START-UP

OPERATION
& SHUTDOWN
SEQUENCE OF
CRU UNIT

Md. Shameem Hossain

 PURPOSE OF PROCESS
 To convert low octane naptha to high
octane reformate product.
 To produce high purity H2 for
Hydrotreating unit.
 ALLOWABLE IMPURITIES
IN CRU FEED
 Sulphur -0.5 ppm wt
 Nitrogen - 0.5 ppm wt
 Water -5 ppm wt
 Chloride-0.5 ppm max
 Fluoride-0.5 ppm max
 SULFUR
 H2S reacts with platinum according to the equilibrium
reaction:
Pt + H2S PtS + H2
and with rhenium according to the equilibrium reaction:
Re + H2S ReS + H2
 it reduces the activity of the catalyst while
decreasing the metallic contact area.
Effect of sulfur contamination:
 Sulfur contamination inhibits the metal function of
the catalyst.
1. A decrease in hydrogen yield.
2. A decrease in recycle gas purity.
3. An increase in hydrocracking (LPG yield increase).
4. An increased coking rate.
 NITROGEN:

Cl OH Cl Cl OH OH

NH3 + H O + Al Al Al
2 Al Al Al + HCl + NH
3
O O O O

and HCl + NH NH Cl
3 4

Effect of nitrogen contamination:

Nitrogen contamination reduces the acidic function and is indicated
by:
•A decrease in octane.
•A slightly increased hydrogen production.
•A reduced reactor temperature drop
 HALOGENS (CHLORINE, FLUORINE):

 The presence of chlorine as chloride in the feed modifies the

acidic function of the catalyst and promotes the hydrocracking
reaction.
 The effect of fluorine as fluoride is similar but it is more difficult to
remove from the catalyst. It is very seldom to find fluoride in the
reformer feed
Effect of chlorine, fluorine contamination:
 Hydrocracking reactions are enhanced:
• Lower liquid product yield.
• Higher LPG and C1 yields.
• Slightly higher octane.
• Decrease of hydrogen production.
 DSN-PONA

 Paraffin-49.5 vol%
 Olefin-0.5,Vol%
 Napthene-29,Vol%
 Aromatic-21, Vol%
 CHEMICAL REACTION

Two types-
 Desired (increase octane number & H
2
purity)
 Dehydrogenation
 Dehydrocyclisation
 Isomarization

 Adverse (decrease octane number & H 2

purity or loss in product yield)
 Cracking
 Hydrogenolysis
 Coking
 CATALYST
 bimetallic catalyst RG 682A consisting of
Platinum & Rhenium
 Promoter on an Alumina support
 Total Catalyst of 3 Reactor=6401 kg
 Dia:1.66mm

1. Pt=0.25 wt%
2. Rh=0.4 wt%
 CALALYST & INERT BALLS
DISTRIBUTION IN REACTOR
 ADSORBENT OF D-304A/B

 Trade Name= AxTrap 857

 Typical Properties
1. Al2O3=90.5 wt%
2. Na2O=8.5 wt%
3. Dia-2 to 5 mm
Appilication: HCl removal from [Link] reformer hydrogen off
gas
Estimated Loaded Weight:1357 kg
ADSORBENT IN D-304A/B
 CATALYST MECHANISM
Two different functions-
 Catalyst Metallic and
 Acidic function.

Reactions Responsible Catalyst

Function
Dehydrogenation Metallic function
Dehydrocyclization Metallic + acidic functions
Isomerization acidic functions
Hydrogenolysis Metallic function
Hydrocracking Metallic + acidic function
Metallic Function(Pt & Rh):
 For a maximum catalyst activity the metal must be highly
dispersed on the alumina support and under the minimum
possible particle size (actual figure is in the rang
Acidic function:
 The optimum level of acidity changes somewhat with the desired
performance (maximization of gasoline and hydrogen yields or
gasoline and LPG production).
 The acidity of the catalyst is dependant on the amount of chlorine
which is fixed on the catalyst at the manufacturing stage of 1.10-6
mm).
 chlorine favours the bonding of metals/support
 low chlorine levels are promoting metals sintering or
agglomeration
 The chlorine content of the catalyst must be in the range 0.9 % to
1.1 wt%.
 Moreover it is known that alumina based catalysts require
some moisture OHto activate
Cl the
OH acidic function
 catalyst support chemical structure
Al Al Al

