Cooling Water Treatment -An Experience at GNFC

By N. B. Bhatt and A.M. Vashi

GNFC AT A GLANCE
Incorporation : Capacity Per Annum Ammonia : Urea : Methanol : Formic Acid : Acetic Acid : Weak Nitric Acid : Conc. Nitric Acid : Calcium Amm. Nitrate : Amm. Nitro phosphate : Captive Power : IT infrastructure : NCPL for Aniline and TDI

May10,1976
4,45,000 MT 5,94,000 MT 1,30,000 MT 8,000 MT 1,00,000 MT 2,47,500 MT 66,000 MT 1,42,500 MT 1,42,500 MT 50 MW VSAT, Info tower, PKI
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GNFC Ammonia Plant

One of the world largest single stream AmmoniaUrea complex Process Route : Partial oxidation of fuel oil Ammonia 1350 MTPD 117 % Urea 1800 MTPD 118%

Capacity Capacity Utilization

Formic acid, Acetic Acid, Aniline, TDI and Methanol plants are dependent on Ammonia plant

Integration of Ammonia Plant with other plants

UREA
C02
SYN GAS METHANOL 1 H2+CO2+CO

NH3 CO

ACETIC ACID

Purge Gas. CO2

AMMONIA 1350 MTPD PLANT

Tail Gas CO

BOILER FORMIC ACID

METHANOL 2

P.G. C02 NH3 CO

Nitro Phosphate Unit

NCPL
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Ammonia Cooling Water System

Induced draft CT : 12 no. of cells CW circulation flow : 34,000 m3/hr Heat Duty : 352 Mkcal/hr CW Supply temperature: 33 Deg C. CW Return temperature: 43 Deg C CW pump capacity : 6800 m3/hr each CW header pressure : 3.1 barg

Old In-house CW Treatment

In-house treatment program developed by GNFC was followed before Dec-99 SHMP Organo-phosphate Zinc phosphate Biocides COC : 3 ~ 4
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Present Cooling Water Treatment

M/S Chembond Drewtreat treatment: First introduced in Urea plant in 1992 Since Dec-99 in Ammonia plant Based on: Zinc glassy ortho -meta phosphate(KW101) Organophosphate-PBTC with low molecular wt polymer(KW1002G) Biocide chemicals : Chorine Dioxide Quaternary Ammonium compound Dichlorophene DBNP (Di-bromo- nitroso-phenolic comp. Bio-dispersant (KW-BD)
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CW Treatment Monitoring

Dedicated CW water cell Monitoring of Analysis and supervision of Ammonia CT by M/s. Chembond Regular activities: Daily : Performance evaluation by CW cell Weekly: CT cells deck algae cleaning Monthly :

Sterilization of side stream filters Review of exchangers performance Corrosion rate monitoring

Quarterly: Review with M/s Chembond modification in treatment; if required Bio-fouling monitoring Inspection and cleaning during shut down

for

Benefits
With better treatment and Modifying the limits of critical parameters COC improved to 6~6.5 Saving in CW make up : 11,000,00 m3/year. Reduction in corrosion rate : From 3~4 mpy to <1.5 mpy Reduction in scaling Reduction in microbiological activity

TVC SRB

: 50000 : 100~200

Sustained performance of surface condensers

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CW parameters
pH Make up CW water circulation 7.0~8.0 6.8~7.2

Conductivity
TH Mg Hardness

Micro mho 200~400

ppm ppm 70~150 25~70

2500max
800~825 250~350

Ca Hardness Chloride
Silica Turbidity

ppm ppm
ppm NTU

50~85 10~25
10~20 1~2

450~550 250max
100~125 10
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Typical CW parameters
Ortho PO4 Poly PO4 Organo PO4 Total PO4 Zinc TDS NH3 TVC SRB Circulating water ppm 5~6 ppm 1.5~3.0 ppm 1.5~3.0 ppm 7~10 ppm 0.5~1 ppm 1500max ppm 10 per ml 50,000 mpn /100 100 ml

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Ammonia Synthesis Gas Cooler E706

A case study

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History of E706
Synthesis Gas cooler- a critical exchanger condenses 50~60% ammonia in synthesis gas loop Original exchanger started leaking within a year of service

Frequent

and severe leakages started within a short span of time

Cause : Flow induced vibrations Replaced in July-1984 :

better design exchanger : SS304 tubes and split flow of CW side installed

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Features of New Synthesis Gas Cooler

New design exchanger installed in 1984 H.T. Area : 1445 m2 Heat Duty : 14.28 MKcal/hr Cooling water : Shell side In/Out temp : 33/43 No of passes : Split flow CW flow : 1500 m3/hr MOC : CS Synthesis gas : Tube side In /Out temp : 79/ 39 Pressure : 230 bar No of pass : 2 , U-tubes No. of tubes : 1095 MOC : SS-304

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Leakage of E706

After 17 years, first leakage noticed in May-2001 Process gas containing 18 % Ammonia leaks to CW side Gas was coming out with from shell side vent

pH Ammonia Conductivity Ca Hardness Chloride Turbidity Total Hardness ORP

IN OUT Diff. 7.4 9.1 +1.7 5~10 ppm 15~50 ppm +10~40 1240 324 236 14 664 +320 1150 272 208 16 572 -300 -90 -52 -32 +4 -92 -620

