional groups of these entrained anion resin beads will mainly
be strongly basic and, under the acidic conditions of regeneration, will take up sulphate as the
bisulphate. During rinsing, the pH of the water phase obviously falls and the bisulphate groups
start to rearrange to the divalent sulphate so occupying two exchange sites instead of just one and
thereby releasing some sulphate. The rinsing of the separated cation resin is rarely taken to
completion so that when it is re-mixed with the regenerated and rinsed anion resin it carries back
a small percentage of anion resin still in the bisulphate form. This continues to release sulphate
when the mixed bed enters service and the large volume of fully regenerated anion resin with
which it has been mixed largely takes this up. However, some sulphate escapes possibly owing
to a small number of bi-sulphated anion beads being close to the bottom of the bed and/or due to
the kinetic response of the OH form anion being impaired.

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Figure 4-15
Resin-on-resin regeneration procedure.

There are other possible leakage routes that can explain the low level input of sulphate into a
mixed bed and its subsequent escape at ultra-trace levels. These include the contribution made
by any weakly basic anion groups present on the small percentage of anion resin entrained in the
cation resin. The effects of these minor sources of sulphate can be significantly reduced by
soaking the resin in high purity water after regeneration and rinsing and/or standing the final
mixed bed for about 24 hours and then rinsing again before it is returned to service. Figure 4-16

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shows the effects of returning mixed beds to service immediately after regeneration and also
after allowing them to stand for 5 days22. The benefit of resting a freshly regenerated bed is, in
fact, largely realised in an overnight or 24 hour standing period. Given the relative infrequency
of regenerations when operating in the ammonium mode these standing times both for the
individual resins and the recombined mixed beds should not cause any problems.

Figure 4-16
Sulphate washout during return to service of regenerated mixed beds—comparing
behavior of beds used without standing and beds allowed to rest for 5 days.

4.7 Regenerant Quality

4.7.1 Need for High Purity Regenerants

Resins intended for use in condensate polishers operating in the ammonium form must, as
already pointed out, be highly regenerated. To achieve the proposed target levels of sodium and
chloride of < 0.08% sodium on cation resin and <1% chloride on anion resin for operation at pH
9.6, it is necessary to use sufficiently pure regenerants. This is because the resins will, as in all
ion exchange processes, reach an equilibrium with the impurities in the regenerant being used.

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This obviously implies care being taken over both the quality of the concentrated regenerant and
over the dilution and rinse water qualities.

4.7.2 Quality of Sulphuric Acid

In most industrialised countries few problems seem to occur in obtaining a satisfactory grade of
sulphuric acid or hydrochloric acid. For condensate polishing use it is suggested that the
impurities of importance are primarily sodium and iron and Table 4-7 gives a specification that
will act as a guide. It is worth noting that acid of sufficient quality to meet these proposed
requirements will also, normally, contain very low levels of other impurities. This can be seen
from the detailed specifications for high quality sulphuric and hydrochloric acids provided by
manufacturers
Table 4-7
Sulphuric Acid Regenerant Specifications

Constituent Weight Concentration

Sulphuric Acid as H2SO4 Greater than 93%

Iron as Fe Less than 50 ppm

Chloride as HCl Less than 20 ppm

Sodium as Na Less than 50 ppm

Appearance Colourless and clear

Suspended Solids None

Source: Condensate Polishing Guidelines for PWR and BWR Plants, EPRI TR101942-1997 Revision

4.7.3 Quality of Sodium Hydroxide

When considering the use of sodium hydroxide as a regenerant for high purity water, the
impurity of most concern is clearly chloride. There are two main processes of manufacture, the
older mercury cell process and the newer diaphragm cell process. The mercury cell is used to
prepare a very pure grade of sodium hydroxide often described as being of “rayon grade” with,
for example, the 50% w/w solutions of this chemical containing < 50 ppm of sodium chloride
with levels in some supplies being even lower. Simple calculations show that chloride impurities
in the sodium hydroxide regenerant will themselves impart unacceptable levels of chloride to the
resin. Thus, very approximately, a 4% NaOH solution prepared from a bulk 50% solution
containing about 330 ppm NaCl (200 ppm Cl-) will be at equilibrium with an anion resin
containing 1% of the anion exchange sites in the chloride form. This means that the chloride
levels on an anion resin, when regenerated with this sodium hydroxide, cannot be reduced below
1% as the chloride content of the sodium hydroxide controls the final equilibrium level. Thus,
supplies of sodium hydroxide containing more than 300 ppm of sodium chloride are not suitable.

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The sodium chloride content of “rayon grade” sodium hydroxide is very much lower so that it is
clearly an acceptable grade of regenerant.

Unfortunately diaphragm cell grades of sodium hydroxide are frequently more easily available
but can contain 10,000-20,000 ppm of sodium chloride and so are completely unacceptable. The
problem of sodium hydroxide quality is even more severe in developing countries with a recent
paper reporting that in one instance supplies of 30% sodium hydroxide contained 4.4% sodium
chloride23.

Diaphragm cell sodium hydroxide can be further purified by techniques such as treatment with
ammonia and the acceptability of these products depends completely on their sodium chloride
levels. Table 4-8 is a guide to the relationship between chloride in the concentrated sodium
hydroxide (50% w/w) and the equilibrium level of chloride on anion resins that results from its
use as a regenerant. A selectivity coefficient of K Cl
OH =22, the use of a 1 M solution (4% sodium
hydroxide) are assumed together with the simplification that the hydroxide concentration in the 1
M regenerant is unity, i.e. [OH-] = 1.

Table 4-8
Guide to the Relationship Between Chloride in Bulk Sodium Hydroxide and the Resultant
Anion Resin Levels

Chloride Content of 50% Sodium Hydroxide, Chloride Content of Anion Resin

- -
Cl ppm Cl %

50 0.25

100 0.49

150 0.74

200 0.99

300 1.46

500 2.42

1000 4.72

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4.8 Regeneration of Resins From Other Designs of Condensate Polishing

Plants

4.8.1 Cation-Mixed Bed Plants

The use of plants of this design in the ammonium form is not common practice. They clearly
have a higher capital cost than naked mixed bed plants and are usually chosen to suit specific
operating requirements and are usually intended to operate in the H-OH mode so as to provide a
very high quality polished water for nuclear steam generating plant. The fact that they employ a
far higher volume of cation resin means that they are well suited for H-OH mode operation even
at high ammonia levels, i.e. high pHs. Nevertheless, it can be argued that the design has some
advantages, in addition to the obvious ones of operating economy, for ammonium form operation
on those stations, such as fossil fired plants, able to accept the reduced quality of water so
produced. The lead cation bed will filter crud thus protecting the mixed bed resins from fouling
and can be cleaned and, if necessary, regenerated independently of the mixed bed. Conditions
for its regeneration will be the same as those for cation resins already discussed. The frequency
of regeneration of the mixed bed can be lower than that of the lead cation bed and be carried out,
for example, every third or fourth cation bed regeneration although this will depend on the anion
impurity loading. The approach adopted for mixed bed regeneration will be exactly the same as
previously discussed. In the event of a persistent, steady state, condenser leak the available
cation exchange capacity will still be higher than a naked mixed bed could offer. However, the
overall plant capacity will be limited by the usable anion exchange capacity and so will not
generally be greater than that of a naked mixed bed plant although a higher anion: cation mix
could be adopted say 1:2 cation: anion resin v/v. In the presence of an intermittent leak the
sodium throw effect will be delayed owing to the increased cation resin inventory but, as has
been pointed out, the height of the peak could be higher – as there is more cation resin, there is
24
simply more sodium to sweep out .

4.8.2 Separate Bed Plants

This design of plant is well suited to ammonium form operation but, again, suffers the
disadvantages that its capital cost is greater than that of a simple mixed bed. Usually it consists
of a train of separate service vessels containing cation-anion-cation resins. In Australia and
Singapore a proprietary stacked bed system is used employing layers of cation-anion and cation
resin contained in a single shell. Some power stations in South Africa use a simple two-bed
system with a cation bed followed by a second vessel containing anion resin. The separated bed
design has the advantage that the regeneration of resins is simpler as cross contamination
problems do not arise. The migration of resin fines from one bed to another remains a possibility
but, as yet, operators of separate bed plants have not reported that it actually occurs to a
significant extent. As with the cation-mixed bed design, the lead cation bed also acts as a crud
filter and can be regenerated and cleaned as frequently as necessary. The regeneration of all
three beds should follow the general procedures, and attain the same targets for residual levels of
impurities, as outlined for resins used in mixed bed plants. However, there is an even more
pressing case to ensure that the final cation bed is well regenerated and rinsed as any anion
impurities that it releases will pass directly into the steam/water circuit. Separate bed polishing
plants are successfully operated in the ammonium form in both Australia and South Africa.

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4.9 Off-Site Contractor Regeneration

The long service runs of ammonium form polishing beds lead to the possibility that off-site
regeneration services can be used with contractors collecting resins for regeneration and
returning cleaned and regenerated resins. Theoretically, this approach has the following
advantages:
• it eliminates the need for a power station to provide a regeneration plant and its associated
chemical storage and effluent disposal facilities
• it saves operator time in relieving them of the task of regenerating resins
• the contractor could also provide the resins used. This would eliminate the need for a power
station to purchase ion exchange resins, monitor their condition and arrange replacement
resins.
• the specialist contractors assume the responsibility of regenerating resins to the very
demanding levels required for ammonium form operation

This approach is known to be in use by one major US utility and EPRI is currently preparing
Guidelines to assist any station interested in adopting off-site regeneration. EPRI TR-104422
contains an early review and costing of off-site regeneration that shows it could be useful for
stations using ammonium form operation.

4.10 References

1. J. R. Emmett and P. M. Grainger, “Ion Exchange Mechanisms in Condensate Polishing”,

Proceedings of the 40th International Water Conference”, Engineers’ Society of Western
Pennsylvania, 1979.

2. S. C. Foor and G. Bachman, “New Advances in Resin Separation Technology for Deep Bed
Condensate Polishing”, Proceedings of the EPRI Workshop on Condensate Polishing and
Water Purification in the Steam Cycle, Scottsdale, Arizona, 1991.

3. H. Kusanao and K. Nawata, “Condensate Polishing in Japanese PWRs”, Proceedings of

EPRI Workshop on Condensate Polishing, Chicago, USA, 1987.

4. D. C. Auerswald, “San Onofre Nuclear Generating Station Polisher System, Performance and
Impact on Steam Generator Chemistry”, Proceedings of EPRI Condensate Polishing
Workshop, Chicago, USA, 1987.

5. D. C. Auerswald and F. M. Cutler, “A New Approach for Mixed Bed Resin Separation,
Cleaning and Regeneration”, Proceedings of the EPRI Workshop on Condensate Polishing
and Water Purification, Scottsdale, Arizona, USA, 1991.

6. P. S. Meyers, “The Amsep Process at Mohave Generating Station”, Proceedings of the EPRI
Condensate Polishing Workshop on Deep Bed and Powdered Resin Systems, Vol. 2, Part B,
New Orleans, Louisiana, USA, 1993.

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7. F. McCarthy and G. O’Connor, “Ammonium Form Operation of Condensate Polishing Plant

for Long Periods in High pH Systems at Moneypoint Power Station”, Proceedings of the
52nd International Water Conference, Engineers’ Society of Western Pennsylvania,1992.

8. J. F. Gianelli et al, “Condensate Polishing, BWR Condensate Polishers Resin Cleaning

Method :Japanese Technology for a US Retrofit”, Ultrapure Water, March 1995. 9.

9. Takeshi Izumi et al, Crud Removal Characteristics of Newly Developed Ion Exchange
th
Resins, Proceedings of the 54 International Water Conference, Engineers’ Society of
Western Pennsylvania, 1993.

10. D. Gunn L. Lloyd and F. Roberts, “Ammonium Cycle Condensate Polishing at Tarong
Power Station”, CEPSI, Jakarta, Indonesia, 1989.

11. EPRI Condensate Polishing Guidelines for PWR and BWR Plants, TR-101942-R, 1997
Revision 1

12. J. R. Emmett and P M Grainger, “Ion Exchange Mechanisms in Condensate Polishing”,

Proceedings of the 39th. International Water Conference, Engineers’ Society of Western
Pennsylvania,1979.

13. E. Salem, “A Study of the Chemical and Physical Characteristics of Ion Exchange Media”,
Proceedings of the American Power Conference, Engineers’ Society of Western
Pennsylvania, 1969.

14. Proceedings of Workshop on Operational Problems of Condenser Polishing Unit, National

Thermal Power Corporation Ltd, Korba, August 2000

15. N. J. Ray, M. Ball and D. J. Parry, “Ion Exchange Purification Plant for the Treatment of
High pH Condensate”, Power Industry Research, 1981, 1, pp79-85

16. A. D. Miller, Effects of Alternate Amines on Deep Bed Condensate Polishers, Proceedings
of the: EPRI Workshop on the Use of Amines in Conditioning Steam/Water Cycles,
September, 1993.

17. M. A. Sadler, H. R. Bolton and E. K. Bullas, “PPQ Water – The Next Challenge!”,
Proceedings of the 52nd International Water Conference, Engineers’ Society of Western
Pennsylvania,1992.

18. S. Fisher and G. Otten, “Are All Type 1 Strong Base Anion Resins Chemically Equal in their
th
Ability to Polish Condensate?”, Proceedings of the 50 International Water Conference,
Engineers’ Society of Western Pennsylvania,1989.

19. D. J. O’Sullivan, P. Powell, H. R. Bolton, E. K. Bullas and M. A. Sadler, “Regeneration of

Condensate Polishing Plant Resins by the Use of the “Resin on Resin” Technique at Aghada
Generating Station”, Ion Exchange Developments, Royal Soc. Chem., Cambridge, UK. 1996.

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20. M. A. Sadler, “The Resin on Resin Technique”, Proceedings of EPRI: Workshop on

Condensate Polishing, 1998, EPRI Report TR-109568.

21. L. Crone, “Experience with Boric Acid Treatment and Condensate Polishing at Millstone 2”,
Proceedings of the EPRI Condensate Polishing Workshop 1991.

22. D. J. O’Sullivan and E. F. McCarthy, “A Review of Condensate Polishing Plant Operation in

the Electricity Supply Board of Ireland”, Proceedings of the EPRI Fifth International Cycle
Chemistry in Fossil Plants, Charlotte, NC, 1997

23. Zhang Chenxin and Chen Long, “The Special Problems Might Be Encountered with the
Operation of Condensate Polishing Systems in China”, Proceedings of the International
Water Conference, Engineers’ Society of Western Pennsylvania, 1998.