O O
This is referred to as chloride elution or leaching by water and
can be represented schematically as follows

OH Cl OH OH

Al Al +H O Al Al + HCl
2

O O
 ALTERATION OF CATALYST ACTIVITY

Decrease of metallic
Decrease of acidic function Increase of acidic function
function
• Elution of chloride due to high • Over chlorinated catalyst due to: • Temporary reversible poisoning
water content in the recycle gas. by sulfur.
–chlorine in the feed
• Nitrogen compounds (loss of Cl • Permanent poisoning by metals.
–or too low water in recycle gas.
through NH4Cl) in the feed.
• High water content in the recycle
gas (upset) on a very dry catalyst
(the acidic function increase is
temporary).

• Decreased octane. • Slight increase in octane. • Large decrease in octane.

• Decreased LPG production. • Decrease in liquid product and H2 • Decreased delta T in first reactor.
yields.
• Increased Cl production related to • Decreased C1 + C2 production.
C1-C4 cut. • Increased LPG production.
• Increased liquid production.
• Increased recycle gas H2 purity. • Decreased C1 production related
• Large decrease of H2
to C1-C4 cut.
• Increased liquid product yield. production.
• Decreased recycle gas H2 purity.
• Decreased recycle gas H2 purity.
• Decreased T in last reactor.
 Desired Reaction:
Naphthenes dehydrogenation:

CH CH
2
HC CH
2
(m) HC
CH
2
+ 3H
2
HC CH HC CH
2 2
CH CH
2
Cyclohexane Benzene

Paraffins dehydrocyclization:

CH
2
CH CH
2
(a CH CH CH
2 2 2
) +H
CH CH CH CH CH CH CH 2
3 2 2 3 3 CH 2 3

C H C H
7 16 7 14

CH CH
2 2
CH CH CH (a CH
2 2 ) H C CH
2 3
CH CH CH CH
3 2 3 CH CH
2 2

Methylcyclohexane
 ISOMERIZATION

These reactions are fast, slightly exothermic and do not affect the number
of carbon atoms. The thermodynamic equilibrium of isoparaffins to
paraffins depends mainly on the temperature. The pressure has no
[Link] paraffins isomerization results in a slight increase of the octane
number
ADVERSE REACTION
 EFFECTS OF HYDROCRACKING
 A decrease of paraffins in the reformate
which results in an increase of the
aromatics percentage (i.e. an increase
in octane) and a loss of reformate.
 A decrease in H2 production.
 An increase of LPG production.
 CATALYST DISTRIBUTION
In this unit (3 reactors) the catalyst
distribution is:
 R1 = 20 %
 R2 = 30 %
 R3 = 50 %
 FIRST START-UP
Chronology-
 Drying of the catalyst
 Complete inerting of the adsorption, stabilization and
deethanizer sections.
 Stabilization section start-up on total reflux.
 Pressurization with hydrogen of the reaction section
and the adsorption section.
 Heating up, reduction of catalyst, sulfiding and
chloriding.
 Oil in.
 Operation of the unit at low capacity and low severity.
 Operation of the unit at low capacity and high severity.
 Start-up of the hydrotreater unit.
 Operation of the unit at nominal capacity and high
severity.
 DRYING OUT
OF THE REACTION SECTION
DIAGRAM
CATALYST DRY OUT DIAGRAM
 CATALYST DRYING
 After catalyst loading, the reaction under a 5 to 9
kg/cm2 gauge pressure of N2.
 The O2 in nitrogen is maintained around 2 to 5
volume % during the whole drying step.
 Furnaces are fired and temperature of all catalytic beds is
increased at a rate of 40deg.C per hour up to 485deg.
 When the catalyst temperature reaches 350deg.C, an
injection of chlorinated compound for about 4 hours, so as
to introduce chlorine (as Cl) equivalent to 0.1 wt % of the
total mass of catalyst
 The catalyst bed temperature is maintained at 485deg.C
for two hours minimum, or until water drained at low
points is lower than 10 liter per hour. Then temperature is
reduced to 350deg.C at a rate of 50deg.C per hour.
 OPTIMUM OPERATION OF THE
REFORMING UNIT:

