DBNPA AS AN ALTERNATIVE METHOD FOR
MICROBIAL CONTROL IN RECYCLED WATER
DUAL MEMBRANE PLANTS
Paper Presented by:
Kevin He
Authors:
Kevin He, Carlota Rodriguez, Mohammad Helmy,
City West Water
Daniel Palm, Dow Chemical Australia
79th Annual WIOA Victorian Water Industry Operations
Conference and Exhibition
Bendigo Exhibition Centre
31 August to 1 September, 2016
79th WIOA Victorian Water Industry Operations Conference & Exhibition Page 104
Bendigo Exhibition Centre, 31 August to 1 September, 2016
DBNPA AS AN ALTERNATIVE METHOD FOR MICROBIAL
CONTROL IN RECYCLED WATER DUAL MEMBRANE PLANTS
Kevin He, Carlota Rodriguez, Mohammad Helmy, City West Water
Daniel Palm, Dow Chemical Australia, Melbourne
ABSTRACT
Industry practices have varied in the control of microbial growth and biofouling of membrane
filtration systems in recycled water applications. Some of the strategies utilised include
chlorination/dechlorination, chloramination, Sodium Bisulphite and Biocide dosing in
Feedwater. Each strategy has its advantages and disadvantages; as well as associated operational
risks including risk of oxidation of RO membranes. It is well documented that any free chlorine
can damage polyamide RO membranes which is further oxidised in presence of transition metals.
RO performance deterioration is typically characterised by reduction in salt rejection and
permeate flow.
Altona Salt Reduction Plant (ASRP) is an UF and RO (two pass) recycled water plant, owned
and operated by City West Water (CWW). It receives tertiary treated effluent from its wastewater
treatment plant. This paper summarises ASRP’s experiences with a non-oxidising and
biodegradable biocide, DBNPA and provides insights into alternative methods to manage
biofouling in membrane filtration systems. The paper will also compare operating cost of using
Chlorine/dechlorination Chloramination and DBNPA dosing.
1.0 INTRODUCTION
DB2,2-Dibromo-3-nitrilopropionamide (DBNPA CAS#10222-01-2) is a non-oxidising
biocide used to reduce microbial and biological fouling in Reverse Osmosis (RO) systems
for industrial water production, off-line cleaning of RO membranes producing potable
and municipal water, ultra-filtration, nano-filtration and microfiltration systems and a
wide range of other industrial and water treatment applications.
DBNPA has been used at ASRP during its operational history, dosed in varying
concentration and at different injection points. The experiences and analysis from
previous operational periods proved there were opportunities to optimise the microbial
control and performance of the plant.
ASRP was offline between 2013 and 2015 and upon recommencement, various strategies
were discussed for microbial control as part of an options analysis. Feasible options
include chlorination with sodium bisulphite quenching and chloramination but
consideration was given to continue with DBNPA. In consultation with DOW Chemical
Australia, a control strategy was selected for a daily shock dose of DBNPA for 60
minutes and at 20 ppm into the feedwater prior to the UF strainers which has increased
lifespan of RO elements and overall plant capacity.
2.0 DISCUSSION
2.1 Plant Hygiene Audit Analysis
Plant microbial audits designed to assess plant hygiene, equipment design and raw
material quality by analysis of swab and liquid samples at ASRP has been intermittently
conducted at ASRP.
th
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Bendigo Exhibition Centre, 31 August to 1 September, 2016
The bacteria colony counts from the hygiene assessments quantify the severity of
biofouling and effectiveness of the microbial strategy. The rating scale in Table 1 is used
to quantify the extent of bacterial growth of plated samples taken from each location;
higher the score, the greater bacteria count.
Table 1: Hygiene report bacteria score
Plating Results Score ~ cfu/ml
No detectable survival 0 <1×101
1 – 9 colonies 1 1×101 - 9×101
10 – 99 colonies 2 1 × 102 – 9.9 ×102
100 – 300 colonies 3 1×103 – 3×103
> 300 colonies 4 > 3×103
The applications of DBNPA in earlier operational periods varied from using it as a CIP
chemical, continuous dose at 1ppm into the RO cartridge filters and intermittent shock
dose via RO displacement tanks. Without any pre-treatment of the feedwater prior to the
RO system, there were many areas for bacteria to spawn and populate thus higher bacteria
counts were detected throughout the system.
