biogeorge paper # 04086

8/10/2019 Biogeorge Paper # 04086

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Plant Experience with Dosing Optimisation of an

Environmentally Friendly Biocide

Hugh FallonContact Energy

Hellabys RdOtara, Auckland

New [email protected]

George J. Licina

Structural Integrity Associates3315 Almaden Expressway, Suite 24

San Jose, CA 95118

ABSTRACT

Initial experience with an environmentally friendly biocide at a brackish water-cooled power

plant showed that the biocide was very effective in controlling microbiological fouling of piping andcondenser tubes. Subsequent activities demonstrated that the biocide could be used more economically

by closely tracking the biocides effectiveness on biofilm activity using an electrochemical biofilmactivity monitor.

Keywords: biocide, monitoring, biofilms, water treatment, cooling water

BACKGROUND

Water treatment, usually with biocides, is the most common approach for mitigation ofmicrobiologically influenced corrosion (MIC) based upon its ease of use. However, the use of a biocide

treatment alone is rarely effective for an already fouled system. The most commonly used biocides areoxidising agents that can also aggravate a corrosion condition that may have been established initially by

microbiological activity, but which may proceed with no further microbiological involvement. In suchcases, the use of a biocide, especially an oxidising biocide, may prevent further infestation but it can alsoprovide alternative and stronger half-reactions that fuel the corrosion activity. Biocide treatments alone


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are only likely to be effective when microbes actively participate in the corrosion process (e.g., bycatalysis of the reduction of oxygen, or by cathodic depolarisation in anaerobic systems), or when

microbes provide alternative reactions that exacerbate corrosion. In summary, biocide treatments are avery effective preventivemeasure against MIC; however, the condition of the corrosion process must

be well understood before biocide treatment is used to remediate an apparent MIC condition.

Contact Energy LTD own and operate the Otahuhu B 380 MW gas-fired single-shaft combined

cycle power station, located in South Auckland, New Zealand (Figure 1). Estuarine water is supplied to

the main cooling water system where the recirculation rate to a 2-pass titanium-tube condenser is some20,000 m3/hr. The velocity through the condenser tubes is 2 m/s. A hybrid 8-cell cooling tower is used

for heat rejection. The design T across the condenser is 9.9C. System losses (evaporation and purge

water) are made up continuously to the main system. Over 22,000 m3of make-up water are taken fromthe estuary each day to maintain the design cycles of concentration of 1.25.

The conductivity of the brackish make-up water can vary significantly between the low and hightide cycles; by as much as 15 mS/cm. Seasonal variations are also notable due to high rainfall totals

during winter and spring. In general, the make-up water conductivity varies between 5 and 35 mS/cmbetween June and November. During the warmer months the average conductivity is more stable, and

changes tend to occur gradually in the range 35 to 50 mS/cm.

The make-up water is treated continuously with industrial grade bleach to provide a free halogen

residual of between 0.5 to 0.8 mg/l. A proprietary stabilised bromine-based biocide is added to therecirculating water system to augment the primary (make-up) oxidant dosing. The bromine product is a

unique, biomimetic, stabilised liquid bromine biocide, with excellent microbiological and biofilmcontrol properties, while exhibiting lower toxicity and lower reactivity than traditional oxidisingbiocides. A total halogen residual in the range 0.1 to 0.40 mg/l is maintained in the main system. All

residuals were reported in plant data as chlorine for convenience and for direct comparison with on-linechlorine analysers. However, the estuarine nature of the water and the injection of the stabilised brominebiocide ensure that the residuals consist of bromine in a mixture of free, stabilised and combined

species. A proprietary scale inhibitor is also dosed to the recirculating water.

That treatment has effectively controlled MIC and biofouling throughout the cooling system.

Biocide Optimisation

Originally, the cooling water chemistry on the plant was quite reactive and the effects of foulingin the system were assessed off-line without the aid of any on-line techniques; clearly without any

predictive indicators. Plant policy was to apply chemicals to provide fixed, target residuals. If aperformance or fouling problem were noted, the amounts of chemicals would be increased. Thechemical program was expensive while this policy was maintained.