 The chloride content of the catalyst

must be maintained between 0.9 to
1.1 wt %.
 The water content in the recycle
gas must be maintained between
15 to 25 volume ppm.
CATALYST HEATING, REDUCTION
SULFIDING DIAGRAM
 CATALYST REDUCTION

 The reaction section is purged with a nitrogen containing

less than 100 ppm vol of CO + CO2 in order to eliminate O2
to a concentration of no more than 0.3 vol. %
 Electrolytic H2 shall be used for the reduction of the metal
oxides
 Repeat once this operation, and then increase the pressure up to 7
kg/cm2 g minimum at separator and start-up the recycle gas
compressor.
 Increase then the pressure to 1.0 kg/cm2 g and depressurize
to flare at separator drum. Repeat once this operation, and
then increase the pressure up to 7 kg/cm2 g minimum at
separator and start-up the recycle gas compressor.
 Beds temperature is progressively increased to 510deg.C at
a rate of 40deg.C per hour, The reduction step starts when this
average temperature is 500deg.C
 This temperature is maintained at least during 4 hours or
until the quantity of water drained is lower than 0.05 % of
the catalyst weight per hour. Check every hour H2S in
recycle gas
 CATALYST SULFIDING

 Sulfiding is performed to reduce temporarily the extra activity of

the catalyst, especially the hydrogenolysis function of the freshly
reduced metallic phase which could lead to cracking with
production of methane.
 The sulfur injection is carried out reactor by reactor starting with
reactor n°2, then reactor n°3 and finally with reactor n°1. This
allow either to let more time for the sulfur to disperse in the last
reactor and to oil-in the unit immediately after reactor n°1
sulfiding.
 The sulfiding step is carried out after reduction, when the catalyst
beds temperature has been reduced from 500deg.C down to
400deg.C at a rate of 50deg.C per hour.
 The sulfiding step lasts for at least 3 hours at 400deg.C.
 For fresh catalyst, the quantity of DMDS to be introduced
corresponds to 0.15 wt. % sulfur on catalyst
 Every 30 minutes, the concentration of hydrogen sulfide at
reactors outlet must be determined using the usual method of
Dräger tubes or equivalent. Such analysis are used to make sure
that each catalyst bed is well sulfided (~ 20 ppm )
 STABILIZER START-UP
 Purge nitrogen then pressure with H2
 Establish 80% level in the stabilizer with
naphtha
 Establish a circulating loop through the
stabilizer reboiler using the reboiler pumps
 Set the flow to design conditions
 Start the stabilizer condenser
 Maintain column pressure around 6 to 7 kg/cm2
gauge by H2
 When the level of the stabilizer reflux drum
indicates 50%, send reflux to the column.
 Operate the stabilizer on total reflux
 DEETHANIZER START-UP
 Purge nitrogen then pressure with H2
 Establish 80% level in the Deethanizer Column
with LPG
 Flow water to the overhead condenser
 Establish a circulating loop through the
Deethanizer reboiler using (E-308)
 Start the Deethanizer condenser
 When the level of the Deethanizer reflux drum
indicates 50%, send reflux to the column.
 Operate the Deethanizer on total reflux.
TYPICAL REFORMING START-UP
 OIL-IN (FIRST TIME)