Figure 1: Schematic of Altona Salt Reduction Plant (22 Sampling locations
denoted by SP)
The hygiene audits conducted at the 11 equivalent sampling locations across the plant
between different operational periods shows a significant reduction in the total bacteria
score. The results emphasize the importance of sterilisation of the feedwater as early
upstream as possible, particularly if DBNPA is used alone as pre-treatment for microbial
and biofouling control. By treating the piping system upstream of the RO membranes, the
DBNPA is attacking any potential source areas for bacteria to spawn and proliferate. The
average total bacteria score during periods where DBNPA dosage was focused only on
the RO system either as continuous or shock dose, returned an average score of 15 (out of
a maximum 44) across the 11 SPs.
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Bendigo Exhibition Centre, 31 August to 1 September, 2016
When the DBNPA dosage was moved to the feedwater stream, a 63% reduction in
bacteria score was realised across the same11 SPs; average total bacteria score was 5.6.
The biocide was able to sterilise previously missed process areas upstream of the RO
system including RO cartridge filters, UF System, UF storage tanks and UF strainers. As
a result, less fouling was observed on the RO cartridge filters and the performance of the
RO membranes improved; there is a direct correlation between bacteria counts and
frequency of RO CIP cleans.
Table 2: Comparison of total bacteria score between periods of different DBNPA
application
2011-13 2015-16
Location of DBNPA RO Cartridge Filter/CIP Feedwater
Application Tank/RO Displacement Tank
No. of Reports 3 8
Average Total Bacteria 15 5.6
Score (lower score is better)
% Improvement 63%
A comprehensive set of hygiene audits over 22 sampling locations (Refer to Figure 1)
across ASRP were conducted on a fortnightly basis (by DOW Chemical) to quantify
effectiveness of the current DBNPA regime. SP1, SP2 and SP18 were locations of
concern due to the absence of DBNPA because they are located either before the dosing
point or after where it has exited the system. Anecdotal evidence supports almost all of
the DBNPA is rejected in the RO concentrate. At a shock dose of 20 ppm, residual
DBNPA was detected through the biocide testing kit between SP3 and SP17 for up to 4
hours from time of dosage. Future works include a secondary biocide dosing point post 1st
Pass RO permeate. However, ASRP has not seen any deterioration in Second Pass RO
performance.
Table 3: Average bacteria score across 22 SPs of current DBNPA application
SP1 SP2 SP18 SP3-SP17
Sampling Feedwater Tank Pre-UF Strainer RO 2nd Pass All Other
Description Feed Process Areas
Average 2.12 2.63 3 1.03
Bacteria Score
SP18 returned the highest average bacteria score of 3, best explained with microbial
growth in areas without DBNPA. The other 19 SPs have shown good results with a
Bacteria Score ranging from 0 – 1.
2.2 RO Cleaning-in-Place Frequency
The ASRP RO membranes are subjected to fouling of foreign materials that are present in
feed water. Typically, organic and biological matters are the primary contributors to
fouling in 1st Pass RO membranes. Metal oxides and inorganic metal precipitates are
controlled by pre-treatment, recovery control, feed pH correction and Antiscalant dosing
systems. Fouling reduces performance of membranes which is represented by reduction in
permeate flow, increased salt passage and a higher pressure drop. A Clean-in-Place
chemical cleaning process is required to remove the fouling on membranes and recover
the performance of the RO system. Excessive fouling leads to frequent CIPs, decreased
plant capacity and increased chemical costs.
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Bendigo Exhibition Centre, 31 August to 1 September, 2016
Greater biological fouling on the RO membranes occurred during periods when DBNPA
application was targeted only at the RO process areas. Characteristics in the Feedwater
into ASRP such as pH, alkalinity and metal concentration has not varied significantly
between different periods of DBNPA application to suggest the primary fouling was other
than biological based. Autopsies of the RO cartridge filter show a slimy brown foulant
indicative of organic or biological matter rather than scaling precipitates.