24. G. Foutch and E. Zecchini, “Sodium Throw in Mixed Bed Ion Exchange”, Ultrapure Water,
November, 1991.

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5
THE SELECTION OF POWER STATIONS FOR
AMMONIUM FORM OPERATION OF THEIR
CONDENSATE POLISHING PLANTS

5.1 Objective

Ammonium form operation of polishing plants cannot be used to advantage by all power
stations. This Section discusses the aspects of power station design and experience that should
be considered before any utility or power station attempts to operate in the ammonium form. Its
objective is to assist stations to decide whether they can usefully and safely operate polishers in
this economical mode. A “road map” to assist in the decision making process is provided.

5.2 Roadmap to Assist Decision Whether to Operate Polishers in the

Ammonium Form

As already discussed, the factors to be taken into account in determining whether a station should
operate in the ammonium form are:
• pH in the steam/water circuit
• Frequency of condenser leaks
• Frequency of start-up/shut downs
• Local restraints on the discharge of ammonia containing effluents or, indeed, any ion
exchange resin regenerant effluents
• Ability to regenerate resins to the required degree. This includes consideration of access to
supplies of sodium hydroxide of the adequate purity and whether sulphuric acid or
hydrochloric acid is used as the cation resin regenerant. The availability of off-site
regeneration services must also be considered
• Chemical instrumentation and its reporting and alarm systems
• Condition of the ion exchange resins in terms of kinetic response, other degradation such as
increased weak base content of the anion resin and physically damaged resin beads
• Ammonia dosing and control systems – are they sufficiently sensitive to adjust to variations
in the demand for ammonia in order to maintain a stable pH in the steam/water circuit

Not all fossil power stations can usefully operate their condensate polishing plants in the
ammonium form and, of those that can, not all wish to do so. One of the stations whose

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The Selection of Power Stations for Ammonium Form Operation of their Condensate Polishing Plants

experiences have been used in these Guidelines, to show how effective ammonium form
operation can be, in fact decided after several years of operating its polishers in the ammonium
form to revert to conventional H-OH form polishing. This was because its management
considered that the superior polished water quality offered by the conventional process offered
greater security.

It is relatively easy to identify and advise on the suitability of the plant for use in the ammonium
form but it is obviously not possible to advise on the suitability of operators. The successful use
of the process on some stations that would at first sight fail to meet the criteria set out in this
document, such as regeneration facilities, is mainly due to the interest and motivation of the staff
involved. Thus, the final decision whether to adopt ammonium form operation should depend
upon local conditions. The availability of interested, trained and motivated staff is, of course, a
very important consideration. With the development of off-site regeneration services and
computer based expert systems, dependence on trained manpower may be reduced but it will still
be an important factor.

Figure 5-1 sets out a simple roadmap to aid the decision of whether ammonium form operation
could be safely and economically used by a power station.

5.3 The pH of Condensate and Feedwater

Ammonium form operation can be applied to virtually any steam water cycle employing
ammonia as the sole volatile pH conditioning agent. Hydrazine is conventionally used, together
with ammonia, for removal of oxygen and should not present difficulties as it is almost
completely decomposed within the steam/water circuit. Within the range normally employed,
the successful use of ammonium form operation does not depend on the pH of operation.
However, the pH to which the water in the steam/water is conditioned with ammonia is
important as it is a guide to the advantage that may be gained from operating in the ammonium
form. This can be seen from simple calculations, shown in Table 5-1, of the run length of an H-
OH form bed to ammonia break-though in the absence of condenser leaks. These are based upon
the design of a retrofitted naked mixed bed polisher as detailed in EPRI Condensate Polishing
Guidelines, TR-104422. The design assumes a bed throughput of 534 m3/h (2350 gpm) and a
cation resin volume of 2.55m3 (90 cubic feet). The data given in Table 5-1 serves as an indication
of the sensitivity of the run length to the pH of the condensate being treated. Obviously the
actual run lengths will depend on the design used and in particular on factors such as flow rate,
resin volumes and regeneration levels.

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Figure 5-1
Road Map for Deciding Whether Ammonium Form Operation is Suitable for Stations and
Steps in its Adoption

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Table 5-1
Run Length of Cation Resin in a Typical Condensate Polisher to Ammonium Breakthrough

pH Bed Life, Days, To Bed Regenerations per

Ammonium Break Year

8.0 242 1 to 2

8.5 52.8 7

9.0 12.7 29

9.2 6.4 57

9.4 3.2 114

9.6 1.5 243

In deciding whether a plant is suitable for operation in the ammonium form consideration must
be given to local conditions. These will obviously play an important part and are discussed
below together with other constraints. When operating in the ammonium form, regenerations/bed
will probably be reduced to about twelve or less per year and this frequency must be compared
with predicted run lengths of a typical H-OH form bed given in Table 5-1. From this table it can
be seen that the pH at which ammonium form operation generally starts to become attractive is
about pH 9.2. However, this will be strongly influenced by local and other factors.

5.4 Frequency of Condenser Leaks and Other Impurity Ingress Incidents

In the presence of a constant input of sodium at steady pH, ammonium form beds successfully
remove the influent impurity as computer models demonstrate1, Figure 3-10. The run lengths to
a 2 ppb sodium breakthrough can in fact be longer, under some pH conditions and sodium input
levels, than those to be expected from an H-OH form bed. This is simply because the latter is
being exhausted primarily by ammonia with the additional load of sodium input and, in contrast,
ammonium form beds are simply removing sodium, Table 5-2.

Thus, the capacity of ammonium form beds to remove influent sodium under steady state
conditions is not a problem. In low to moderate in-leakage situations, depending on pH, it can
exceed that of H-OH form beds. It is certainly large enough to protect the steam water cycle
from the effects of condenser leaks of the size typically encountered and to provide time for a
controlled shut down in the face of massive in-leakage.

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Table 5-2
Indication of Run Lengths of Condensate Polishers in the H-OH Mode and in the
Ammonium Form, pH 9.6

H-OH Form Operation at pH

9.6, Time to 0.1 2S/cm Ammonium Form
Specific Conductivity Operation at pH 9.6 Time to
Sodium In Influent, Endpoint 2 ppb Sodium Endpoint,

ppb Hours Hours

10 38 106

100 37 66

500 33 48

1000 28 40

The recommended action to be taken by an operator of an ammonium form polisher when faced
with a condenser leak is to remove the contaminated polisher beds from service and replace them
with H-OH form beds. This requires that H+ form resins should be available for use within a day
or two of leaks developing. However, if condenser leaks occur too frequently on a particular
power station then the use of polishers in the ammonium form must be called into question.
Every power station must review its own particular circumstances taking into account factors
such as the delay before a sodium throw occurs after a short term leak or other impurity ingress,
the extent and quality of their instrumentation, number of boiler/turbine units and staff
availability. Nevertheless, the general advice given to a station experiencing frequent condenser
leaks is that the safest course of action is to operate its polishers in the conventional H-OH mode.

The above advice is clear but the difficulty lies in defining what constitutes “frequent” condenser
leaks. General guidance is given in Table 5-3 and suggests that units with a condenser leak
frequency of one every three months are unsuited for ammonium form operation. It is dubious
whether those with a frequency of one leak/six month period should operate in this mode with
the suitability of any unit then increasing with the decreasing leak frequency.

Condenser leaks represent the most common route for impurities to enter a steam/water circuit.
Other routes, such as contaminated drains, do exist and should be one of the local factors taken
into account.

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Table 5-3
Frequency of Condenser Leaks and Acceptability for Ammonium Form Operation

Condenser Leaks/Generating Unit Acceptability for Ammonium Form

Operation

> 1 Leak/3 Month Period Unacceptable

1 Leak every 3-6 Months Doubtful, Consider With Regard to Local

Conditions

1 Leak every 6-12 Months Possible, Consider With Regard to Local

Conditions

Less Than 1 Leak/12 Month Period Suitable

5.5 The Frequency of Unit Start Ups

Condensate polishers are particularly useful during the start up of units as they can significantly
shorten the time needed to bring a unit on-load thus making savings in water and also, in some
cases, in the more expensive light-up oil. The ability to be able to programme the return to load
of a unit with the possibility of a “hold” for condensate quality reasons being minimised makes
condensate polishing a useful operational tool. However, the water in condenser hotwells after a
shut down is frequently heavily contaminated with crud and with ionic impurities that have
entered by various routes during the period off-load. If this water is passed to an ammonium
form condensate polisher it will contaminate these resins so leading to a shorter operational cycle
and effectively to a waste of ammonia and therefore money. It is also alleged that ammonium
form resins are not as effective as H-OH form resin in filtering crud although plant evidence for
this is lacking.

Because of these reasons, condensate polishing plants that are normally operated in the
ammonium form are nearly always used in the H-OH form for start-ups. It is often difficult to
assess the degree of contamination to which these beds have been subjected. It is, therefore, good
practice to change them, when steady state conditions have been achieved. The fresh beds are
then allowed to ammoniate in service for subsequent operation in the ammonium form. It is not
impossible to use ammonium form resins at start-up but it is simply not convenient or economic
to do so. Thus, it is advised that units that are two shifting should not, as a general rule, employ
ammonium form operation of their polishers. The beds would not be in service long enough to
ammoniate and the alternative of using pre-ammoniation could be costly. Furthermore, the beds
would probably become heavily crud contaminated and would pick-up ionic impurities that
would result in a gradual deterioration of polished water quality or even be thrown unexpectedly.

5.6 Chemical Instrumentation and Testing of Condensate Polisher Systems

Continuous surveillance of conditions in the steam/water circuit is desirable on any design of

power station and advice on the minimum level of instrumentation is given in several EPRI

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Guidelines. Continuous monitoring of ammonium form condensate polishing beds is particularly

important for operation in this mode as it allows on-line ammoniation to be managed, early
warning of effects such as possible sodium throw to be obtained and generally provides
information on polished condensate quality. The basic instrumentation required is very simple
consisting of cation conductivity and sodium measurements of condensate entering and leaving
the polishers. This is the same as recommended in the EPRI Guidelines dealing with fossil
power stations as Figure 5-2 shows.

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Figure 5-2
Cycle chemistry diagram for a drum unit on all-volatile treatment (plants with reheat)—core parameters only.

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The inlet sodium instruments measure the sodium being loaded onto the bed so giving warning
of, under certain conditions, possible future throws of the impurity. Similarly, the cation
conductivity measurements give an indication of the anionic load on the polishers which under
normal, condenser leak free conditions will be mainly carbon dioxide and volatile organic acids
such as acetic and formic acid. Under these conditions the levels of carbon dioxide are of
particular interest as under condenser leak free conditions they form the main anion impurity
load. Direct, continuous, measurement of trace levels of carbon dioxide is possible but these
instruments are not often used.2,3. However, an approximate guide can be obtained from cation
conductivity measurements with a nominal correction being made for the effects of organic acids
based on grab sample measurements using ion chromatography.

The sodium and cation conductivity instruments at the outlet of the polishing plant warn against
deterioration in the polished water quality by measuring impurity levels and, more importantly,
indicate trends. The simple addition of a specific conductivity measurement at both the inlet and
outlet would be useful in indicating ammonia levels or, in the presence of in-leakage, provide
confirmation of the extent of the leak. Pressure drops across the individual beds should also be
continuously measured and recorded and the mass flow and throughput related to each bed
should be measured and recorded. Thus, for ammonium form operation the addition of specific
conductivity instrumentation before and after the polishers, together with pressure drop
instrumentation, is advised.

This chemical information should be clearly displayed and recorded, with appropriate alarm
settings in the control room and/or water treatment plant control room. Ideally, all of this
information should be supplied to an “expert” chemical control computer system arranged to
give early notice of any deterioration in bed performance and condition. This information should
include estimates of the total sodium accumulated on the cation resin (hence early warning of
possible sodium throws) and estimates of the level of carbonate on anion resins. In addition,
pressure drops of the various beds should be monitored and alarmed.

Routine grab sampling and analysis for both common cation and anions should back indications
from these simple and reliable instruments. These analyses should include ion chromatographic
tests for ammonia, sodium, chloride, sulphate, acetic acid and formic acid. It is to be noted that
high levels of carbon dioxide and/or organic acids are, at the least, a nuisance when operating in
the ammonium form. They can usually be minimised by improved make-up water procedures.
Continuous monitoring for carbon dioxide could be considered by stations particularly troubled
by this impurity.

Routine total iron measurements in and out of the mixed beds are useful as a measure of the
filtration efficiency of the beds. They also act as a guide to the rate of build-up of crud on the
resins with the results supporting pressure drop measurements. These could be backed by
periodic special sampling exercises under start-up, steady state and shut-down conditions in
which simpler iron analysis procedures could be used for at least some of the more highly crud
contaminated samples.

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5.7 Operation of Ammonium Form Condensate Polishing Plants

Any form of condensate polishing benefits from the attention of informed, interested and
motivated operators. This is particularly true of polishers operated in the ammonium form.
Currently, within the power industry, conventional fossil plants are facing severe competition
from nuclear power stations, co-generators and the more thermally efficient CCGTs. Staff
numbers are generally falling and with them the number of operators on a station conversant
with ion exchange processes. Ammonium form operation does generally demand more attention
than conventional H-OH form polishing and this is most necessary during operational transients.
On the other hand the long periods of several months between regenerations, relative to the few
days when operating in the H-OH mode, leads to a saving in effort as shown by Figure 5-3. This
figure shows the economies achieved on a 3x300 MWe drum station in 1990/914.

Figure 5-3
Moneypoint Generating Station: ammonium form operation annual cost savings.

5.8 Differences Between Conventional H-OH Mode Condensate Polishing

and Ammonium Form Operation

In considering whether to operate polishing plant in the ammonium form rather than in the
conventional H-OH form it is useful to review the advantages and disadvantages discussed in
Section 2. The theory and practice of operating in the H-OH form is relatively simple. Resins
remain in service until a pre-selected bed life of 2-10 days, or even more depending on the pH of
operation, is achieved. During this time they act as reasonably effective filters removing 50-90%

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of particulate impurities, the efficiency falling with influent levels of particulates, and the
majority of all ionic impurities including the very weakly dissociated impurities such as silica.
From a well designed and operated H-OH form mixed bed, with resins in good chemical, kinetic
and physical condition, leakage levels of impurities below 1 ppb, and as low as 0.01 ppb, are
obtained. Impurities once removed are securely held on the resins provided the resins are
removed from service before break-though of ammonia or other influent impurity occurs.
Monitoring of polisher beds operating in the H-OH mode is simple. They are producing
essentially pure water so that any leakage of ionic impurities, above levels considered normal
and acceptable, signifies either that the beds have exhausted or that a problem has occurred. Any
power station, fossil or nuclear, irrespective of design or operating pattern can employ H-OH
form polishing assuming that it is equipped with deep bed polishers.