A more sensible approach was considered to be the application of chemicals, especially thebiocides, according to the system demand and the system performance. That biocide optimisation effortis a wide-ranging and thorough instrumentation project with the aim of using the smartest technology tofully monitor and optimise the system. As a part of that program, the plant installed two

BI?GEORGE electrochemical biofilm activity probes (Figure 2), a DATS model heat exchanger,and other instruments in a test program intended to evaluate the suitability of the probe for use at the

plant, then to use the probe output data as part of a water treatment control management system, whichwould add biocide on a schedule and at concentrations that would keep system surfaces free of biofilm


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polarisation cycle that is applied. As shown in other systems, the electrochemical biofilm probe will foulquite quickly (in a few days) and the trends for applied and generated currents will rise to significant

values compared to the baseline if there is significant fouling potential in the system.

In the course of the optimisation activity, probes have been isolated from the biocide treatedflow, have been exposed outside of the system in a bucket of make-up water, and have been exposed inboth inlet and outlet streams.

RESULTS

Initial Exposures

Figures 6 and 7 illustrate the initial performance. When the probe was exposed to the biocide-

treated water at a flow comparable to that experienced by the condenser tubes, little or no evidence ofany biofilm activity was seen, which was consistent with visual examinations of system surfaces. This

behaviour was not unexpected as noted above. There were indications of biofilm on April 29th and June12th, however, in both cases, the system itself was able to clean up the probe.

Those initial results led to modifications of the flow conditions experienced by the probe,starting with a period of stagnation.

Effects of Flow Rate and Biocide Treatments

The objective of subsequent changes in the exposure of the biofilm probe in terms of flow ratesand exposure to biocide were intended to permit the probe to foul, then to observe the response of theapplied and generated currents to biocide dosing. In general, those conditions showed that once a system

(including the probe surfaces) is fouled, it may not be easy to establish the previously clean conditions.It should also be pointed out that since the biofilm probe will be encouraging biofilm formation even

while the water has oxidant in it, non-polarised surfaces may be recovered with more ease than the probeelectrodes. Finally, the changes in flow and dosing conditions past the probe permitted the biofilm'sresponse to stress to be observed.

As shown in Figure 8, on July 16th , the biofilm probe was exposed to dead leg conditions (i.e.,

flow through the condenser outlet tapping point was isolated). In addition, the applied potential wasincreased from 200 to 400 mV and the applied potential time was increased from 1 hour to 90 minutes.Baseline and alarm setpoints were not reset. The intent was to observe when and if the probe would foul,

then to introduce process water to it and to note the response of that biofilm to flow.

As of July 18th the applied current trend started to increase dramatically. There was a coincident

large negative deviation on the generated current trend at the same time.

On July 30th 2002 at 10:16, the process flow was introduced to the biofilm probe again at a lowflow of less than 1-liter per minute. The applied current decreased somewhat from its earlier peak and

was then steady, up to July 31st, when both the applied and generated trends started to increasesignificantly.


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On August 7th 2002, flow past the biofilm probe was measured as 0.6 litres per minute. Biocide(stabilised liquid bromine) dosing was increased (from a 10% pump stroke setting to 20%) for

approximately seven hours. The overall flow out of the rack was set to about 1.25 litres per minute forthis time period. The generated current began to decrease from 12:15 on the same day.

On August 13th at 08:35 the flow from the rack was increased to about 6 l/min and the next daythe bromine biocide dosing was doubled (10% to 20%) from 08:00 to 14:00. Between August 17th and

22nd, the rack flow decreased from 6 to 3 litres per minute, due to some mud accumulation further down

the drain line, which decreased the flow rate over a number of days, and both the generated and appliedcurrent trends were starting to increase again.

On August 22nd at 15:30, the probe was swapped over to the inlet line tapping point (the line that

furnished the DATS) with a flow of 28 l/min. The toxicitywould only be slightly higher on the inlet sideof the condenser; as such, this is more an indication of the effect of flow on the biofilm than the effect of

toxicity.

At 15:00 on September 3rd2002, the applied potential was again changed downward, from 400

mV applied for 90 minutes to 200 mV for 1 hour. Those adjustments reflect the pre-July 16th settings.Between August 22nd when the probe location tapping was changed, and September 3rd when the

potential and time were changed, the applied current and generated currents changed from 3.4A and0.15A, respectively (both being quite steady), to values after the setting changes of 1.75A and (still)

0.15A, respectively. On Friday September 6th , when the bromine biocide dosing was turned off from10:45 to 15:15, the generated current values did not change significantly.