During periods where the feedwater was not treated by DBNPA, a combination of
influent nutrients and bacteria colonies potentially encourage biological growth in un-
sterilised areas prior to the RO membranes. This leads to rapid fouling on the RO
cartridge filters and subsequently RO membranes trigger set points for CIPs. CIPs reduce
plant capacity as a RO train needs to be taken offline and is a costly exercise due to
chemical consumption. Most typically, the RO membranes at ASRP undergo a Caustic
Soda followed by a Hydrochloric Acid clean for each CIP.
The frequency of CIP cleans significantly reduced when DBNPA was used as pre-
treatment to the feedwater, directly relating to reduced RO membrane fouling. Pre-
treatment aims to prevent microbial outbreaks upstream thus relating to reduced chances
of rapid fouling. For example, a CIP was required on average once every 60 days
compared to 105 days in 2nd Pass RO Trains between the two different DBNPA
operations.
Table 4: Average time since last CIP (days)
2011-13 2016
Location of DBNPA No. of RO Cartridge Filter/CIP Feedwater
Application Trains Tank/RO Displacement Tank
1st Pass RO 3 46 86
2nd Pass RO 2 60 105
3.0 DBNPA PROPERTIES
DBNPA is a fast-acting biocide that demonstrates a broad spectrum of activity, at low
concentration, against bacteria, fungi, yeast, cyanobacteria (also referred to as blue green
algae) and true algae. It is completely miscible with water and begins to function
immediately upon addition into the feed water and antimicrobial control is rapidly
achieved if properly dosed. Recommended dosage rates for DBNPA are between 1 –
200ppm dependent on the system and degree of fouling and the addition of sodium
bisulphite or other reducing agents must be suspended at least 15 minutes prior to
addition of the product to prevent neutralisation and deactivation. When added to an RO
system, DBNPA is rejected by the thin-film composite membrane layer, and at use
dilution, shows excellent compatibility with all materials of construction of the RO
membrane module.
DBNPA offers an advantageous combination of quick kill properties followed by fast
chemical degradation, including hydrolysis. The dominant degradation pathway at use
conditions involves reactions with nucleophilic substances or organic material invariably
found in water. Nucleophilic degradation forms cyanoacetamide. When the
disposal/storage of concentrate involves exposure to UV-radiation additional degradation
will occur.
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Bendigo Exhibition Centre, 31 August to 1 September, 2016
When sufficiently diluted, DBNPA and its degradation products become biodegradable.
The ultimate degradation products formed from both chemical and biodegradation
processes of DBNPA include ammonia, carbon dioxide, and bromide ions.
4.0 COMPARISON COST WITH OTHER ALTERNATIVES
Below is a brief introduction to different strategies utilised to control of microbial growth
and biofouling of membrane filtration systems in recycled water applications and its
target doses.
Table 5: Chemical consumption and cost analysis
Pre-Treatment Chemical Target Usage/day Cost/day Cost/ year Total
Strategy Concentration (L/day) (AUD/day) (AUD/year) Cost/year
(ppm) (AUD/year)
Chloramination Aqua Ammonium 2 (as NH3) 124 187 68,135 $ 153,755
Hydroxide3
(25% w/v as
Ammonia)
Sodium 9 (as Cl2)2 920 235 85,620
Hypochlorite4
(13% w/v as
Chlorine)
Chlorination / Sodium 15 (as Cl2) 742 390 142,350 $ 534,895
Dechlorination Hypochlorite4
(13% w/v as
Chlorine)
Sodium 22.51 1,533 1,075 392,545
Metabisulphite5
(31% w/v)
Biocide continuous DBNPA3 5 280 1,830 667,950 $ 667,950
(20% w/w)
Biocide (shock DBNPA3 20 47 300 109,500 $ 109,500
dosing) (20% w/w)
1
Based on 1.5:1 SBS to Chlorine ratio; 2Based on 4.5:1 Chlorine to Ammonia ratio; 3Chemical delivered in a 1,000L
IBC; 4Chemical delivered into 2 x 20,000L tanks, 5 Chemical delivered into 1 x 2,000L tank
Chloramines: can be used as a disinfectant and can be effective in control of
biofilms. Chloramine can last longer than chlorine in water and produces fewer
disinfection by-products (EPA 2015). Monochloramine is the most effective
Chloramine disinfectant. Chloramines are usually formed by adding anhydrous or
aqueous ammonia to water containing free chlorine (HClO). The process of
chloramination depends on pH and concentration, pH levels below 7.5 or chlorine
to ammonia ratios exceeding 5:1 increase the formation of dichloramine (NHCl2)
and nitrogen trichloride (NCl3) which are undesirable by-products (Water Quality
Association 2013).