The main attraction of operating condensate polishing plants in the ammonium form is that the
beds enjoy, in the absence of condenser leaks or frequent shut down/start-ups, significantly
longer service runs. Run lengths of one to two months are common with a few stations claiming
run lengths of up to 6 months. Significant savings in terms of regenerant chemicals, water and
manpower are achieved. However, not all power stations can sensibly or usefully employ
ammonium form polishing. Nuclear power stations such as the main type of pressurised water
reactors, with recirculating steam generators, cannot use ammonium form operation as it will not
yield the quality of polished water that they demand. As already pointed out, fossil stations
suffering frequent condenser leaks and/or frequent start-ups are unlikely to benefit from its use.
Its employment also demand that the resins used be very highly regenerated and this dictates the
provision of an effective regeneration plant or the use of competent off-site contractor
regeneration services.

The behaviour of ammonium form polishing plants towards impurities is complex as has been
detailed in these Guidelines. AFO polishers can and routinely do, comfortably meet the desired
targets for polished water quality with leakage levels of sodium, sulphate and chloride of less
that 0.3 ppb being achieved even from polishers operating at pH 9.6. Most ammonium form
polishers are allowed to ammoniate on-line and this causes a disturbance to the polished water
levels. They will remove influent impurities, both particulate and ionic, from condensate so
offering full protection to the steam/water circuit. However, in contrast to beds operating in the
H-OH mode, the ionic impurities can subsequently be released if chemical conditions change
such as the pH increasing or influent levels falling.

In summary, ammonium form polishing is not suitable for all power plants but can be used by
some with significant economies being made. Even on these, its successful use demand that the
operators be well aware of the fact that the characteristics of ammonium form operation are very
different from those of conventional H-OH beds. It is believed that improvements can be made
to simplify its use on those power stations for which it is judged suitable and these are discussed
in Section 7.

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5.9 The Suitability of Different Types of Condensate Polishing Plant for

Operation in the Ammonium Form

5.9.1 Separate Bed Plants.

Separate bed condensate polishing plants, employing deep beds in separate vessels are
commonly used in Germany5. Although these are well suited to being used in the ammonium
form, German operators prefer to run in the H-OH form. A proprietary design of separate bed
plant employs layers of cation-anion-cation resins in individual compartments contained in one
vessel6. The design is successfully used in Australia and Singapore and on some stations they are
operated in the ammonium form. Figure 5-4

Figure 5-4
Tripol service vessel diagrammatic internal arrangement.

Satisfactory experience in the use of separate bed polishers operated in the ammonium form has
also been reported from South Africa. Eskom, the state owned power utility, has operated
cation-anion type separate bed polishing plants at 3 large coal fired stations (6x600 MWe) for a
many years7. Fifteen of these units employ air cooled condensers and three use water cooled
condensers8. Experience has, therefore, shown that separate bed polishers are well suited to
ammonium form operation on fossil power stations. This assumes adequate care to minimise the

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possibility of resin fines transport, both by design and maintenance of the vessels, and in
thoroughly washing resins after regeneration.

5.9.2 Mixed Bed Condensate Polishers

The mixed bed condensate polisher is the most commonly used design as it is both effective and
has the lowest capital cost of any of the deep bed designs. A few have the protection of a
preceding filtration stage and the advantages of this in protecting the bed from iron fouling will
not be lost if ammonium form operation is adopted. The great majority of the plant experience
of operating in the ammonium form has been obtained on naked mixed bed plants so there can be
no room to doubt that they can be successfully used in this way. The most critical requirement is
that they must have the ability to regenerate resins to the very high degree required, i.e. the
sodium on cation resins reduced to <0.08% and the chloride on anion resins to <1.0%. They must
obviously be free of problems such as difficulties in moving resins to and from vessels as this
will affect their ability to regenerate. This, and other issues involved in resin regeneration, is
discussed in Section 4. Several approaches, ranging from the use of high efficiency separation
and regeneration with the subsequent use of a final resin purification stage (e.g. ammonia
washing or “resin on resin”) to the use of the ammonium sulphate density separation process,
have been reviewed. Conventional separation/regeneration techniques are generally not
adequate although stations in South Africa and in Ireland have modified them, together with the
procedures used, and have operated very successfully for many years in the ammonium form9.
However, these modified regeneration plants and procedures may demand an increased level of
operator involvement, relative to the effort required in the use of improved designs of
separation/regeneration plants.

Most simple mixed bed plants use a resin mixture of about 2:1 cation:anion resin by volume.
This gives a nominal ratio of the cation :anion exchange capacity, on a chemical equivalents
basis, of approximately 3.3:1. It is to be noted that these capacities refer to total capacities and
not operating capacities. As already discussed, operating capacities are significantly lower with
that of the cation resin being about 50% of the total capacity and the anion resin operating
capacity probably being an even lower percentage. A 2:1 v/v mixture of cation and anion resins
is reasonable under H-OH operating conditions as the cation exchange capacity controls the
service run length of a bed under leak free conditions. When a condenser leak occurs, the cation
resin has to perform the dual duties of removing both the ammonia and the influent impurity
cations.

Under ammonium form operating condition the demands are different with only the impurity
cations to be removed. However, there is still merit in maintaining a high cation:anion resin ratio
as, under ammonium form conditions, the cation resin capacity for sodium is generally lower
than that of the anion resin capacity for chloride. As already discussed, the respective
equilibrium capacities vary with pH and impurity levels as shown by plots of the respective
equilibrium capacities Figures 5-5 and 5-6. Another advantage is that as the cation exchange
operating capacity is increased, the time for a sodium displacement wave to pass through the bed
should also increase thus giving the operator more time to react. However, the higher the ratio of
cation resin in the mixed bed the lower must obviously be the ratio of anion resin so that the
operational capacity for removal of anions is consequently reduced. Furthermore, according to
Foutch, the peak sodium throw during on-line ammoniation could be higher when there is a high

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ratio of cation resin in the mixed bed,10. Probably the strongest reason for retaining a high
cation:anion resin ratio is that, in the event of a condenser leak the beds will have to revert to
H-OH form operation and must have the available cation and anion exchange capacity to
usefully operate in this form.

Figure 5-5
Equilibrium capacities of cation and anion resins for sodium and chloride at pH 9.2,
Na
( K NH = 0.8, K Cl
OH = 22).

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Figure 5-6
Equilibrium capacities of cation and anion resins for sodium and chloride at pH 9.6,
Na
( K NH = 0.8, K Cl
OH = 22).

5.9.3 Cation Mixed Bed Polishing Plants

The cation mixed bed plant has several advantages when used in the mode for which it is
primarily designed, i.e. the H-OH form. The leading deep cation resin bed acts as a filter and
protects the mixed bed from iron fouling. It provides a significantly increased cation exchange
capacity allowing the polishers to operate for useful periods of time at high pH in the H-OH
mode. The fact that the water leaving the lead cation bed is either neutral or slightly acid allows
the anion resins in the mixed beds to operate at their peak kinetic efficiency. The lead cation bed
can be safely run to a higher break-though point than normally used on simple mixed bed plants
so making a small gain in operating capacity. In the absence of condenser leaks this lead cation
bed can be regenerated independently of the mixed bed thus allowing the latter to continue in
service for many weeks. Cation-mixed bed polishers are very robust and well suited for high pH
operation although, of course, frequent regenerations of the lead cation bed are necessary. The
ratio of cation: anion resins in the mixed bed can be optimised for anion removal with the cation
resin volume being reduced to that necessary to remove cation leakage from the lead cation
exchange vessel and from the anion resins themselves. Probably the most successful application
11
of this design has been at San Onofre with its performance being well documented . However,
cation-mixed bed plants are about 50% more expensive than naked mixed bed plants and, outside
of Europe, relatively few are in use.

As already pointed out, cation-mixed beds are primarily designed for high pH operation in the H-
OH mode and it is not known whether any are operating in the ammonium form. However, there
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are no reasons why they cannot be very successfully operated in the ammonium form provide
that the mixed beds are regenerated to the high standards required. This could well involve
improving regeneration facilities as discussed above in Section 5.6 or the use of off-site
regeneration for the mixed beds at least. The filtration provided by the cation bed will continue
to be useful. Given reasonably frequent regeneration, and cleaning of the cation bed to remove
crud, the protection that it offers to the mixed bed should allow that bed to continue in service for
many months. In the absence of condenser leaks, the life of the mixed bed will be determined by
is exhaustion by carbon dioxide with experience at Moneypoint showing that, on some stations at
least, 6 month runs are possible. The difficulty of gauging when the available OH form anion
exchange capacity has been reduced below a level considered acceptable for dealing with a
condenser leak can be overcome to some extent by estimating the carbon dioxide load on to the
bed as described by Crone12.

5.10 Up-Grading Condensate Polishing Resin Regeneration Processes for

Ammonium Form Operation.

The paramount necessity of regeneration processes achieving very low levels of troublesome
impurities such as sodium and chloride on resins intended for service in the ammonium form has
already been discussed. The type of regeneration plant normally supplied to a fossil station is
unlikely to achieve the target of <0.08% sodium on cation resin and, ideally, an improved
separation system should be installed to replace the existing separation system. The chloride
target of <1.0% is somewhat easier to attain using conventional regeneration procedures
provided that sulphuric acid is used as the cation resin regenerant. If anion resins become
contaminated in service or are supplied in the Cl- form, or they must be fully converted to the
-
OH form, before use.

The adoption of one of the newer forms of high efficiency separation/regeneration procedures is
advised and this will necessitate plant modifications. As already discussed, some stations have
shown that conventional regenerating plants can, with care and some modification, achieve the
regeneration targets required. Experience on PWRs is also of interest as these power stations aim
to achieve, for their H-OH form polishers, the same level of regeneration as is now advised for
ammonium form polishers on fossil stations. Thus, Crone has described how the regeneration
system at Millstone 2 PWR was improved without major expenditure12, 13. However, the point
that must be stressed is that procedures such as these can be more manpower intensive and
require the attention of trained and motivated operators. The use of separation and regeneration
procedures that are simple, robust and reliable in their operation, and which produce regenerated
resins of the appropriate quality every time of use, is obviously attractive. This points to the
adoption of the newer separation procedures or, alternatively, the use of specialist off-site
regeneration services.

5.11 References

1. J. C. Bates and T. Johnson, “The Development of a Computer Model Amm-Leak for

Sodium Leakage from NH4-OH” Beds”, Ion Exchange Technology, Ellis Horwood,
Chichester, UK, 1984.

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2. E. Maughan, G. Gericke and G. Lok, “An On-Line Analyser for the Measurement of
Dissolved Carbon Dioxide”, Ultrapure Water, July/August 1992.

3. K. Tittle, “ The NorthWestern Region Prototype Carbon Dioxide Monitor”, Proceedings of

the EPRI Condensate Workshop, Richmond, Virginia, USA, 1985.

4. D. J. O’Sullivan and E. F. McCarthy, “A Review of Condensate Polishing Plant Operation in

th
the Electricity Supply Board of Ireland”, Proceedings of the 5 EPRI International
Conference on Cycle Chemistry in Fossil Plants, 1997.
th
5. J. Falke, “Condensate Polishers in Separate Bed Configurations”, Proceedings of the 5
International Conference on Cycle Chemistry in Fossil Plants, 1997.

6. P. W. Renouf and J. Smith, “Operating Experience with a Tripol Ammonia Cycle”,

Proceedings of the 41st International Water Conference, Engineers’ Society of Western
Pennsylvania,1980.

7. W. A. Marchewka, J. D. Aspden and J. B. Conlin, “Condensate Polishing at Elevated

st
Temperatures”, Proceedings of the 51 International Water Conference, Engineers’ Society
of Western Pennsylvania,1990.

8. J. D. Aspden, Private Communication.

9. F. McCarthy and G. O’Connor, “Ammonium Form Operation of Condensate Polishing Plant

for Long Periods of Time in High pH Systems at Moneypoint Power Station”. Proceedings
of the EPRI Condensate Polishing Workshop, 1991.

10. G. Foutch and E. Zecchini, “Sodium Throw in Mixed-Bed Ion Exchange”, Ultrapure Water,
November, 1991.

11. D. C. Auerswald, “ San Onofre Nuclear Generating Station Polisher System Performance and
Impact on Steam Generator Chemistry”, Proceedings of EPRI Polishing Workshop”,
Chicago, USA, 1987.

12. L. Crone, “Operating Experience at Millstone 2 with Full Flow Condensate Polishing”,
Proceedings of EPRI Workshop on Condensate Polishing, Phoenix, Arizona, USA, 1991.

13. L. Crone, “Experience with Boric Acid Treatment and Condensate Polishing at Millstone 2”,
Proceedings of the EPRI Condensate Polishing Workshop, 1989.

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6
GUIDANCE ON OPERATION OF POLISHING PLANTS
IN THE AMMONIUM FORM

6.1 Return to Service of Regenerated Resins

6.1.1 Condition of Cation and Anion Resins

The critical need for very effective regeneration of ion exchange resins intended for service in
the ammonium form has already been discussed in Section 3. The lower the impurity levels on
the resins the higher the quality of the final polished water. For operation at pH 9.6, resin
regeneration targets have been proposed with < 0.08% of the exchange sites on the cation resin
being in the sodium form and 1.0% of the active sites on the anion resin allowed to be in the
chloride form. Anion resin regenerated to meet these proposed purity standards is always
-
returned to service, whether as a mixed bed or as a separate bed, in the OH form. Cation resin
can be returned to service either pre-ammoniated or in the H+ form. As discussed below, there
are advantages and disadvantages in either of these options. However, it is clear that most, if not
all, operators return the cation resin to service in the, as regenerated, H+ form and allow it to
ammoniate in-service.

6.1.2 Pre-ammoniation of Cation Resin

At the end of the normal regeneration process applied to resins returning from service in
ammonium form polishers, cation resin is predominately in the H+ form with probably about 5%
of the exchange sites still in the ammonium form, Figure 4-9. For a further cycle of service in
the ammonium form it will, at some stage, obviously be necessary to fully ammoniate this resin.
This can be carried out in-service, as discussed below, or by converting the cation resin fully to
the ammonium form before it enters service. There are two apparent advantages in pre-
ammoniation. They are :-
• It reduces the disturbance caused to impurity levels in the steam/water circuit that is caused
by the sodium throw that normally occurs when beds are allowed to ammoniate in service.
Pre-ammoniated beds should, assuming steady state/no in-leakage conditions, enter service
yielding sodium leakage levels that are determined by the sodium levels on the resin and the
pH of operation. They should then continue to operate with this level of leakage until the bed
is removed from service. This allows their in-service leakage behaviour to be predicted if
analysis of the resin is known, (see Section 8). In fact this level of sodium leakage should
decline slightly over very long service runs.