On September 10th 2002 the bromine biocide dosing schedule was changed from a continuous

mode to a1 hour off/1 hour on schedule from 19:00 to 08:00 on the 11th . The applied and generatedcurrent trends appeared to show a slight decrease during this on/off test. Note that the hypochloritedosing was on as normal to the make-up water during that time.

The plant was shut down for the weekend on Friday September 13th . Just before shutdown the

recirculating water temperature was a fairly steady 25C. Over the weekend, the recirculating watertemperature went as low as 6.5C (on the 14th). Bromine biocide dosing was from 08:00 to 16:00 for the

14th and 15th. The plant restarted on the 15th at 17:00 and the recirculating water got to 31.5C by 20:00.

On Monday Sep 16th, the bromine biocide dosing was set to a 1-hour off/ 1 hour on schedule.

The applied current decreased from 1.43A on the morning of the 13th to 1.11A on the morning of the

17th while the generated current remained steady at -0.08A. All or part of the applied current reductionmay have been due to the temperature shock during the weekend.

On Tuesday September 17th , samples (swabs) were taken from the biofilm surfaces, the BioBox

(a transparent Perspex box with a tortuous flow path, which encourages sedimentation and fouling), andthe recirculating water corrosion coupon. Water samples were taken from the probe tapping point (upperlevel) and the BioBox. This completed this dead-leg/biofilm production trial.

In parallel with the tests of the on-line probe (as detailed above), an identical probe was exposed

to another set of controlled test conditions. Initially, the unit was left suspended in a bucket of untreatedseawater to which some sugar was added. The unit went quickly into alarm on a high applied current.The biofilm activity on that probe peaked on July 19th with significant scatter in the trend plots. The

applied current levels had begun to decrease significantly after July 19 th . The probe in the bucket test


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levels that are consistent with, and in some cases, better than, the baseline conditions that weredetermined in the initial phases of the study.

Figure 12 shows the relative chemical treatment costs for the plant over the past 2 years. The

electrochemical biofilm activity probe has been incorporated into an overall water treatmentmanagement system that hasallowed the site to optimise the use of the stabilised bromine-based biocideto the extent that a 25% saving in chemical costs has been realised to. Further, total savings of up to 40%

compared to pre-optimisation costs are expected in the medium term as the dosing is changed to a fully

performance-based approach, with the electrochemical biofilm probe systemas an integral part of theoverall biocide management program.

The biocide optimisation activities are continuing as the plant begins to approach its goal of

continuously exposing the probe to actual process water that has been treated less aggressively withbiocide such that the biocide content of the water is just sufficient to keep surfaces clean. These

activities have continued to show that the stabilised bromine biocide is effective and that tools such asthe electrochemical biofilm probe are effective in helping to optimise those treatments such that theplant has already reduced biocide usage.

CONCLUSIONS

The electrochemical biofilm activity probe was shown to be sensitive to biofilm formation in theplant system.

The electrochemical biofilm activity probe system definitely promoted preferential biofilmdevelopment on the sensor probe. That aspect of the system providesa useful lead factor for the plant,

where fouling will develop on the probe before it becomes established on the general non-polarisedsurfaces of the main system.

Biofilm can become readily established if dosing control is lost; biofilm can also develop instagnant areas.

Once established, biofilm is not easily removed, to the extent that it would be difficult to re-establish the previously clean conditions of the plant.

Maintaining clean conditions on the biofilm probe surfaces ensures the main plant conditions are

also clean. Sessile analysis of the probe and cooling system surfaces supports this claim.

The stabilised liquid bromine biocide is clearly effective in maintaining surfaces free of biofilms,

whether those surfaces are heat exchanger tubes or probe electrodes.

The biocide was also demonstrated to effectively return a probe surface with some

microbiological fouling to a condition consistent with a clean surface.

The electrochemical biofilm activity probe has been incorporated into a total water treatmentmanagement system that is allowing the site to optimise the use of the stabilised bromine-based biocide

to the extent that a 25% saving in chemical costs have been realised to date.


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Further total savings of up to 40% compared to pre-optimisation costs are expected in themedium term as the dosing is changed to a fully performance-based approach, with the electrochemical

biofilm probe systemas an integral partof the overall biocide managementprogram.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the cooperation and support of Mr John Rickerby, Mr. Harry

Habib and Mr. Ralph Woulfe of Contact Energy Limited, Mr. Elie Tanos of Chemtrack,and Mr. RoyMenzies of Ondeo-Nalco.