Chlorination/dechlorination: Chlorine is a highly effective method of
disinfection however, chlorine attack will irreversibly damage the FILMTEC™
RO membranes. Dechlorination upstream of the membranes is required to protect
the membranes from oxidation. In theory, 1.34 mg of sodium metabisulfite will
remove 1.0 mg of free chlorine (DOW n.d. a).
Biocide: Biocide can be dose continuously like chlorine, monochloramines or can
be slug dosed.
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Bendigo Exhibition Centre, 31 August to 1 September, 2016
20ppm for slug dose and 5 to 10ppm for continuous dose (DOW n.d. b). Fouling
microorganisms can build up a resistance to biocide over time, slug dosing biocide
minimises the likelihood of this happening.
The daily and annual cost associated to each strategy has been estimated based on the
recommended chemical doses of each strategy, the ASRP daily flows treated (14MLD),
chemical concentrations, specific gravity of the chemicals as currently provided by supplier
and its costs based on the contract with chemical supplier currently in place.
5.0 CONCLUSION
ASRP has improved its plant performance with no additional pre-treatment for biofouling
such as chlorination or chloramination. The sole DBNPA application at head of the plant
at 20 ppm and for 60 minutes a day, has helped to optimise ASRP operations by reducing
frequency of CIP cleans, extending life of process assets and lowered bacteria colony
counts throughout the plant.
The items for future implementation include:
1. Infrequent Chlorine Disinfection of the Feedwater Tank (SP1), upstream of the
DBNPA dosing point to attack biological species which have shown to be immune
to DBNPA, followed by Sodium Bisulphite quenching
2. Secondary DBNPA dosing point post RO 1st Pass Permeate Tank for sterilization
between 1st Pass RO and 2nd Pass RO due to DBNPA being rejected in the 1st Pass
RO concentrate.
The future works aim to prevent microbial outbreak in potential ASRP’s process areas,
specifically at the feedwater Tank into the plant, as well as expanding the control to all
biological species. Preliminary investigations have shown a once a month Sodium
Hypochlorite shock dose followed by DBNPA is a very effective control measure.
6.0 REFERENCES
DOW Water & Process Solutions n.d. a, Section 2.6.3 Chlorination / Dechlorination of
FILMTEC™ Reverse Osmosis Membranes, Technical Manual, DOW Water & Process
Solutions n.d, viewed 29 June 2016,
<[Link]
/[Link]?filepath=liquidseps/pdfs/noreg/609-
[Link]&fromPage=GetDoc>
DOW Water & Process Solutions n.d. b, Section 2.6.5 DBNPA of FILMTEC™ Reverse
Osmosis Membranes, Technical Manual, DOW Water & Process Solutions n.d., viewed
29 June 2016,
<[Link]
[Link]?filepath=liquidseps/pdfs/noreg/[Link]&fromPage=GetDoc>
EPA 2015, Public Water Systems, Disinfection By-products, and the Use of
Monochloramine, EPA, viewed 29 June 2016, <[Link]
water-systems-disinfection-byproducts-and-use-monochloramine>
Water Quality Association 2013, Chloramine Fact Sheet, WQA Organization, viewed 29
June
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