 The catalyst bed temperature being stabilized at 400deg.C, the

reaction section pressure is increased to a minimum of 8 kg/cm2 g
by injection of start-up hydrogen.
 The hydrotreated feed from NHT unit is introduced to the
reactors at 60% of the design rate in about 10 minutes
 The furnaces are controlled to maintain 400deg.C at the
inlet of each catalytic bed
 The inlet reactor temperature can be increased by 10deg.C during
the first hour, then pushed to 460deg.C at a rate of 25deg.C per
hour.
 The quantity to be introduced amounts to 10 ppm wt
calculated as Cl concentration in the feed rate to the unit.
Check with catalyst samplers that the chlorine content of
the catalyst is lower than 0.8wt%. The Cl concentration in
feed can be increased-up to 20 ppm wt.
 START-UP PREPARATION
Instrument air : In service
Utility air : In service
Cooling water system : In service
Individual user isolated, drain open
Nitrogen system : In service
Checked for proper oxygen content
Steam : In service
Drains and traps have been checked
Fire water : In service
Fuel gas : Ready to use
Inside the unit battery limit the system is blanketed with
nitrogen, oxygen content has been checked.
Flare system : Ready to use
The main header flare of the unit is kept open to atmosphere
and isolated with a blind from the flare collector at the battery
limit.
Hydrocarbon closed : Ready to use
sewer
Process water : Ready to use
Electrical equipment : Ready to use
 NORMAL START -UP
 Pressurization with hydrogen of the CRU Reaction
section & the adsorption section up to 12kg/cm2
 Pressurization with H2/N2 of the CRU Stabilization
section up to 10 kg/cm2
In the same time start long Cold circulation through
TK-006-P-201-C-201-D-305-C-301-TK-006
0R
TK-006-P-201-D-305-C-301-TK-006
[Link] Heater piloting H-304 and start to heat up 190 0C
[Link] frist Compressor K-301 A/B Prior to Check up.
[Link] Start heater of CRU Reaction section H-301/302/303
up to 460C at 40 c/hr
[Link] in CRU R/S when Temperature in Reactor at 460 0C
 START UP DIAGRAM OF CRU

T-006 P-201 A/B C-201 D-305 C-301 T-006

DSN

D-201

OR

D-305 C-301 T-006

T-006 P-201 A/B

DSN

D-201
 START UP DIAGRAM OF CRU

E-301 H-301
T-006 P-201 A/B C-201 R-301 H-302

DSN

D-302 K-301A/B D-301 A-301 E-301 R-303 H-303 R-302

K-302A D-303 D-304A/B NHT H2

Fuel
Gas
 START-UP PHASE
 First temperature level: 460deg.C
 Second temperature level: 470deg.C
 Third temperature level: 480deg.C
 High severity operation:  480deg.C
WAIT Increase summary:
RI Tdeg.C 460 max 470 max 480 max > 480 > 500

H2O in R/G ppm > 200 < 200 < 100 < 50 < 30

H2S in R/G ppm > 10 < 10 <5 <2 <1

Chloride injection rate ppm 10 – 5 5 3 2 0.2 - 1

wt
COMMISSSION D-301 AND D-303 &
K-302A
 ROUTED PRODUCT FROM TK-006 TO TK-002
 When temperature 460 0C ,start CCl4 Dosing pump.
 When H2 produce in CRU R/S available, then Start
K-302A
 COMMISSION FUEL GAS SYSTEM
 THEN START NHT BY USING CATALYTIC HYDROGEN
AND FUEL GAS
 OPERATION OF CRU UNIT
 Control philosophy of the Process:
 flow rate of the naphtha feed from NHT unit;
 control of reactors inlet temperatures, by adjusting
the heaters duty, with impact on final reformate
quality (octane number) and quantity;
 H2/HC ratio controlling the hydrogen flow rate of
recycle compressor
 reaction section pressure controlling the hydrogen flow
rate sent to absorption section;
 stabilization section pressure by adjusting the fuel gas
quantity send to network;
 reformate and LPG specifications acting on the
column operating parameters
OPERATING PARAMETERS(CHANGE OF
FEED RATE)

• increase of feed rate by  increase of temperature by 2deg.C.

10%

• increase of feed rate by  increase of temperature by

20% 3.5deg.C.

• increase of feed rate by  increase of temperature by 8deg.C.

50%

• decrease of feed rate by  decrease of temperature by 2deg.C.

10%
• decrease of feed rate by  decrease of temperature by 4deg.C.
20%
• decrease of feed rate by  decrease of temperature by
50% 13deg.C.
CHANGE OF REFORMATE OCTANE
NUMBER

• RON (clear): 85 to 90  temperature increase of ~ 1.8deg.C per

octane point.

• RON (clear): 90 to 95  temperature increase of ~ 2.4deg.C per

octane point.

• RON (clear): 95 to 100  temperature increase of ~ 2.8deg.C per

octane point.

• RON (clear): 100 to 102  temperature increase of ~ 3.5deg.C per

octane point.
 RECYCLE GAS WATER CONTENT.
WATER AND CHLORIDE INJECTION

Recycle gas Chloride content, (Cl-),

content, ppm weight in feed
ppm volume
15 - 25 0.2 to 1.0

25 - 35 1.0 to 1.5

35 - 50 1.5 to 2.0

 50 3.0 (Decrease reactor inlet temperature to 480deg.C).