REFERENCES

1. G. J. Licina, George Nekoksa, The Influence of Water Chemistry and Biocide Additions on theresponse of an On-line Biofilm Monitor, CORROSION/95, Paper No. 527, NACE International,

1995.

2. G.J. Licina, L.P. Venhuis, Biocide Optimization Using an On- line Biofilm Detector, International

Water Conference, Paper 00-060, October 2000.

3. G.J. Licina, Monitoring Biofilms on Metallic Surfaces in Real Time, CORROSION/2001, PaperNo. 442, NACE, Houston, TX, 2001.

4. M.H. Dorsey, et al., Monitoring for Corrosion and Microbiological Activity in a Cooling WaterSystem, CORROSION/2002, Paper No. 441, NACE-International, 2002.

5. G.J. Licina, Experience with On-Line Monitoring of Biofilms in Plant Applications, CoolingTechnology Institute, 2003.

6. P.G. Kutzora, L.B Peterson, G.J. Licina, Monitoring Biofilms on Cooling Water System Surfaces,

Electric Utility Chemistry Workshop, University of Illinois, 2003.

7. W.E. Garrett, G.J. Licina, "Monitoring Microfouling in a Once-Through Service Water System",

Eighth EPRI Service Water System Reliability Improvement Seminar, 1995.

8. G.J. Licina, Optimizing Biocide Additions via Real Time Monitoring of Biofilms,CORROSION/2004, Paper No. 04582.


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TABLE 1RESULTS FROM SWABS FROM BIOFILM ELECTRODES AND EPOXY PROBE BODY

Electrodes Titanium Epoxy Titanium Epoxy

Date 9/17/2002 10/25/2002 10/25/2002 10/31/2002 10/31/2002

Microscopic Examination

(1000X Magnification)

Sludge + - - - -Siliceous Material - + - + -

Protozoa - - - - -

Nematodes - - - - -

Diatoms + - - - -

Unicellular Algae + - - - -

Filamentous Algae - - - - -

Unicellular Bacteria +++ - - - -

Filamentous Bacteria - - - - -

Amphipods (Larvae,nymphs etc)

Yeast/Filamentous Fungi - - - -

Culturing( CFU/ml)

Yeasts ND ND ND ND ND

Moulds 100 10 10 10 10

TVC at 25 Deg C 14000 21000 800 21000 800

Anaerobic SRB ND 10 ND 10 ND

Total Anaerobic Bacteria 600 50 600 50

Pseudomonas ND 13000 700 13000 700

Clostridium ND 50 ND 50 ND

Heterotrophic Iron ppt.

Bacteria

100 200 20 200 20

Nitrifying Bacteria ND ND ND ND ND

Denitrifying Bacteria ND ND ND ND ND


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FIGURE 1 - Aerial photograph of the site

FIGURE 2 - Electrochemical Biofilm Activity Probe


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FIGURE 3 - Results from Biofilm Optimisation Study Brackish Water-cooled Incineration Plant (fromReference 2)

FIGURE 4 - Probe Tapping on Cooling Water Return Line

FIGURE 5 - View of Probe Installed in Tap


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Applied Current Data

C99-101/399-109

0.0

0.5

1.0

1.5

2.0

4/10/2002

4/17/2002

4/24/2002

5/1/2002

5/8/2002

5/15/2002

5/22/2002

5/29/2002

6/5/2002

6/12/2002

6/19/2002

6/26/2002

7/3/2002

AppliedCurrent,microA

mps

FIGURE 6 - Applied Current Trend April 2002-June 2002 (Color code: Yellow = baseline beingestablished; Green = probe is clean; Red = probe is fouled)

Generated Current Data

C99-101/399-109

-1.00

-0.80

-0.60

-0.40

-0.20

0.00

0.20

0.40

0.60

0.80

1.00

4/10/2002

4/17/2002

4/24/2002

5/1/2002

5/8/2002

5/15/2002

5/22/2002

5/29/2002

6/5/2002

6/12/2002

6/19/2002

6/26/2002

7/3/2002

GeneratedCurrent,mic

roAmps

FIGURE 7 - Generated Current Trend Aril 2002 June 2002


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Otahuhu CCPP

ONLINE PROBE (Condenser Outlet BioGeorge Probe)

Generated Current Data Jul 16 to Sep 17 2002

16/9/200219:00ST-70dosingoff(TIM

ER1)

15/9/200216:55:Plantre-star

13/9/200220:55:Plantshutdown

10/09/2002:ST-70dosingoff(TIMER1)