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Leakage of E706
Consequences
5 ~10 ppm Ammonia in CW circulation system Elevated pH of CW outlet to 8.5 Chlorination limitation High microbiological growth - nitrifying bacteria CW supply pH tends to remain low Biomass fouling in the exchangers Gas pocketing in the exchangers Back pressure in the E706, less CW flow through it Scaling in the exchangers of CW system
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Repair of E706 :1
In October 2002 S/D
CW side back-flushed:
Sludge of ammonia salts was flushed out

Tube bundle Inspected from CW I/L nozzle:

Found completely blocked with white sludge

Bundle pulling out was not possible Chemical cleaning with 5% sulphamic acid
Results was not satisfactory

Shell was cut open from one side and cleaned with high pressure Jetting Hydro-test at 12 barg was carried out:
3 leaky tubes plugged

Leakage Persisted

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Scaling in E706

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E 706 SHELL SIDE SCALING

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Repair of E706 : 2
In Jan 03 S/D

In Jan03 opportunity Chemical cleaning with 5% sulphamic acid Leak test was taken. No leakage identified,

Why? During normal operation, press diff. between shell and tube is very high 230 bar, cracks open up at high pressure Shell is low pressure part Leakage not detectable with hydro test at 12 bar pressure
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Repair of E706 : 3
In April 03 S/D
A special ammonia test carried out Shell plates cut and the bundle cleaned with hydro jetting Shell pressurised to 1 bar with N2 and further to 2 bar with Ammonia Leakage detected by placing Ammonia test paper on the tube sheet and observing color change to blue 12 tubes were detected and plugged However, CW outlet ammonia pick up and pH still indicated leakage after start-up
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To Sustain Operations
Challenging task : To maintain the thermal performance of E706 E706 performance deteriorated due to scaling and gas back pressure, syn gas outlet temp increased to 50 deg C from 39 deg Load on down stream refrigeration unit was increased, steam consumption increased by 4 Mt/hr

Measures Taken:
1.0 Local gas release provision 2.0 Managing Micro biological activity 3.0 Managing scaling
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1. Local Gas Release

Local venting
10 no. of 1 tapping were taken on-line from the shell and connected to a 4 vent header Shell side Safety valve was dropped & line extended up to CT height

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SAFETY VALVE LINE VENT GAS HEADER

E706

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2.0 Managing Micro biological activity

In presence of ammonia, it is difficult to achieve free chlorine For effective microbiological activity control:
Dosing of Chlorine dioxide started More stable and effective even at higher pH value Does not react with Ammonia and organic comp. Bromine based biocide was also started
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2.0 Managing Micro biological activity

Additional bio-dispersant dosing was started Frequency of Sterilization of side stream filters increased : once a week CW system and exchangers Monitoring by measuring ORP Nitrate Nitrogen, nitrifying bacteria monitored

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3.1 Managing Scaling

Measures taken to contain scaling: 1. Local Polymeric Dispersants dosing Effectiveness checked by analyzing Ca-Hardness at CW inlet and Outlet, before and after dosing

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3.1 Managing Scaling

Before dosing dispersants
pH Ca H TIP E706 IN 6.8 450 6.7 E706 IN pH Ca H TIP 6.8 452 10.3 E706 OUT 8.5 440 5.4 E706 OUT 8.9 448 10.6 Diff +1.7 -10 - 1.3 Diff +2.1 -4 +0.3
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After dosing dispersants

3.2 Managing Scaling

2.

3.

Back flushing: Loose scale partially removed by the exchanger back flushing during short interruptions Nitrogen Bumping: Twice in a day Low pressure N2 blowing for half an hour was done in the exchanger for removing loose scale The removal of scale is ensured by analyzing CW outlet sample indicating rise in Turbidity by 50 ~90 NTU and rise in Ca-Hardness by 10 ~25 ppm.
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Effect of Nitrogen Bumping

E706 CaHardn ess Rise in CaHardness Turbidity Rise in Turbidity

CW Inlet CW Outlet Before Bumping CW outlet After Bumping

464 460 480

--4 +20

18 28 95

-+10 +77

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3.3

Managing Scaling

4. Local CW make up at E706 inlet To reduce Hardness- a key factor for scaling CW outlet hardness was reduced from 700 ppm to 550 ppm 5. Local Sulphamic acid dosing To reduce local pH Special arrangement made for dosing
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E706

LOCAL WATER MAKE-UP

SULPHAMIC ACID DOSING TANK

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Plant Operation could be sustained for 3 years till the replacement of the exchanger in April 2004 with the effective problem specific treatment
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Conclusion

The problems related to cooling water systems can lead to heavy production and energy loss. This can be effectively handled without affecting production and continuity of the plant by thorough understanding of the process as well as CW chemistry involved. Cooling water treatment is a specialized subject. A lot of research and improvements are taking place in this field. This knowledge is available to industry through experts in the field. Industry should adopt the relevant features of advancements for improvement in the system.
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THANK YOU

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