 100 5.0 (Decrease reactor inlet temperature to 460deg.C).

 SULFUR CONTENT - HYDROGEN
SULFIDE CONCENTRATION
 Sulfur content - hydrogen sulfide
concentration

• H2S content in the recycle gas should not be more

than 1.0 ppm vol. and should normally be less than
0.5 ppm vol.
• For instance 5 vol. ppm in stabilizer off gas
corresponds to about 1 vol. ppm in the recycle gas.
ADJUSTMENT OF OPERATING CONDITIONS
Pressure:
 All the hydrogen producing reactions i.e. dehydrogenation,dehydrocyclization are
enhanced by low pressure.
 The lower the pressure the higher the yields of both reformate and hydrogen for a given
octane number. This is the reason for minimizing unit pressure drop and operating at
the lowest practical pressure.
 The low pressure below the design pressure results in higher pressure drop which
favors high yields, favors also coke build up
 Operator action on pressure is limited:
• Operating pressure rise is limited by equipment design pressure.
• Operating pressure lowering is limited by recycle compressor design power and intake
volume.
Temperature:
increase of the reactor inlet temperature results in :
• An increased conversion of the non aromatic compounds of the feed mainly the
paraffins. But since the hydrocracking reaction is more favored than the cyclization of
paraffins, the end result is:
 increased octane
 decrease in reformate yield.
 increase of the coke deposit.
 Decreases the H2 purity.
Space velocity

Weight of feed (per hour)

Weight Hourly Space Velocity
WHSV
: =
Weight of catalyst

 A decrease in the space velocity means an increased

residence time, hence a higher severity results
1. increased octane,
2. lower reformate yield,
3. higher coke deposit
4. Decreases H2 purity.
When changing feed rate,
An important rule is:
• For feed increase: Increase feed first, then adjust temperature
increase to meet octane.
• For feed reduction: Lower temperature first, then adjust feed
reduction to meet octane. H2 Pure hydrogen (mole/hour) in recycle
=
Hydrogen to hydrocarbon ratio: HC Naphtha flow rate (mole/hour)

 Recycle hydrogen is necessary in the reformer operation for

purposes of catalyst stability
 It has the effect of sweeping the reaction products and
condensable materials from the catalyst and supplying the
catalyst with readily available hydrogen
 An increase in H2/HC ratio will move the naphtha through
the reactors at a faster rate and supply a greater heat sink
for the endothermic heat of reaction. The end result is an
increased stability
 A lower H2/HC ratio decreases the hydrogen partial pressure
and increases coke formation
 It is strictly recommended to operate with a H2/HC ratio
equal to (or higher than) the design figure.
 EFFECT OF PROCESS VARIABLES

Increased RONC Reformate yield H2 yield Coke deposit

Pressure

Temperature

Space velocity

H2/HC ratio

A + 0.85 N

Naphtha End boiling point

Quality Initial boiling point

 SHUTDOWN OF CRU
 When shutting down, steps should be taken to
prevent catalyst or equipment damage from
expansion, contraction, thermal shock or unusual
pressure surges.
 The procedure consists of switching-off the
feedstock under hydrogen rich atmosphere in order
to reduce the cracking of heavy components in
contact with a too hot catalyst.
• Reduce reactor inlet temperature to 460deg.C at a rate of
25deg.C/hr
• Simultaneously, decrease the feed rate to 60% of its design value.
• Stop chlorinated agent and/or water injection to feed.
• Cut-off the feed and maintain the recycle gas circulation during two
hours at 460deg.C at reactor inlet.
• Cool down the catalytic beds to 350deg.C at a rate of 50deg.C per
hour, then switch-off furnaces.
Short period shutdown:
 This shutdown is typically less than 24 hours to carry out minor
repairs without opening any major equipment.
 In this case, shutdown the compressor and leave the reaction
section under pressure.

 Long period shutdown:

 This shutdown is required for major repair of some equipment or
some sections of the unit.
 whole unit is drained and inerted
 the recycle gas circulation must be maintained until the catalyst
beds are totally cooled down.
 The recycle compressor is then shutdown and the reaction section
depressurized.
THANKS TO ALL