06/09/2002:ST-70dosingofffo

r4.5hours

03/09/02:EAPPto200mVfor

1hour

22/08/02:Pro

beswappedfrom

Outlet

toIn

lettappingpoint

16/07/02:Dead-legestablished;IAPPt

o400mV(from

200mV)for90min(from(60min)

30/07/02:Processflowre-establis

hed;Sampleflow=0.5

l/min

07/08/02:Processflowincreasedto1.25l/min;

7-hourST-40testwithtwicetheproductra

te

13/08/02:Processflow

incr

easedto6l/min

16/08/02:Flowdecreasedto3l/min

-0.40

-0.20

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

2.00

2.20

07/15/02

07/18/02

07/21/02

07/24/02

07/27/02

07/30/02

08/02/02

08/05/02

08/08/02

08/11/02

08/14/02

08/17/02

08/20/02

08/23/02

08/26/02

08/29/02

09/01/02

09/04/02

09/07/02

09/10/02

09/13/02

09/16/02

09/19/02

GeneratedCurrent,microAmp

FIGURE 8 - Generated Current Trend July 2002 through September 2002

Otahuhu CCPP


ONLINE Probe

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

9/30/2002 10/7/2002 10/14/2002 10/21/2002

AppliedCurrent,

microAmps

FIGURE 9 - Continuous exposure to treated cooling water


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Otahuhu CCPP

26June 03 YTD


0.0

0.5

1.0

1.5

2.0

2.5

3.0

26-Jun-03

3-Jul-03

10-Jul-03

17-Jul-03

24-Jul-03

31-Jul-03

7-Aug-03

14-Aug-03

21-Aug-03

28-Aug-03

4-Sep-03

11-Sep-03

Date

AppliedCurrent,microAmps

FIGURE 10 - Applied Current History 2003

Otahuhu CCPP

26June 03 YTD

Generated Current Data

PlanttripJuly15th,14:1

Watertemp28degreest

10degreesCelsius

PlantstartJuly17th,13:30

Watertempto28degreesCelsiu

5-dayplantoutagebegin

Dead-legintroduced

PlantstartJuly23rd,15:00

Watertempto30degreesCelsiu

Errorinprobe,July31st,10:0

Probefunctional,Aug7th,10:

P

robeinitialisedJune26t

Flow=30l/min

-1.00

-0.80

-0.60

-0.40

-0.20

0.00

0.20

0.40

0.60

0.80

1.00

23-Jun-03

25-Jun-03

27-Jun-03

29-Jun-03

1-Jul-03

3-Jul-03

5-Jul-03

7-Jul-03

9-Jul-03

11-Jul-03

13-Jul-03

15-Jul-03

17-Jul-03

19-Jul-03

21-Jul-03

23-Jul-03

25-Jul-03

27-Jul-03

29-Jul-03

31-Jul-03

2-Aug-03

4-Aug-03

6-Aug-03

8-Aug-03

10-Aug-03

12-Aug-03

14-Aug-03

16-Aug-03

18-Aug-03

20-Aug-03

22-Aug-03

24-Aug-03

26-Aug-03

28-Aug-03

30-Aug-03

1-Sep-03

3-Sep-03

5-Sep-03

7-Sep-03

Date

Genera

tedCurrent,microAmps

FIGURE 11 - Generated Current History 2003


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Otahuhu B Combined Cycle Power Station

Total Chemical Cost Trend for Cooling Water Treatment

Plant

Outage

Plant

Outage

Optimization Project

Commences

Projection for

2004

08-Feb-01

22-Mar-01

03-May-01

14-Jun-01

26-Jul-01

06-Sep-01

18-Oct-01

29-Nov-01

10-Jan-02

21-Feb-02

04-Apr-02

16-May-02

26-Jun-02

08-Aug-02

19-Sep-02

31-Oct-02

12-Dec-02

23-Jan-03

06-Mar-03

17-Apr-03

29-May-03

10-Jul-03

21-Aug-03

02-Oct-03

13-Nov-03

25-Dec-03

05-Feb-04

18-Mar-04

29-Apr-04

10-Jun-04

22-Jul-04

02-Sep-04

14-Oct-04

25-Nov-04

RelativeChemicalCostfor

CoolingWaterTreatment

FIGURE 12. Relative Chemical Costs from Initial Biocide Optimisation Activities

biogeorge paper # 04086

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