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Guidance on Operation of Polishing Plants in the Ammonium Form

• Pre-ammoniated beds obviously do not remove ammonia from influent condensate in

contrast to the behaviour of beds being ammoniated in service. Thus, ammonia levels in
water circulating in the steam/water circuit remain constant, assuming steady state no in-
leakage conditions. This makes control of chemical conditions within the steam/water
circuit, and ammonia dosing in particular, easier to monitor and adjust

Thus, pre-ammoniation should lead to simpler control of all impurity levels in the steam/water
circuit and hence to more consistent water quality and possibly to less operator involvement in
monitoring and control. Figure 6-1 shows the sodium leakage from one of the few reported test
runs carried out to compare pre-ammoniation with in-service ammoniation. The results are not
particularly favourable to the pre-ammoniation approach possibly because the sodium levels on
the resins used were particularly low at 0.03% 1. It would be useful to obtain further
comparisons. They do, however, show that the average sodium, as measured at about 0.33 ppb, is
reasonably close to the leakage predicted, 0.24 ppb. On the basis of these test results there was
little real advantage in pre-ammoniation but, of course, these were very well regenerated resins
and the benefit will vary with the sodium content of the resin.

Figure 6-1
Pre-ammoniation and on-line ammoniation of resins containing 0.03% sodium at Aghada
Generating Station, 1981

Pre-ammoniation is inconvenient for several reasons. It imposes another step in the regeneration
process adding not only to the time and effort required but also to the effluent disposal problem
although it should be possible to minimise the latter. In the 1983 Aghada trials, it was reported
that pre-ammoniation required twice the stoichiometric quantity of ammonia possibly because of

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Guidance on Operation of Polishing Plants in the Ammonium Form

the need to complete the process relatively quickly and as part of the regeneration process. Even
then, the cation resins went into service with still some remaining capacity to remove ammonia.
On-line ammoniation simply takes the chemically equivalent quantity of ammonia and does not
demand effort by operators or produce effluents.

Another important constraint is the need that stations, normally operating in the ammonium
mode, still occasionally have for H-OH form beds. During unit start-ups, when the possibility of
contaminated water with high crud levels being treated by the resins is high, it is desirable to use
H-OH form polishing. This is not essential, but desirable, and in any event the contaminated bed
will probably be replaced and regenerated shortly after the start-up and the cost and effort of
ammoniation, if pre-ammoniated beds are used, will be lost.

A similar requirement for the occasional use of H-OH form resins arises in the event of a
condenser leak. In this situation it is recommended that any contaminated ammonium form beds
be replaced by H-OH form beds within one to two days of a condenser leak arising. The plant
should then be operated in this mode until in-leakage problems are solved even if this requires
reducing pH levels within the circuit temporarily. This is prudent “fail-safe” advice to avoid the
possibility of slow release of any of the influent impurities removed, by ion exchange, starting to
be released or ”thrown” – a process than can occur about 2-3 days after an in-leakage incident. It
is, however, worth pointing out that, with care, ammonium form resins could continue to be used
throughout an in-leakage incident until the quality of the polished water becomes unacceptable.
This situation could arise if, for example, they were the only resins available. Any ammonia
form beds exhausting in service could also, if essential, be replaced by fresh ammonium form
beds. As discussed below. The question of the capacity for impurities shown by ammonium
form bed is complex and in some situations they can effectively show a higher capacity than
shown by H-OH form beds. Despite this, the general advice in the event of a condenser leak
remains the same. It is to remove contaminated ammonium form beds from service within 2-3
days of the incident and replace them with fresh H-OH form beds and operate in this
conventional mode until such time that the in-leakage problem is solved.

The above advice is easy for those stations employing in-situ ammoniation. However, if off-site
regeneration of resins becomes a more widely used method of servicing polishing plants then it
may be attractive for resins to be supplied and held in reserve by stations in the ammonium form.
If this development takes place the matter of the use of pre-ammoniated resins under impurity
ingress conditions, such as start-ups and condenser leaks, will need to be re-examined.

6.1.3 In-service Ammoniation of Cation Resins

The great majority of power stations operating polishers in the ammonium form employ in-
service ammoniation of their cation resin. It is obviously simpler and avoids the additional step
during or after regeneration and uses less ammonia. Its disadvantages are mainly concerned with
the disturbance that occurs to the polished water quality shortly after ammonia breakthrough
occurs. The problem of sodium throw that usually occurs at this time has already been discussed
and is again shown in Figures 6-1, and 6-2. Assuming the use of well regenerated resins and
depending on pH, the sodium throw will, at pH 9.6, peak at about 0.5 -1 ppb remaining about
this level for about 5-10 days before gradually falling to a new quasi steady state level of about
0.3 – 0.6 ppb. Thus, for about 5-10 days, or even longer on some stations, the sodium

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Guidance on Operation of Polishing Plants in the Ammonium Form

concentration in polished water from the affected mixed bed will be relatively high. However,
assuming a polishing plant employing two parallel streams, each treating 50% of the condensate,
then the combined outlet sodium levels would be expected to increase to about 0.4-0.8 ppb for
some days every month. This assumes a bi-monthly service cycle of each ammonium form bed
but, of course, it is quite possible to extend this to two or three months so further reducing the
frequency of these ammoniation disturbances.

The fact that a polisher bed ammoniates, and then gradually stops removing ammonia from
condensate, obviously calls for ammonia dosing levels to be adjusted. This has caused problems,
in the past, on some stations with over dosing resulting with higher circuit pH levels and as a
consequence a disturbance to sodium and other impurity leakages. Given modern
instrumentation and dosing systems this need not happen. The great majority of power stations
operating polishers in the ammonium form routinely use on-line ammoniation. It obviously
causes minor effects upon impurity concentrations within the steam/water cycle but it must be
borne in mind that the highest impurity concentrations seen during these transient conditions are
well within operating targets for fossil power plants.

Figure 6-2
Impurity levels in polished water at Moneypoint Generating Station showing operation in
the ammonium form at pH 9.4-9.5.

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Guidance on Operation of Polishing Plants in the Ammonium Form

6.2 Operation of Polishing Plants in The Ammonium Form in the Absence

of Condenser Leaks or Other Upsets

6.2.1 Polished Water Quality

Under steady state conditions, and assuming the absence of condenser in-leakage, other impurity
ingress incidents, start-ups or pH swings, impurity concentrations in polished water from
ammonium form bed will be constant and depend primarily on the impurity concentrations on
the resins, i.e. regeneration effectiveness and the pH of operation. The results from five power
stations in three different countries are reviewed in Table 6-1 and examples are shown in Figures
3-9, 6-2, and 6-3. These indicate sodium levels ranging from about 0.1 ppb to about 0.6 ppb with
lower levels of the other common impurities.
Table 6-1
Impurity Levels in Water from Ammonium Form Polishers (Under Steady State, No In-
leakage, Conditions)

Power Station Sodium Chloride Sulphate pH

ppb ppb ppb
1
Aghada (1983) < 0.6 0.3 0.6 9.6

Mohave 0.13 < 0.2 <0.1 9.55

2
(1993)

Moneypoint < 0.3 < 0.3 < 0.4 9.4-9.6

3
(1991)
4
Stanwell (1996) 0.2-0.3 0.2 0.2 9.3-9.35
5
Tarong, (1986) 0.3 - - ~ 9.4

Such impurity levels place the water quality from ammonium form plants well within any
demand made for fossil power plants including those now being made for steam for cooling Gas
Turbines.

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Guidance on Operation of Polishing Plants in the Ammonium Form

Figure 6-3
Sodium in water from ammonium form condensate polishers, Tarong Power Station,
Australia, 1986

6.2.2 Crud Filtration Behaviour

Iron Corrosion Product Filtration

One of the useful functions of any condensate polishing plant is the on-going filtration duty that
it performs so limiting the transport and deposition of corrosion product. Whilst studies have
been made of the filtration behaviour of bed polishers, and a useful general assessment derived,
it must be pointed out that the filterability of iron oxides varies. It depends upon the type of
oxide and on the particle size with crystalline forms, such as magnetite, being more easily
filtered than the amorphous forms more frequently seen during commissioning and at some start-
ups. Thus, care must be exercised in comparing the iron filtration behaviours of different plants
and polishers operated in different modes.

Cutler reviewed the filtration abilities of deep bed plants and commented that amorphous iron
crud is more efficiently removed by polishers operating in a low pH environment indicating that
H+ form cation resins would perform better than ammonium form resins6. This author reported
that some stations using ammonium form plants at start-up “ experienced prolonged start-ups”
but could not be sure whether the cause was the ionic state of the cation resin or the
preponderance of red iron oxide in the condensate that even H+ form resin would have had

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difficulty in filtering. Japanese workers using synthetic hematite had previously found that
cation resins were more effective at removing particles of this material at low pH rather than at
high pH7. So that generally the feeling given by the literature is that ammonium form beds will
+
be less effective as filters than H form cation resins.

This feeling does not receive strong support from the actual plant experiences that have been
reported as these indicate that the crud filtration properties of ammonium form polishing beds are
similar to those seen on beds operated in the conventional HOH mode. EPRI Condensate
Polishing Guidelines, 1996, advises that “deep bed demineralizers removal efficiencies are
expected to be 60-85% for iron, 75 to 95% for copper and 70 to 90% for nickel”8. A coal fired
drum boiler station reports, from operations at about pH 9.6 in the ammonium form, typical iron
levels at the polisher inlet of 1-10 ppb and in polished water of 2-4 ppb indicating about 50%
removal at these relatively low levels3.

Workers on the separate bed polishing plant at Matimba Power Station, South Africa, reported
that, during commissioning, inlet iron levels of 18—427 ppb were reduced to 12-16 ppb across
the lead cation bed. This was at pH 9.5 and at steady state conditions on this air-cooled power
station an inlet value of 34 ppb Fe was reduced to about 3 ppb9. Later reports from this station
showed that the vast air cooled ferrous condensers were still leading to condensate iron levels of
10-30 ppb which was being reduced by the separate bed polishers, but primarily by the leading
cation bed, to between 4-7 ppb. They noted high differential pressure drop problems and iron
fouling of cation resins. In view of this, pH levels in the circuits were increased to pH 9.8 so
reducing iron levels at the inlet to the polishing plant to 2-12 ppb and, at the outlet, to 0.2-4 ppb.
o o 10
Condensate temperatures on this station range from 40 to 80 C (100 to 180 F) .

The proprietary design of separate bed polishers in use in the ammonium form at Stanwell,
Australia, reduced start-up crud levels of 80-90 ppb to about 5 ppb although it is assumed that
start-ups were carried out with the resins in the H-OH mode. Steady state inlet iron levels were
reported to be 10-20 ppb with, again, outlet levels of less than 5 ppb4.

Copper Filtration.

Corrosion products containing this metal are now generally of less concern as modern
steam/water circuits avoid the use of copper. Under H-OH form condensate polishing conditions
the removal of copper, both as particulate and dissolved forms, is at least as good as iron and
probably better. Cutler reports soluble copper being reduced from 110 ppb to 3.5 ppb and
particulate copper from 170 ppb to 35 ppb during start-up tests on a fossil station using a pilot
scale separate bed plant under conditions not considered as optimum6. It is difficult to see why
this performance would not be matched if the resins were used in the ammonium form but
information on the topic is difficult to find.

It is known that both anionic and cationic complexes of copper can be formed. Anion complexes
with chloride, exhibit a considerable affinity for “quarternary ammonium anion exchange resins”
(i.e. for strongly basic anion resins)11. Other processes involving the removal of copper, such as
its recovery from cuprammonium rayon spinning effluent, using ammonium form carboxylic
acid resins are widely reported. Neither of these uses approach the ultra-dilute conditions found

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in ammonium form condensate polishing but at least they point to copper being an impurity
readily removed by ion exchange processes.

6.2.3 Possible Problems During Service Runs of Ammonium Form Beds

Increase Of Differential Pressures Across Service Beds

In the absence of impurity ingress incidents, such as condenser leaks, most ammonium form
plants operate without problems so that the decision to remove them from service for
regeneration is often based upon operational convenience. However, on some stations the crud
load is sufficiently high that differential pressures across the beds gradually increase so that after
a few weeks it becomes unacceptable thus making replacement essential. The experience at
Matimba has already been discussed in Section 6.2 and clearly, on this station crud build-up was
dictating service lives of the ammonium form beds. Other stations claim to have run ammonium
form polishers for up to 150- 200 days without experiencing pressure drop problems so this
problem is clearly station specific.

Exhaustion of Anion Resin with Carbon Dioxide

Most power stations operate with a trace of carbon dioxide in their steam/water circuits. This
originates from pick-up in storage tanks and air in-leakage into the steam water circuit with some
also being contributed by the breakdown of traces of complex organic impurities that themselves
enter the circuit as impurities in make-up water. After a very long ammonium form service run,
it has been observed that carbonate begins to break through condensate polishing beds rising
from a background of about 1 ppb to about 10 ppb as deduced from cation conductivity readings
(0.12 µS/cm). Ion chromatographic analysis confirmed the absence of significant concentrations
of other anions such as acetate or formate3. If unchecked, this conductivity would probably have
continued to increase until EPRI action limits of 0.15 µS/cm were exceeded. Again, this situation
developed slowly with plenty of time for operators to note what was happening and to take
action. The time that the bed had been in service was unusual, but experimental, and normally
the run would probably have been terminated before carbonate breakthrough. The experience is
nevertheless a useful indication of the possibility of the carbonate capacity of anion resins being
exceeded, leading to unacceptably high cation conductivity values in the polished condensate.
The in-leakage of carbon dioxide and its organic precursors obviously vary from station to
station

Exhaustion of Anion Resin with Weak Organic Acids

The other common background anion impurities are the weak organic acid such as acetic and
formic and simple hydroxy acids such as glycolic acid. Acetic acid is usually present in greater
concentrations than the others with the source of these organic impurities normally being the
thermal decomposition of more complex organic molecules that enter the steam/water service in
make-up water having originated in the raw water. Under most ammonium form polishing
conditions it is carbon dioxide that contributes most to the background cation conductivity with
levels of the organic acids being typically less than 1 ppb. Figure 3-15 shows that the

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equilibrium capacity for acetate is very low particularly at high pH. There is, therefore, the
theoretical possibility that this capacity could become exhausted so that levels of acetate entering
the polisher will be equal to those leaving the polishers. As long as these acetate levels remain at
the low ppb levels this effect will pass unnoticed with the contribution to the cation conductivity
of the polished water being low. On a few power stations, organic acid levels in the steam/water
circuits could be high, owing to unusually high levels of organic contaminants in make-up water
or from the use of organic products to condition the steam/water cycle. Under these conditions it
is conceivable that breakthrough of acetate could occur to such an extent that cation
conductivities of the final polished water exceed EPRI Guideline values. This situation should
develop slowly with ample time for operators to identify the unusual problem and to remove
beds from service for regeneration.

6.3 Operation of Polishing Plants in the Ammonium Form in The Presence

of Condenser Leaks or Other Upsets

6.3.1 Predicted Behaviour of Ammonium Form Beds

The theoretical behaviour of an ammonium form bed in the face of a condenser leak has already
been described in Section 3. Ammonium form cation resins show a low selectivity towards
sodium and so it is the behaviour of this impurity that is, as usual, the most significant. The ion
exchange of this ion, by the ammonium form cation resin, results in the release of an equivalent
quantity of ammonium ion, i.e.

NaCl + R-NH4 + R-OH = R-Na + R-Cl + NH4OH

The anions associated with the sodium are removed by the OH form anion resins so that any
ammonia released by the resins is effectively present as the hydroxide and causes an increase in
the pH of the system. Section 3 details how a 500 ppb sodium input at pH 9.2 @ 25oC (77oF)
causes the displaced ammonia to increase the pH to about 9.39 and the consequence of this is a
small increase in the equilibrium sodium leakage. The effect is not as pronounced at higher pH
levels as the dissociation of ammonia is less. Slightly enhanced sodium leakage resulting from
ammonia displacement can be seen in the results of the simulated condenser leak test carried out
on the Moneypoint Power Station polishing plant, Figure 6-4

The second characteristic of ammonium form beds is their behaviour following the cessation or
diminution in size of a condenser leak. Such a change in conditions results in equilibrium
changes and a reduction of the capacity of the cation resin to hold sodium. The consequence of
this is that some of the impurities removed, whilst the leak was active, slowly begin to be
released. This behaviour, also shown to a lesser extent by the anion resin, has been demonstrated
both by computer simulations and by column tests12. Figure 6-5. The advice that contaminated
beds should be removed from service within a few days of a leak ceasing is based upon these
predictions and is obviously aimed at preventing impurity “throws” occurring. The actual delay
before such an impurity throw occurs will vary depending on the design of the plant and in
particular features such as the flow rate, the volume of cation resin and the pH of operation.

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Figure 6-4
Simulated sea water leakage test into condensate to an ammonium form condensate
polishing plant at Moneypoint Generating Station, pH 9.6.

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Figure 6-5
Sodium concentration profiles, in ppb (µg/kg), during displacement from an ammonium
form bed operating at pH 9.6—following sodium contamination of the bed.

6.3.2 Ion Exchange Capacity for Influent Impurities

As already previously described, behaviour of the ion exchange capacity, as it relates to resins
operating at high pH in the ammonium form, is complex. It is controlled by the pH of operation,
decreasing with pH, by the concentration of the influent impurity and by the selectivity shown to
it by the resin. So for sodium, in view of the low selectivity shown towards it by ammonium
form cation resins, equilibrium capacities can be very low, Figure 3-3. In actual service it is, of
course, the operating capacity that is of interest, i.e. the capacity any resin exhibits up to the
point that the leakage of an impurity into polished water exceeds limits set by an operator.
Experimental work has shown that the operating capacity of cation resins for removal of sodium
under ammonium form conditions is very approximately 50% of the calculated equilibrium
capacity. It would be useful to obtain information from actual plants to support these indications
and also to obtain data on operating capacities of anion resins.

Figures 3-3 and 3-4 show the calculated equilibrium capacities for both sodium and chloride.
From these graphs it appears that the available capacity for sodium at a low input level, but at
high pH, is only a fraction of that achievable in the H-OH form. Thus, assuming the use of an

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Guidance on Operation of Polishing Plants in the Ammonium Form

ammonium form cation resin with a volume capacity of 2 eq/l, at pH 9.6 and a sodium input of
100 ppb, the equilibrium capacity would be about 0.16 eq/l giving an operating capacity of about
0.08 eq/l. If operating in the H-OH form an operational capacity of about 1 eq/l would be
expected, over ten times higher. In considering these figures the fact that, in ammonium form
operation, the background ammonia is not being removed must be remembered. This means that
despite the ammonium form cation operating capacity being lower it is all available for sodium
removal. Obviously, in H-OH mode operation, a significant proportion of the available capacity
is used in removing the ammonia background but this proportion obviously varies with pH.

In reality condenser leaks are rarely constant and, as shown in Figure 6-6, they fluctuate in
intensity with leakage paths blocking and unblocking possibly under the influence of tidal
conditions or other external effects13. The disturbed period shown in this figure, with sodium inlet
concentrations reaching 230 ppb at pH 9.2, resulted in sodium levels in the polished water
exceeding 2 ppb within a few days. It is important to note that these results date back to 1979 and
relate to the use of less well regenerated resins than would now be considered suitable for use in
the ammonium form. However, the figure is still useful in showing the fluctuating levels of
influent sodium that can be seen on some stations.

Figure 6-6
Ammonium form condensate polisher performance in face of a condenser leak of variable
size on a 500 MW unit without optimum regeneration facilities, 1979.

In face of this behaviour and in view of their characteristic, under some conditions, of
subsequently releasing impurities, the advice is to remove contaminated ammonium form beds
from service as soon as operationally convenient. If this prudent course of action is followed the

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full operating capacity of an ammonium form bed to sodium is rarely tested although,
theoretically it can be greater than an H-OH form bed. What matters is whether such beds can
withstand condenser leaks and the plant examples shown below indicate that they can.

The above remarks apply to the removal of sodium. The behaviour of chloride, and the capacity
shown by anion resins towards it, follows the same pattern as that for sodium. However, as the
selectivity shown towards this impurity is very significantly higher, the actual capacities are
significantly higher although still varying with pH and the influent concentration.

The behaviour of weakly acidic impurities, such as acetic acid, formic acid, fluorides and silica,
in ammonium form condensate polishing, has not been investigated in any depth, probably
because they are not perceived to be a problem. Certainly, the precursors of weak organic acids
and silica should be capable of being controlled by attention to the preparation of make-up water.
However, a few fossil stations, unwisely, still rely on using condensate polishers to act as the
polishing stage for make-up water. At the low concentrations to be expected within a
steam/water circuit it is likely that the capacity offered to these weak anionic impurities will be
perfectly adequate. In this respect the Moneypoint results are interesting showing acetate and
formate levels in influent condensate of below 1 ppb even after a 200 day service run of an
ammonium form bed at pH 9.6.

Oldbury on Severn Nuclear Power Station operates it naked mixed bed polishers in the
morpholine form at very high pH (pH 9.5 to 9.7). The anion exchange in this mode of operation
is the same as in ammonium form beds – simply OH form anion resins operating in a high OH-
environment. The organic amine, morpholine, is used at high concentrations, 30 – 60 ppm, and
shows some breakdown with acetic and formic acids being amongst the decomposition products.
It was observed that “morpholine form mixed beds operating at high pH initially have a high
removal efficiency for organic acids such as acetate but that the percentage of the acids slipping
the beds gradually increases linearly with time until essentially no removal is taking place”14.
Figure 3-16 shows this progressive slippage with up to 60 ppb of acetate eventually building up
in the steam/water circuit

Now, this is a very extreme case with a known source of organic acids within the steam water
cycle, i.e. from the decomposition of morpholine. It is however possible that, given a make-up
water containing high levels of organic impurities, and attempts being made to operate for long
periods of time in the ammonium form, a similar, though not as extreme, situation of acetate
leakage could arise on a fossil plant. As discussed in Section 3 the equilibrium capacities for
acetate are low and dependent on pH and input levels so breakthough could easily occur. EPRI
Guideline values on cation conductivity in steam, of 0.15 µS/cm, may then be exceeded. Whilst
such events have not been reported it is sensible to protect against them by assuring the purity of
any make-up water used.

6.3.3 Behaviour of Sodium, Chloride and Sulphate During Condenser Leakage

Conditions on Actual Polishing Plants

In the event of a condenser leak it is to be expected that the ammonium form condensate
polishing plant will effectively remove the influent impurities. The plant should then continue to
yield polished water of acceptable quality until the leak ceases or the capacity of the plant to

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remove influent impurities is exhausted. The question of its effective capacity has already been
discussed in Section 3 and depends both upon pH and the concentration of the impurity being
exchanged. In practice it is acceptable and it must be noted that, in ammonium form operation,
all of the effective ion exchange capacity is devoted to the removal of sodium or other impurity
cations. In contrast to the action of the cation resin in conventional H-OH mode polishing, none
of this capacity is used for the removal of ammonia.

The immediate performance of an ammonium form bed in the presence of a condenser leak is,
therefore, theoretically completely acceptable for all fossil power station applications. The fact
that ammonium form beds cannot be relied upon to retain, for more than a few days, any
impurities previously removed has already been discussed and the necessary actions to minimise
any problems resulting from impurity throws identified. Interest then centres upon actual full-
scale plant experience of ammonium form beds under in-leakage conditions. Ammonium form
polishers have many times been subjected to tests in which sea water or other contaminants are
deliberately injected into the water flowing into the plant with the earliest test results dating back
to the late 1960’s. More recent tests are however of greater interest in view of the improved
water qualities suggested by EPRI Guidelines. These include:

(a) Aghada Power Station, Ireland. A test on the full flow deep mixed bed polishing plant on
this 270 MWe single unit gas fired station was carried out in 1982. Sea water was injected to
give measured inlet concentrations of 150-180 ppb of sodium and 250-290 ppb of chloride
over a period of approximately 90 minutes. The operating pH was about 9.6 and results
show a very slight increase in sodium leakage from 0.24 ppb to a maximum of 0.27 ppb,
almost certainly caused by the ammonia displacement/pH effect. Chloride levels in the
polished water were not affected. Figure 6-7 and 6-8.

(b) Moneypoint Power Station, Ireland. The ammonium form polishing plant on one of the 300
MWe units on this three unit coal fired drum station was tested in 1991 by the injection of
seawater over a period of 2 hours to give a maximum of 324 ppb sodium and 520 ppb
chloride. The polisher had been in service for 80 days prior to the test. Operating at pH 9.6,
sodium leakage levels increased slightly from their steady state values of 0.18-0.2 ppb to give
0.22-0.25 ppb, Figure 6-4. Chloride leakage levels also showed a slight change from 0.25-
0.27 ppb increasing to about 0.28-0.30 ppb. Again, it can be assumed that these changes
were due to the slight pH increase, from pH 9.55 to pH 9.61, resulting from ammonia
displacement. A cation conductivity increase from 0.107 to 0.141 was also observed as this
was obviously not caused by chloride or sulphate it was concluded that it was caused by
bicarbonate being displaced by the influent chloride and sulphate

(c) Oldbury on Severn Nuclear Power Station, United Kingdom. This is a gas cooled nuclear
power station of the Magnox type with once through boilers. Conditions in its steam water
circuit are generally similar to those in most PWRs and like stations of this class it has been
troubled by two phase FAC. This problem has been largely overcome by conditioning the
steam/water circuit with a high concentration of morpholine, 60 ppm, and operating the
polishers in the morpholine form. Morpholine form operation is very similar to ammonium
form operation with the only real difference being the slightly higher selectivity that
morpholine form cation resins exhibit towards sodium relative to that shown by ammonium
form resin

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A simulated leak test was carried out on a morpholine form mixed bed in 1985 with sodium
chloride being dosed into the inlet to give a sodium content of about 120 ppb for 5 hours.
The sodium content of the polished water gradually increased from 0.4 ppb showing a slight
increase during the actual test period but 48 hours later it was 1 ppb and in 96 hours a level
of 2 ppb sodium leakage had been reached. The morpholine form bed was obviously
releasing the sodium that it had taken up during the period of the simulated leak. Figure 6-9.

(d) Tarong Power Station, Australia. Tarong is a 4x350 MWe coal fired power station operated
in Queensland, Australia. A small leak was simulated by injecting cooling water to give a
sodium level of 13.6 ppb for a period of 14 hours when the pH within the circuit was about
pH 9.3. There was a slight increase in the sodium level in the polished water to about 0.3
ppb and the normal rise in direct conductivity owing to the displacement of ammonia to a pH
of about 9.36. The polisher was left in service for a further 22 hours after the test was ended
with the only parameter to show a slight further rise being the direct conductivity.

Figure 6-7
Aghada Generating Station polishing plant trials, simulated sea water leak test, chloride in
condensate.

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Guidance on Operation of Polishing Plants in the Ammonium Form

Figure 6-8
Aghada Generating Station polishing plant trials, simulated sea water leak test, sodium in
condensate.

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Guidance on Operation of Polishing Plants in the Ammonium Form

Figure 6-9
Results of a simulated condenser leak test on polishing plant operated in the morpholine
form at pH 9.5.

The simulated leak tests described above are useful in that they give station personnel confidence
and also in that the results generally support theoretical predictions that ammonia displacement
will lead to immediate small rises in sodium leakage and that chloride leakage will hardly alter.
Only the Oldbury on Severn tests were continued long enough after the sodium injection period
to see the delayed release of sodium which in this case at pH 9.49 (30 ppm) took about 4 days to
reach 2 ppb. Advice in these Guidelines conservatively advises taking contaminated beds out of
service in 2-3 days but this advice assumes the more forcing pH 9.6 conditions and the
sodium/ammonium situation. The Oldbury data was obtained on a morpholine conditioned
circuit at pH 9.5. As already discussed, slightly lower levels of sodium leakage would be
expected owing to the higher selectivity coefficients shown by cation resin towards sodium when
operating in the morpholine form rather than the ammonium form.

All of the above condenser leak simulations involved steady impurity input levels and, as already
discussed, during a real leakage situation the influent concentrations will vary. However, the
results all show that ammonium form beds can and do combat the ingress of impurities at the
time of in-leakage and for some days beyond. The advice to operators to remove a contaminated
bed from service within 2-3 days of an in-leakage incident and revert to H-OH form is sound but
is for the “guidance of wise men”. Under real plant conditions, when the in-leakage situation is
often confused, operators must always be prepared to take an ammonium form bed out of
service, or leave in service, based on their judgement, trends in the polished water quality and
local operational demands. Nevertheless, for security, it is desirable to return to H-OH form

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Guidance on Operation of Polishing Plants in the Ammonium Form

polishing, using a fresh charge of resins, as soon as convenient when a disturbed in-leakage
situation becomes apparent.

6.3.4 Regeneration of Ammonium Form Resins after a Condenser Leak Incident.

One of the most important tasks of any condensate polishing plant is to protect the steam/water
circuit from the effects of a condenser leak or other in-leakage incident. Larkin has shown in
EPRI TR-104422 that the other, often less widely appreciated, advantages of condensate
polishing also bring significant economic benefits. These include improvement to unit reliability
and availability, reduction or elimination of the need to chemically clean boilers, improved
turbine cleanliness, faster start-ups, reduced boiler blowdown and many more. By themselves,
these advantages make a convincing argument for the use the technique. However, the safe-
guarding of the steam water circuit in the event of a condenser leak remains, in the eyes of many
operators, the most obvious of the advantages of condensate polishing although with the
improved condenser design and tube materials now in use, in-leakage events have fortunately
become less frequent.

Most condensate polishing resins, whether used in the H-OH form or ammonium form are
returned for regeneration not having been contaminated by an in-leakage incident and so
containing relatively low levels of impurities. As already discussed ammonium form resins
could be returned for regeneration containing less sodium than they held when entering service
and scarcely higher levels of chloride. Following ammonium form service under “no in-leakage”
conditions few problems should be experienced in the regeneration of resins. This, of course,
assumes that the resins are in good condition, effective separation of mixed beds and the use of
appropriate regeneration techniques as discussed in Section 4.

Resins contaminated by in-leakage of impurities, however, pose a potential problem. Every case
must be reviewed separately and with lightly contaminated resins it may simply be necessary to
double or triple regeneration levels. Ideally, any resins over which a doubt exists should be
checked after regeneration to see that their residual impurity levels meet the pH 9.6 criteria of <
0.08% Na and <1% Cl or the targets set by operators if the lower pH is used in the steam/water
circuit. Normal analytical procedures can be followed or the simple tests suggested in Section 8
may be of use in this task. More severely contaminated resins should receive special treatment
to ensure that they are purified sufficiently. The actual procedures to be used will depend on the
level of contamination but include:-

Regeneration of Contaminated Cation Resins

Increasing the levels of regeneration, to about 360 g/litre of sulphuric acid can, depending on the
extent of the contamination, normally regenerate cation resins that have picked up sodium during
service. It has been claimed that soaking the resins overnight in a charge of the acid also helps in
the process of eluting impurities. Whatever is done, it is important that the sodium content of the
regenerated resin is checked and if not satisfactory the regeneration procedures are repeated.
Suggestions for a quick method of checking the sodium content of these resins are given in
Section 8. More effective, but tentative, cation resin regeneration procedures have already been
discussed in Section 4 and involve the use of regenerants such as ammonium sulphate. Now, this

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Guidance on Operation of Polishing Plants in the Ammonium Form

regenerant may not be available or be able to be used by all stations and in this situation there is
little alternative to simply repeating conventional acid regeneration procedures. Specialist
contractors operating off-site regeneration facilities may, however, be better placed to use
ammonium sulphate. This is a new approach and with the exception of Mohave few, if any,
other power stations have attempted to use this alternative regenerant.

Whatever approach is used for the regeneration of contaminated cation resin it is strongly
recommended that it be checked for sodium impurity content after regeneration and before
service. Not all stations will be unable to comply with this advice and for these it is essential that
the behaviour of the regenerated resin be carefully monitored when it is placed in service and
particularly at the ammoniation stage.

Regeneration of Contaminated Anion Resins

Anion resins that have picked up chloride during service can, if the contamination is relatively
low, be brought back to an acceptable chloride content by increasing the levels of regeneration,
to about 360 g/litre of sulphuric acid. Again, it has been claimed that soaking the resins overnight
in a charge of sodium hydroxide also helps in the process of eluting impurities and usually there
is no great time pressures on regeneration processes on plants operating in the ammonium form.
It is important that the chloride content of the resin is checked after the selected procedure. If it
is not satisfactory, i.e. less than 1% Cl or whatever target adopted by the station, then the
regeneration procedure should be repeated or more effective procedures adopted.

More effective anion resin regeneration procedures have already been discussed in Section 4 and
involve displacement of the chloride by an anion to which the resin shows a higher selectivity.
The two anions conventionally used are sulphate or carbonate. The contaminated anion resin can
be put into the sulphate form by the use of dilute, say 5% sulphuric acid or a similar
concentration of ammonium sulphate. The fully sulphated resin will then require conversion
back to the OH form by the use of a high level of sodium hydroxide, say 360 g/l used at a
concentration of about 4%. It is a consequence of sulphating resins under power station
conditions that a percentage remains in the sulphate form even after a high level regeneration
with sodium hydroxide. Resin analysis at Moneypoint showed about 20% of their anion resins
still remaining in the sulphate form even after attempts to regenerate the fully sulphated resin to
the OH form. Results from other stations support this experience. This, of course, represents an
effective loss in anion exchange capacity but has little if any effect on the subsequent in service
leakage of sulphate.

Other workers have employed sodium bicarbonate in 5% solution followed by 384 g/l of sodium
hydroxide used in a 4% solution15. Whilst effective stripping of chloride is to be expected, and
this should be confirmed by analysis of the regenerated resin, a residual of bicarbonate on the
resin will probably also result. Again, more information would be welcomed from stations
attempting to use this approach for stripping chloride from contaminated resins.

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6.4 References

1. M. A. Sadler, D. J. O’Sullivan, J. C. Bates and M. E. Costello, “Ammonium Form Operation

th
of Condensate Polishing Plant at Aghada Generating Station”, Proceedings of the 45
American Power Conference, 1983.

2. P. Meyers, “Experience with Amsep at Mohave”, Proceedings of EPRI Condensate

Polishing Workshop, Seattle, 1995.

3. F. McCarthy and G. O’Connor, “ Ammonium Form Operation of Condensate Polishing Plant

for Long Periods of Time in High pH Systems at Moneypoint Power Station”, Proceedings
of EPRI Workshop on Condensate Polishing, Phoenix, Arizona, USA, June 1981.

4. R. N. R. Robinson and L. A. Chapple, “Operation of the World’s Largest Tripol Condensate

Polishing Vessel at Stanwell Power Station, Queensland, Australia,” Ion Exchange
Developments and Applications, Royal Society of Chemistry, Cambridge, UK, 1998.

5. D. Gunn, L. Lloyd and F. Roberts, “Ammonium Cycle Condensate Polishing at Tarong

Power Station”, CEPSI, Jakarta, Indonesia, 1989.

6. F. M. Cutler, “Effectiveness of Iron Removal by Deep Bed Polishers”, Proceedings of EPRI

Condensate Polishing Workshop, June 1991.

7. K. Ishigure et al, “Adsorption of Model Crud on Ion Exchange Resin Beads”, Proceedings of
British Nuclear Energy Society Conference on Water for Nuclear Reactors, 1983.

8. EPRI TR-104422, Condensate Polishing Guidelines, 1996.

9. W. A. Marchewka, J D Aspden and J B Conlin, “Condensate Polishing at Elevated

st
Temperatures”, Proceedings of 51 International Water Conference, 1990.
10. O. Sadie, Matimba Power Station: “Experience Obtained with the Effect of High All-Volatile
and Oxygenated Treatment on the Steam/Water Circuits”, Eskom International Conference
on Process Water Treatment and Power Plant Chemistry, Midrand, South Africa, November,
1997.

11. R. Kunin, Ion Exchange Resins, Robert E Krieger, Publishing Co, Florida, 1982.

12. M. Ball, M. A. Jenkins and R. J. Burrows, “Ammonium Form Cation Resin Operation of
Condensate Polishing Plant”, Ion Exchange Technology, Ellis Horwood, 1984.

13. M. A. Sadler, J. C. Bates and G. R. Mills, “ The Application of a Triple Resin Condensate
Polishing Plant System at Fawley Power Station”, VGB Conference on Power Station
Chemistry, 1980.

14. M. A. Sadler, J. C. Bates, M. R. Darvill and G. W. Ellis, “Morpholine Form Condensate

Polishing at Oldbury on Severn Nuclear Power Station”, pp34-48, Ion Exchange for Industry,
Ellis Horwood, UK, 1988.

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15. D. J. O’Sullivan, P. Powell, H. R. Bolton, E. K. Bullas and M. A. Sadler, “Regeneration of

Condensate Polishing Plant Resins by the Use of the Resin on Resin Technique at Aghada
Generating Station” Ion Exchange Developments and Applications, Proceedings of IEX’96.
Royal Society of. Chemistry, Cambridge, UK, 1996.

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7
CONCLUSIONS

7.1 Use of Condensate Polishing

Full flow condensate polishing is a proven method of maintaining purity in the steam/water
circuits of most types of thermal power stations. It protects against the occasional, but very
serious, ingress of ionic impurities from incidents such as condenser leaks. It continuously
removes particulate impurities and the traces of ionic impurities that enter even well maintained
steam/water circuits. Fossil power stations are not as demanding as most types of nuclear stations
but they also require condensate and feedwater of very high quality. This requirement becomes a
necessity if they choose to protect their circuits from corrosion product transport by adopting the
effective oxygenated treatment of feedwater. The annual savings made by the use of condensate
polishing have been calculated to be at least $1600/MWe for a 360 MWe fossil unit. These
savings are derived from faster start-ups, reduced chemical cleaning, reduced blowdown and
reduced turbine losses and are in addition to the protection offered against condenser leaks.
However, despite these considerable savings, operators still have a very great interest in
minimising both the capital and operating costs of condensate polishing but without sacrificing
the benefits.

7.2 Methods of Reducing Condensate Polishing Costs

The conventional method of operating deep bed condensate polishing plants is with the anion
and cation resins in the forms to which they are converted by normal regeneration. This mode of
operation, the H-OH mode, is simple to use, simple for non-chemists to understand and simple to
monitor. Its main disadvantage is that the length of time that H-OH beds remain in service is
usually short as the cation resin exhausts owing to the ammonia it removes by ion exchange.
This removal of the ammonia added as a conditioning agent, is both a cost and a nuisance.
Service run lengths of polishing plants are very dependant on the pH of operation (ammonia
content of the condensate) and vary from a few days to well over 40 days.

Power stations suffering from very frequent polisher regenerations will have an interest in
making operational economies by extending the service lives of their beds. Techniques such as
“by-pass polishing”are often used. This simply means using polishers only during start-ups and
in times of “need” such as when condenser leaks arise. Whether full or partial by-pass polishing
is employed, it suffers the drawback that if a large condenser leak suddenly occurs a significant
time is required to get the polishers back into full flow operation. One power station has
vigorously tackled this problem and, by plant modifications, claims to be able to get a polisher
back in full flow service in less than one minute. So the technique could possibly be developed
and deserves some attention. However, another drawback is that, with the polishers being by-

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Conclusions

passed, particulate impurities such as corrosion products are not constantly removed - neither are
the ever present traces of ionic impurities.

7.3 Ammonium Form Operation of Deep Bed Condensate Polishers

The other widely used method of achieving operational economies is to operate the polishers
with the cation resins fully converted to the ammonium form. In this form they do not remove
ammonia and, in the absence of condenser leaks, beds can run for several months. Claims are
made that an annual operational saving of about $300/MWe result from its use. However,
ammonium form operation of polishing plant can be difficult to use and is most certainly not
suitable for all power stations. Its characteristics are very different from the simple,
conventional, H-OH mode of operation and because of this some stations have suffered
problems.

EPRI has always taken a cautious approach to ammonium form operation of deep bed polishing
plants and continues to do so. This report has been prepared in the recognition that many
stations currently operate their polishers in the ammonium form mode and that a great deal of
interest continues to be shown in the technique. As already stated, not all power stations can, or
should, use ammonium form operation but some can successfully make savings provided they
are aware of the differences between conventional H-OH form condensate polishing and
technique of operating polishers at high pH.

7.4 Advantages of Ammonium Form Condensate Polishing

The advantages of ammonium form operation are:

• Properly used it can routinely and consistently produce a condensate that meets all EPRI
targets applying to fossil power plants but not nuclear plants.
• Its use can allow a power station to increase the pH used in the steam/water circuit and
maintain full flow condensate polishing without the capital expense of enlarging its polishing
plant.
• It provides full protection against condenser leaks and other condensate contamination
incidents.
• Its ability to remove particulate impurities is approximately equal to that of conventional H-
OH mode condensate polishers.
• In the absence of condenser leaks or frequent start-ups, ammonium form beds can enjoy
service runs of several months.
• Significant savings in regenerants, water and manpower can be made together with a
reduction in effluents resulting from the regeneration process.

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Conclusions

7.5 Disadvantages of Ammonium Form Condensate Polishing

Unfortunately there are marked disadvantages associated with ammonium form condensate
polishing:
• The concentration of impurities in water from resins operated in the ammonium form will
always be higher than that achievable from the same resins if they were to be used in the H-
OH form. To counter the higher impurity leakage experienced during ammonium form
operation, the resins employed demand a higher degree of regeneration than resins used in
the conventional way. This ideally requires the use of high efficiency separation/regeneration
equipment and techniques.
• Ammonium form polishing is not suitable for use by all power stations. Fossil stations
suffering frequent condenser leaks and/or frequent start-ups will not benefit from its use. The
water quality produced is not acceptable for nuclear power stations such as PWRs with
recirculating steam generators.
• The commonly used approach of returning fresh polisher beds to service in the “as
regenerated” H-OH form, and allowing them to ammoniate in-service, results in a temporary,
but significant, increase in the sodium content of the final polished water. This increase
generally lasts for 5-10 days depending on conditions. Given effective regeneration, the
increased sodium leakage reaches a maximum of about 1 ppb and therefore remains within
EPRI target and action limits. The use of poorly regenerated resins will obviously result in
significantly higher leakage levels.
• The capacity shown by ammonium form beds for ionic impurities varies with both pH and
impurity influent level. Although these capacities, particularly that shown towards sodium,
are lower than shown by conventional polisher beds, ammonium form beds still provide
acceptable protection against condenser leaks as shown by both theory and experience.
• Ion exchange resins, when operating under ammonium form conditions, do not securely hold
the impurities that they have removed from condensate. These impurities can subsequently
be released (“thrown”) if conditions change - such as influent levels falling or pH increasing.
This behaviour, very different to the behaviour of resins used in the conventional mode, has
led to a recommendation that any contaminated ammonium form beds should be withdrawn
from service within 2 to 3 days of any condenser leak or other incident.

7.6 Possible Developments

Ammonium form operation was studied in the 1960s and 1970s and its characteristics
understood by the specialists concerned. A number of useful proprietary developments followed
mainly aimed at reducing the levels of impurities on regenerated resins. Since that time little
progress has been made and so some ideas are included to stimulate discussion and, hopefully,
work on these topics. These suggestions include simple procedures for checking the purity of
resins after regeneration and before use, for monitoring the sodium content of the ammonium
form beds when in use, possible ways of reducing the fouling of beds by corrosion debris, and
consideration of improved regeneration procedures.

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8
POSSIBLE DEVELOPMENTS IN THE USE AND
MONITORING OF AMMONIUM FORM CONDENSATE
POLISHERS

8.1 The Evolution of Ammonium Form Operation

The theory, benefits and problems of operating condensate polishers in the ammonium form
were known and discussed in the 1960’s 1,2. Enhanced sodium leakage and sodium throw were
some of the characteristics identified at a very early stage. Procedures were developed and
patented in an effort to overcome these problems and can still be found in use today. They
include techniques such as ammonia washing of resins, lime washing of resins and caustic
floatation of anion resins. Since these formative days there seems to have been few other
developments specifically aimed at improving ammonium form operation apart from better
techniques for mixed bed separation and the use of separate bed designs of polishers.

Resins regenerated to the required standards are capable of being routinely and successfully
operated in the ammonium form. They have been shown to yield, even at high pH, polished
water of a quality suitable for all fossil boilers including those used for the generation of steam
for the cooling of gas turbines. Despite the successful use of ammonium form polishing by some
power stations, it is still a more demanding mode of polisher operation than the H-OH mode and
users continue to meet difficulties.

The notes in this Section are intended as an exploration of some possible procedures, which if
developed, could make ammonium form operation more acceptable. The difficulties that occur
when operating ammonium form polishers are usually connected with the behaviour of sodium
so that these suggestions centre on controlling the leakage of this impurity. In particular the
avoidance, or minimisation, of sodium throw effects associated with on-line ammoniation and
the sodium throw effects that often follow condenser leaks will be considered. These are
controlled by the overall purity of the ion exchange resins being used and, in Section 8.2, a
procedure is suggested that, if successfully developed, may allow operators to rapidly check the
sodium content of cation resins.

Although sulphuric acid is the most widely used regenerant for the cation resin employed in
condensate polishers some large countries employ hydrochloric acid. There are indications that
the use of this acid may be responsible for the high leakage levels of chloride seen when mixed
beds using cation resin regenerated with hydrochloric acid are subsequently used in the
ammonium form. More information is needed and the leakage mechanisms must be studied and
understood. However, if the problem is caused by the use of hydrochloric acid then it is believed
that action can be taken to minimise its effect and this is also discussed.

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The concept of stable and unstable ammonium form beds, with reference to possible sodium
throw is mentioned and an approach to monitoring the sodium inventory of a mixed bed or cation
bed when in ammonium form service are considered. Possible methods of achieving long
service runs of these beds are mentioned and the issue of pre-ammoniation or in-service
ammoniation discussed.

8.2 On-Site Regeneration Control Techniques

8.2.1 Requirement for On-Site Regeneration Controls

It has already been stressed that the successful use of ammonium form condensate polishing
depends on the resins being used containing very low levels of impurity ions, such as sodium and
chloride. Suitable regeneration procedures are known and have been proven in use for many
years. Without doubt, further improvements could be made but, for reasons of complexity or
safety, their use may be confined to specialist contractors, assuming that these services evolve as
expected. The development of the following simple procedures for checking resins would,
however, be of immediate assistance to those stations operating in the ammonium form and
using on-site regeneration of resins.

8.2.2 A Simple Procedure for Checking the Sodium Content of Cation Resins

A simple and rapid method of determining the sodium content of cation resin after regeneration
and after any post regeneration purification procedures would be of value to operators of
ammonium form polishers. Such tests would indicate whether the resultant mixed bed will
behave acceptably when in service in the ammonium form. Analytical methods for the sodium
3,4
content of cation resin and the chloride content of anion resin are well established . These are
not lengthy procedures, but usually involve the use of laboratory based equipment and, of course
the personnel trained to use them.

A quick go/no-go test for sodium, that plant operatives can use with the minimum of training,
would be particularly useful. Such a test could be based on the use of the simple and
inexpensive sodium selective electrode. Sodium monitors have a well established role on power
stations and employ “glass electrodes” as the sensing element. These ion selective electrodes are
not specific for sodium but show a response to other cations and particularly the hydrogen ion.
Their response to H+ is minimised by increasing the pH of the solution being tested by the simple
expedient of adding a volatile alkali. Originally, ammonia was used with volatile amines such as
ethylamine or di-isopropylamine being adopted later with different instrument makers choosing
different amines. The fact that cation exchange resins show a very high selectivity towards
diaminoethane has already been mentioned in Section 4, as has its possible use in displacing
sodium from cation resin. Thus, it may be possible to displace sodium from the resin into
solution and, at the same time, to provide the appropriate pH for sodium electrode measurements
to be made. The possibility of developing this suggestion into a useful method for checking
cation resins for sodium content is currently being explored in ESKOM, South Africa5.

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8.3 On-Stream Monitoring of the Sodium Inventory of Ammonium Form

Mixed Beds

The throw of sodium during on-line ammoniation has previously been discussed. It is also
important to address the problems of sodium throw, and the less commonly seen chloride throw,
that can take place from ammonium form polisher beds when in service. These can occur,
following a condenser leak, if contaminated beds are not taken out of service within a few days
of the incident.

On a typical fossil power station, operating under steady state conditions, a stable ammonium
form bed can be considered to be one whose sodium inventory is gradually falling over its time
in service. An unstable bed, and one likely to throw sodium, is a bed whose sodium inventory is
increasing or has recently, and perhaps suddenly, increased. A simple means of making a mass
balance of sodium entering and leaving an ammonium form bed is therefore suggested thus
indicating whether the bed is gaining or loosing sodium, i.e. whether it is stable or unstable.

A simple stand-alone system could be used involving an on-line computer monitoring system
based on input from conventional low cost instruments such as cation conductivity and sodium
together with mass flow indications. Sodium and cation conductivity measurements before and
after condensate polishing plants are, of course, recommended by all the relevant EPRI
Guidelines. Such a computerised programme would simply estimate the mass of sodium into
and out of a bed to give the chemist early warning of whether it is gaining or loosing sodium so
warning of any potential problems. Modern sodium monitors should be able to provide the data
at the low ppb levels involved. The extension of an expert system such as EPRI “ChemExpert”
to monitor the sodium inventory of ammonium form mixed beds would, of course, be a great
advantage. If specific conductivity measurements are also made then it is possible for pH levels
6
of condensate to be calculated using the procedure proposed by Maurer .

It may be possible to use the same general approach to gain an indication of the build-up of
anions on the mixed bed and so to provide information on which the judgement to regenerate
could be based. However, unlike sodium measurements, cation conductivity measurements are
not specific and relate to carbon dioxide and organic acids as well as the potentially more
dangerous chloride and sulphate. Thus the actual anion load going onto the mixed bed would
have to be estimated based both on the measured cation conductivity and knowledge of the
normal anion impurity concentrations obtained by periodic grab sampling and ion
chromatographic analysis.

8.4 Early Detection of Sodium Throw Following a Condenser Leak

As already discussed the throw of sodium from ammonium form cation resin can result if the
polishing plant experiences a condenser leak and the operators fail for one reason or another to
take the actions described in Sections 3 and 6. The sodium throw displacement waves take
several days to exit from a bed. It would be a useful safeguard if the sodium concentrations in
the water phase are monitored at some point in the bed, before the bottom collector system, as an
early warning of a such a wave making its way though the bed. The instrumentation required is
simple enough, an on-line sodium monitor, but the acquisition of a representative sample is often
difficult. Sampling from intermediate positions within a resin bed has been tried before and

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problems experienced owing to the presence of disturbed reaction fronts. The exhaustion or
reaction front in conventional down-flow ion exchanger is normally depicted as being straight
and passing through the vessel in an even manner. Figure 8-1 shows the disturbed flow patterns
that can occur owing to ineffective inlet flow distribution resulting in resins in the centre, or
alternatively at the periphery, becoming fluidized to some extent. These flow distribution
problems are not uncommon, with Renouf and Deans describing flow distribution problems on
spherical vessels7. Problems with the design of bottom collector systems produce similar effects
so it is unwise to rely upon single point mid-bed samplers. A multi-point sampler is needed to
withdraw water samples from several points over the diameter of the bed at the selected level.
Samples taken from these devices can then be blended for presentation of a composite sample to
the sodium monitor.

Figure 8-1
Adverse effects of fluidizing resin.

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8.5 Ammonium Form Bed Run Length Extension

8.5.1 Constraints on Extending the Service Runs of Ammonium Form Polishers

Figure 4-9 shows the impurity content of a cation resin after an effective regeneration and before
it entered service on a polisher operating in the ammonium form. The sodium level was 0.08%
but after 150-200 days of operation in the ammonium form on a unit free from condenser leaks
the sodium content had fallen to 0.02%8. This behaviour is simply confirmation of predictions
that, in the absence of sodium input from sources such as condenser leaks, the sodium on the
cation resin reduces, during its period in ammonium form service, to a level significantly lower
than can normally be achieved by regeneration. The sodium pick-up during regeneration is
almost certainly due to residual cross contamination effects.

This sodium leakage behaviour also means that an ammonium form polisher is constantly
contributing traces of sodium to the steam/water circuit. As long as the total sodium in polished
water remains acceptably low this is not a matter of concern in view of the other benefits
obtained by the use of polishing in this mode. Thus, in the absence of problems such as
condenser leaks, shut down/start ups or the build-up of crud, the cation resin itself is obviously
not a constraint on extending the run length of ammonium form beds. The main restrictions on
the length of service runs become the gradual exhaustion of the anion resins and the need to
ensure that cation resins do not become iron fouled.

8.5.2 Anion Resin Exhaustion

The service lives of ammonium form mixed beds are affected by the condition of anion resin as,
even in the absence of condenser leak, they are slowly being exhausted by traces of carbon
dioxide in condensate and to a lesser degree by the traces of simple organic acids. These
impurities enter the steam/water circuit, as carbon dioxide and complex organic impurities,
through air in-leakage, in make-up water and, to a lesser extent, via dosing chemicals. The
concern over this gradual exhaustion of anion resins is that in the event of a condenser leak that
there may be insufficient remaining capacity to remove influent anion such as chloride. The
problem is the difficulty in predicting the degree of exhaustion without taking the inconvenient,
and operationally unwelcome, step of actually sampling and analysing the resin.

A similar problem of predicting anion resin exhaustion was faced by operators of H-OH form
condensate polishers on PWRs wishing to reduce sodium leakage stemming from cross
9
contamination at the regeneration stage . At Millstone 2 PWR they sought to minimise anion
resin regenerations and so adopted the system known as “skipped anion regenerations”. Mixed
beds returned for regeneration, after they became exhausted to ammonia or amine, were
separated and the cation resin regenerated in the normal way. It was then simply recombined
with the anion resin, that had not been regenerated, and the mixed bed rinsed and returned to
service with the result that sodium leakage levels decreased. Their problem then became that of
identifying how often this procedure could safely be applied, i.e. when did the anion resin require
regeneration. It is this same question, and the approach, which is of interest in the present
context.

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Assessments of the probable anion load were made at Millstone 2 on the basis of experience
gained from analysis of the anion resin actually being returned for regeneration and an
approximate knowledge of the carbon dioxide levels and other anionic impurities normally
present in the steam/water circuit. They worked on the basis that it was prudent at all times to
have sufficient anion resin in the OH form so that the polishers would be able to protect the
steam generator in the event of a condenser leak of a designated size. From these various
factors, and by the addition of a safety margin, a safe maximum operating period of the anion
resin was then predicted.

The Millstone 2 approach can be loosely described as being based on “station experience”. If
backed by adequate instrumentation, and particularly by a computer control programme such as
ChemExpert, it could be usefully employed by plants running in the ammonium form. The
Moneypoint data shows that about 50% of the anion resin remained in the OH form even after
service runs of up to 200 days so that such an approach need not be too restrictive.

Whilst the approach of providing an adequate reserve of OH exchange capacity is prudent, some
plant experience has indicated that carbonate form anion resins still exhibit a capacity for
removing chloride. The behaviour of carbonated anion resins under condensate polishing
conditions is likely to be complex and has not, as yet, been thoroughly explored. It would be
useful if the matter could be studied by both experimental and by computer modelling.

8.5.3 Crud Removal and Resin Fouling

One of the functions of condensate polishing plants is that of removing particulate corrosion
products. Fossil power stations are, because of costs, unlikely to be provided with a filtration
stage ahead of the resin beds so that the mixed bed, or the leading cation bed in cation-mixed bed
or separate bed systems, performs this duty. Iron oxide crud removal behaviour of cation resins
is of particular interest to operators of BWRs and a considerable effort has been devoted to
understanding the mechanisms involved. One group of researchers reported that crud capture by
resins could be classified into three types, loosely captured iron, tightly captured iron and iron
incorporated into the resin bead10. Another worker states that in the filtered crud from a BWR
power station two different forms of iron could be identified. The infragranular fraction, i.e.
surface iron crud, is the predominant form of iron and the comprised large particles of magnetite,
haematite, goethite, and lepidocrocite. Ultrasonic or backwashing could easily remove this
surface retained crud11. The intergranular iron, consisting of ultra-fine colloidal particles of
polymerised amorphous ferrihydrite was reported to be more difficult to remove. Sawicki
suggested that the ion exchanged iron becomes precipitated through hydration, polymerisation,
coagulation and agglomeration.

Clearly crud behaviour on resins is a complex matter with the general view being that iron oxides
left on resins for a long period become more difficult to remove. It is obviously prudent not to
allow crud to remain on cation resins for extended periods. Those stations with heavy crud
levels in their condensate will, of necessity, have to clean and regenerate their resins frequently
so as to minimise pressure drop losses. The stations that will probably be most interested in
extended runs of ammonium form polishers will be those on base-load with reasonably low iron
in condensate levels, say less than 5 ppb. Ways of minimising the effect of crud must therefore

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be sought for these stations with any procedures developed allowing long bed runs between
regenerations without interfering with the crud removal capabilities of the resin beds.

The cation-mixed beds and separate beds that are in use represent a small minority of all
polishing plants but have the advantage that the leading cation bed can be back-washed without
having to regenerate the other resins in the system. For the more numerous naked mixed beds
older techniques such as the use of cation-layer mixed beds could possibly be employed without
major plant modifications. During the regeneration process in a 2:1 mixed bed, one half of the
cation resin is reserved whilst the mixed bed is formed of the remaining cation resin and anion
resin. This 1:1 mixed bed is transferred to the service vessel and the reserved cation resin
subsequently added to provide a top cation resin layer. Now, if backwashing facilities could be
installed at the cation resin layer mixed bed interface, or just above, then it should be possible to
periodically take the vessel out of service for an hour or so and back-wash the top cation resin
without disturbing the mixed bed. By this method it may be possible to run a naked mixed bed
polisher until assessments of the available OH form anion exchange capacity indicate that
regeneration of the mixed bed is necessary.

8.6 Avoidance of Sodium Throw by Using Pre-ammoniated Cation Resins

The benefits of using pre-ammoniated cation resins to minimize the disturbances caused by on-
line ammoniation have already been mentioned. If a polisher bed is ammoniated before service,
it should enter service yielding a constant sodium leakage. In the absence of condenser leaks or
pH fluctuations, it should then continue to produce a polished water of consistent quality for the
remainder of its service run that can be several months. In contrast, if on-line ammoniation of
resins is used, there is the well known sodium throw effect at ammonia breakthrough and the
need to adjust ammonia dosing levels. Pre-ammoniation of cation resins appears attractive and
the most commonly used procedure of achieving this is that of simply circulating ammonia
solutions through the resins. Unfortunately it introduces another step into the regeneration
procedure, it is not efficient in its use of ammonia and produces yet more effluent for disposal.

It is therefore useful to consider other possible techniques such as the use of ammonium salts
such as ammonium sulphate. This chemical can be used very effectively as the primary cation
resin regenerant in place of an acid. At the same time its use converts the cation resin to the
desired ammonium form. Used in this way it would not introduce another step or further
complexity into the regeneration process. Ray and his co-workers, who reported that the sodium
3
content of a gel cation resin was reduced from 100% to 0.05% by treatment with 800kg/m of
12
ammonium sulphate, showed its effectiveness . Ammonium sulphate has been used, for some
years, as part of the proprietary Amsep process at Mohave Power Station although here the
resultant ammonium form cation resin is then fully regenerated to the H+ form. Resins prepared
in this way show on-line ammoniation sodium throws as low as 0.2-0.3 ppb and subsequent
steady state sodium leakages to about 0.1 ppb13. This low sodium throw peak, when operating at
pH 9.55 at 63oC (145oF), suggests that the actual sodium on cation resin was less than 0.02%
confirming the earlier CEGB work. Thus, the use of ammonium sulphate as the main cation
resin regenerant offers the prospect of very effective regenerations and the preparation of the
resin in the desired ammonium form. Costs and availability of suitable supplies of the chemical
have not yet been established and may be an obstacle to its use.

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Another possibility is ammoniation of regenerated H+ form cation resin by diffusing ammonia

across a membrane. For this purpose it may be possible to use hollow fibre membrane
contactors through which concentrated ammonia, drawn from bulk stocks, are circulated in a
closed circuit thus overcoming problems of ammonia odours and minimising waste of ammonia
and production of effluents. The design and cost of vessels to achieve ammoniation by this
procedure need to be explored. Unfortunately, although it seems feasible, such a diffusion
process is likely to be a very slow process.

Despite the apparent advantages of pre-ammoniation, virtually all power stations operating
polishers in the ammonium form currently choose to use on-line ammoniation as it avoids
another stage in the regeneration process. If off-site regeneration services become available and
economically acceptable, it would be less of a problem for contractors to adjust their
regeneration processes to supply cation resins in the ammonium form. However, for start up
purposes, when polisher beds frequently become contaminated with crud and, during times of
condenser leakage, it is generally advised that stations revert to H-OH form operation. Whilst
this is desirable, and contractors should be prepared to supply H+ form resin on demand, their use
is not essential14. Ammonium form beds could be used during these disturbed periods if the
condensate polishers are given an appropriate level of surveillance. The ammonium form beds
will probably need to be changed when steady state operation is attained.

8.7 The Reduction of Sodium Throw During On-line Ammoniation

The sodium throw that follows on-line ammoniation typically peaks at 1-2 ppb, depending on pH
and plant design, and lasts for about 5-10 days. Even higher levels of sodium throw are seen
when inadequately regenerated resins are used. This increase in sodium leakage, and the need to
significantly reduce ammonia dosing levels so as to control the circuit pH, is an unwelcome
disturbance to cycle chemistry conditions. As discussed above, pre-ammoniation would
eliminate the effect but has its own disadvantages that may be overcome by developments or the
adoption of off-site contractors. Another approach is to retain the use of on-line ammoniation
but attempt to reduce the sodium on resin levels well below the 0.08% target currently proposed.
Again, the use of ammonium sulphate appears the easiest method of achieving these very low
sodium levels, as work at Mohave shows, but they have been achieved by conventional
regeneration procedures during special tests15.

Another conceivable regenerant for off-site use would be a divalent amine such as
diaminoethane as this has been shown in EPRI sponsored studies to be very effective in stripping
sodium from cation resins16. This claim was supported by later work in which diaminoethane was
17
used to reduce the level of sodium on a macroporous cation resin to 0.003% . Following its
conversion to the diaminoethane form, the cation resin will have to be returned to the H+ form by
sulphuric acid regeneration. Assuming the use of economical levels of sulphuric acid,
regeneration will probably not be complete owing to the high selectivity of the amine for cation
resin. Thus, some of the cation exchange sites, say about 10%, will remain in the amine form
leading to an effective loss of available cation exchange capacity.

The amine regeneration approach indicated above has never been tested other than in bench scale
experiments. Its cost is therefore unknown and safety and effluent issues have not been
investigated. Even assuming the idea can be developed it is uncertain whether a process

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involving use of a volatile organic material will be looked upon favourably for use on power
stations. Overall, the use of ammonium sulphate looks a more promising approach to achieving
very low levels of sodium on cation resin thus reducing the magnitude of the throw of sodium
during on-line ammoniation.

8.8 Possible Methods of Reducing Chloride Leakage from Ammonium

Form Mixed Bed Polishers using Cation Resin Regenerated with
Hydrochloric Acid

As discussed in Section 4, some countries such as Germany use hydrochloric acid for the
regeneration of cation resins used in water treatment out of choice. Other countries, such as
India, use this acid because it is more readily available. The advantages and disadvantages in its
use have also been discussed and generally, for ammonium form condensate polishing purposes,
sulphuric acid is the preferred choice. The experience reported by Indian power stations using
hydrochloric acid and operating their polishers in the ammonium form points towards the use of
this regenerant being responsible for the high chloride levels that they have noted in their
18
feedwater and boiler water . However, proof that the use of this acid is really responsible has
not, as yet, been provided. The argument is that owing to anion in cation resin cross
contamination a proportion of the anion resin inventory is converted into the chloride form at
every regeneration and this leads to the high chloride leakage subsequently seen.

As already pointed out, a number of power stations use hydrochloric acid because of the local
supply situation and not out of choice. It would be useful if a way could be found to allow them
to continue to use this acid and to be able to satisfactorily operate their polishers in the
ammonium form. A possible approach can be suggested and is based on a simple post
regeneration treatment of the hydrochloric acid regenerated cation resins. They could be treated
with the minimum amount of sulphuric acid to ensure conversion of any entrained anion resin
from the chloride form to the sulphate form. Such a treatment may also strip chemisorbed
hydrochloric acid from the cation resin itself but, again, this requires demonstration. Thus, a
station will continue to use hydrochloric acid for the regeneration of make-up plant resins and
condensate polishing plant resins but will hold a small stock of sulphuric acid for the post
treatment of cation resin to be used in ammonium form condensate polishing. The volume of
anion resin requiring sulphation only represents about 1 to 5% of the cation resin so the rate of
use of sulphuric acid per regeneration will be very low. This taken together with the low
frequency of regeneration of ammonium form polisher resins means that relatively small
volumes of the acid need to be held in stock and this should ease supply difficulties.

Variants of the approach of post treating the cation resin can be suggested with attempts to
carbonate the entrained chloride form anion resin also being attractive. Whatever is devised, the
procedure must be simple and use chemicals readily obtainable in a satisfactory quality in
developing countries. The process obviously must not contaminate the cation resin. At this
point in time the sulphate approach seems most attractive but other approaches may well be
suggested.

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8.9 The “Ideal” Design of Service Vessel for Ammonium Form Operation

Possible designs of regeneration equipment have already been discussed in these Guidelines so
the question now arises of whether there is an ideal design of service vessel. Both South African
and Australian stations successfully use separate bed plants that not only avoid all resin
separation problem but also offer the facility, whether it is used or not, to independently
backwash the lead cation bed to minimise iron build-up and possible iron fouling. Separate bed
plants are reported to be significantly more expensive than naked mixed bed plants although this
claim is contested by one user of a proprietary separate bed design,19. So, opinions on separate
bed plants remain divided with, it must be said, the actual users being convinced of their
usefulness on fossil plants.

The possible use of a cation resin layer over a mixed bed in a conventional vessel was mentioned
in Section 8.5. Again, the cation resin layer is aimed at removing crud so lengthening the service
life of an ammonium form bed, assuming that an increasing pressure drop caused by
accumulation of filtered particulate impurities is the determining factor. Designs using a
separate cation resin layer, or bed, would assist the process of routinely removing this cation
resin for cleaning. It is likely that any such designs will be more expensive than a simple naked
mixed bed but it would be interesting to see the costs and advantages explored.

Finally, attention must be drawn to on-going work, initiated and funded by EPRI, on the search
for lower cost service vessels. Currently, studies are focussed on the use of radial flow service
20
vessels with computer simulations yielding encouraging results . Vessels of this type could
offer the prospect of lower capital cost polishing plants so allowing the economical use of two or
three bed systems if these can be shown to be the designs preferred by users for ammonium form
operation.

8.10 References

1. F. J. Pocock and J. F. Stewart, “Research on High-Flowrate Condensate Polishing”,

Proceedings of the American Power Conference, 1964.

2. E. Salem, “A Study of the Chemical and Physical Characteristics of Ion Exchange Media
Used in Trace Contaminant Removal”, Proceedings of the American Power Conference,
1969.

3. ASTM Standard, D-4191.

4. ASTM Standard D-4327.

5. D. Aspden, Private Communication, 19/02/01

6. H. Mauer, “On-line pH Monitoring by Measuring Differential Cation and Specific

Conductivity”, Power Plant Chemistry, Volume 1, No2, August 1999.

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7. P. W. Renouf and G. Deans, “Performance Analysis and Upgrading of Spherical Condensate

st
Polishers”, Proceedings of the 51 International Water Conference, Engineers’ Society of
Western Pennsylvania, 1990.

8. F. McCarthy and D. O’Connor, “ Ammonium Form Operation of Condensate Polishing Plant

rd
for Long Periods in High pH Systems”, Proceeding of the 53 International Water
Conference, Engineers’ Society of Western Pennsylvania 1992.

9. L. E. Crone, “Optimisation of Deep Bed Condensate Polishers in the Presence of

Ammoniated Feedwater”, Proceedings of the EPRI Condensate Polishing Workshop, 1987.

10. Ichiro Inami et al, “Mechanism of Crud Removal by Deep Bed Resins“, Proceedings of the
50th International Water Conference, Engineers’ Society of Western Pennsylvania,1989.

11. J. A. Sawicki, “Mossbauer Analysis of the Form and Distribution of Iron in Low Cross-link
Resins”, Proceedings of the EPRI Condensate Polishing Workshop, Seattle, 1995.

12. N. J. Ray, M. Ball and D. J. Parry, “Ion Exchange Purification Plant for the Treatment of
High pH Condensate”, Power Industry Research, 1, 75-85, 1981.

13. P. Meyers. “Experience with Amsep at Mohave”, Proceedings of the EPRI Condensate
Polishing Workshop: Deep Bed and Powdered Resin Systems” 1993.

14. F. M. Cutler, “Effectiveness of Iron Removal by Deep Bed Polishers”, Proceedings of EPRI
Condensate Polishing Workshop, 1991.

15. M. A. Sadler, D. J. O’Sullivan, J. C. Bates and M. E. Costello. Ammonium Form Operation

of Condensate Polishing Plant at Aghada Generating Station”, Proceedings of 45th American
Power Conference, Engineers’ Society of Western Pennsylvania 1983.

16. A. Miller, “Effects of Alternate Amines on Deep Bed Condensate Polishers”, Proceeding of
the EPEI Workshop on The Use of Amines in Conditioning Steam/Water Cycles, 1993.

17. M. A. Sadler, H. R. Bolton and K. Bullas,”PPQ Water – The Next Challenge!”, Proceedings
of the 53rd International Water Conference, Engineers’ Society of Western Pennsylvania,
1992.

18. Proceedings of Workshop on Operational Problems of Condenser Polishing Unit, National

Thermal Power Corporation Ltd, Korba, August 2000.

19. R. N. R. Robinson and L. A. Chapple, “ Operation of the World’s Largest Tripol Condensate
Polishing Vessel at Stanwell Power Station, Queensland, Australia, Ion Exchange
Developments and Applications, Royal Society of Chemistry, Cambridge, United Kingdom,
1998.

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Possible Developments in the Use and Monitoring of Ammonium Form Condensate Polishers

20. D. Shallcross and P. Renouf, “Modelling Radial Flow Ion Exchange Performance for
th
Condensate Polisher Conditions”, Proceedings of 6 EPRI International Conference on
Cycle Chemistry, Columbus, Ohio, USA, June 2000.

8-12
 EPRI Licensed Material

A
ION EXCHANGE RESIN SELECTIVITY COEFFICIENTS

Table A-1
Effect of Degree of Crosslinking on Selectivity Coefficients of Various Cations for
Polystyrene Cation Exchange Resin at 25°C

% Divinylbenzene
4 8 12
Monovalent Cations
H 1.0 1.0 1.0
Li 0.9 0.85 0.81
Na 1.3 1.5 1.7
NH4 1.6 1.95 2.3
K 1.75 2.5 3.05
Cs 2.0 2.7 3.2
Cu 3.2 5.3 9.5
Divalent Cations
Mn 2.2 2.35 2.5
Mg 2.4 2.5 2.6
Fe 2.4 2.55 2.7
Zn 2.6 2.7 2.8
Co 2.65 2.8 2.9
Cu 2.7 2.9 3.1
Ni 2.85 3.0 3.1
Ca 3.4 3.9 4.6

Source – EPRI TR-101942, 1997, Revision 1

A-1
 EPRI Licensed Material

Ion Exchange Resin Selectivity Coefficients

Table A-2
Selectivity Coefficients of Various Anions for Polystyrene-Based Strong-Base Anion-
Exchange Resins at 25°C

Relative Affinity
a b
Ion Type I Type II
Hydroxide (reference) 1.0 1.0
Fluoride 1.6 0.3
Acetate 3.2 0.5
Formate 4.6 0.5
Iodate 5.5 0.5
Bicarbonate 6.0 1.2
Chloride 22 2.3
Nitrite 24 3
Bromide 50 6
Nitrate 65 8
Bisulfate 85 15
Iodide 175 17
Benzenesulfonate >500 75
-
a) Reactive group, CH2N (CH3)3
-
b) Reactive group, (CH2N (CH3)2C2H4OH

Source – EPRI TR-101942, 1997 Revision 1

Table A-3
Selectivity Coefficients of Various Amines on Common Cation Resins at 25°C

Species Dow Amberlite Ambersep

Monosphere 120H 200H
650C
Sodium 1.48 1.41 1.83
Ammonia 1.87 1.77 2.31
Morpholine (Mo) 1.01 1.26 0.18
Diaminopropane 0.0548 — —
Diaminoethane (DAE) 6.64 5.96 10.8
Aminomethylpropanol (AMP) 1.06 1.45 0.12
Ethanolamine (ETA) 1.17 1.19 0.75

Source – EPRI TR-101942, 1997, Revision 1

A-2
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