WATER MANAGEMENT

BONUSREPORT

Wastewater treatment:
A refinery case study
This refiner used an in-house initiative to troubleshoot plant-wide
process water problems
M. SHAFIQUE, Z. U. KIRMANI, A. KHURSHID, N. ALAM and N. AHMED,
Attock Refinery Ltd., Rawalpindi, Pakistan

ll refineries produce wastewater with varying contaminant

levels that require further treatment before discharge. Because
wastewaters are collected from various processes, problems
do arise. Hydrocarbon-processing facilities must comply with local
and federal standards on water quality exiting the facility. Exceeding
such limits will trigger an incident and fine in most cases.
In this case history, the Attock refinery used two wastewater
streams: oily and non-oily to carry process wasterwater to treatment facilities. Unfortunately, this refiner exceeded discharge
limits for the facility and needed a plan to handle high pH and
chemical oxygen demand (COD) from spent caustic and oil/water
emulsion formation in wastewater.

HBU-I
(distillation
unit)

Spent
caustic
treater

10 to 64. These crude oils are processed in four different crude

mixes: light-sweet, light-sour, heavy and high total acid number
(TAN) crudes. This refinery has a nameplate crude capacity of
40,000 bpsd and uses four distillation units namely HBU-20,000
bpsd and HBU-5,000 bpsdboth processing light sweet crudes;
CDU-5,000 bpsd processes a light sour crude; and HCU-10,000
bpsd capacity processes heavy crude and a reforming unit.
Wastewater produced from these crude distillation units
(CDUs), desalters and crude/product tanks is categorized as oily
wastewater. Wastewater from boilers and cooling towers is categorized as the non-oily stream. Oily wastewater after leaving the
plant battery limit is collected in the API oil-water separators and
finally collected in the equalization tank. From the equalization
tank (C-sump), the oil is collected from the top and the oil-water
emulsion is sent to primary treatmentthe slant-rib coalescer
(SRC) and dissolved air flotation (DAF) units. Fig. 1 is a detailed
scheme of oily/non-oily streams at ARL.
Previously, wastewater exiting the refinery premises occasionally
violated pH and oil & grease (O&G) values as well as exceeded
COD limits set by the National Environmental Quality Standards
and Pakistan Environmental Protection Act 1997.1,2 Table 1 summarizes the wastewater quality results from the ARL facility.

HBU-II
(distillation
unit)

Reformer

The approach. The main concerned parameters to be con-

The facility. Attock Refinery Limited (ARL) is based at Rawalpindi, Pakistan. ARL is one of the few refineries that can process a
complicated mix of 70 different crude oils with APIs ranging from
Distillation
unit

Heavy crude
unit (HCU)

Desalter
cuff header

APIseparator

Boiler house

Cooling
tower

APIseparator
Tanks
drain

trolled were pH, total suspended solids (TSSs), O&G and COD.
Therefore, these parameters were analyzed in all effluent streams
to gauge their total impact on the main refinery effluent streams.
From Fig. 1, boiler blowdown water was sent to the non-oily
stream, and it was the main contributor for high pH and TSS valTABLE 1. Wastewater quality before treatment

C-sump
Legend
1. Red (non-oily wastewater
stream)
Two SRC
2. Black (oily wastewater
units (100
stream)
gpm each)

Renery
exit
FIG. 1

Sample No.
DAF
unit (100
gpm each)

APIseparator

Block diagram of refinery process units and wastewater

streams at ARL.

Parameter

NEQS limits

ARL values

Temperature, C (Max)

40

pH value

30

6 to 9

9.5

O&G, ppm (Max)

10

20

COD, ppm (Max)

150

300

BOD, ppm (Max)

80

40

TSSs, ppm (Max)

200

180

TDSs, ppm (Max)

3,500

2,500

Phenols, ppm (Max)

0.1

0.05

HYDROCARBON PROCESSING NOVEMBER 2009

I 67

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Select 62 at www.HydrocarbonProcessing.com/RS

WATER MANAGEMENT

BONUSREPORT

ues. The treating plant for naphtha and kerosine generated spent
wastewater streams, which pass through the pre-treatment and
caustic that was disposed of in the oily stream. This wastewater
primary treatment along with oily water. The high pH of the
stream was the main contributor for high pH, COD and O&G
caustic was also responsible for creating strong oil/water emulsions
levels. The quality of the oily stream impaired the total efficiency
that directly decelerated operating efficiencies for the API separaof the pretreater. Wastewater from the heavy crude unit (HCU)
tors, equalization tanks, and SRC and DAF efficiencies.
had a high oil content.
The oily water, rich in surfactants with a high COD (700
Characteristics of the process wastewater at ARL include:
ppm), is produced from the HCU desalter and was another source
Blowdown water produced from three boilers and softener
strong of oil-and-water emulsions that impaired API separator
backwash is rich in TSS and total dissolved solids (TDSs) with
efficiency and downstream SRC and DAF treatments.
a pH value greater than 12. Water treatment chemicals used in
Blowdown water from three cooling towers is another
boilers are phosphate based for scaling control, sulfite based as
stream that is directed to the non-oily wastewater stream. The conoxygen scavenger and ammonia to control pH in boilers. Before
cerned parameters for this stream include pH, TSSs, TDSs, COD
the study, blowdown water with high pH and TSS values was
and occasional O&G. Water treatment chemicals used in cooling
sent to the non-oily wastewater stream and it was mixed with
towers are phosphate based to control scaling, biosperse and deothe treated oily wastewater before exiting
sperse to control oil, sodium hypochlorite
the refinery. This stream exceeded the ARLs quality circle designed
for bacterial contamination, and sulfuric
total wastewater quality specifications
acid for pH control.
and resulted in violations of the National and implemented cost-effective
All of these streams were individually
Environmental Quality Standards.
analyzed
for their physical and chemical
indigenous solution of refinery
Spent caustic is produced from a
properties on a laboratory scale.
naphtha treating plant. This downstream wastewater to meet National
sweetening unit processed sour naphtha Environmental Laws.
Action plan. First, the boiler blowand kerosine; alkyl mercaptans in the
down water was analyzed for its neutralnaphtha and kerosine oil were converted into alkyl disulfides. By
ization with hydrochloric acid and sulfuric acid. However, to
combining caustic soda solution in the presence of charcoal and
be more cost-effective and to reduce chemical consumption,
catalyst, nearly 99% of all mercaptans, as well as oxygen and nitrosulfuric acid was selected for further studies. Table 3 summarizes
gen compounds, can be dissolved from petroleum fractions.
neutralization results with sulfuric acid to control pH, and TSSs
The refinery kerosine treater had a design capacity of 1,600
TABLE 4. Analysis of spent caustic
bpd; the naphtha treater was designed for 4,400 bpd. The main
reactions involved in the sweetening process are:3
Sample
Initial
Initial
RSH, Phenol, COD,

H 2 S + 2NaOH
Na 2 S + 2H2 O

source
LWK. settler

Na 2 S + H 2 S
2NaHS
RSH + NaOH
NaSR + H 2 O
2NaHS + 2O2
Na 2 S2 O3 + H 2 O
2RSNa + O2 + H2 O
2NaOH + RSSR
The treater used 3% caustic strength for the naphtha/kerosine
pre-wash, and 8%10% caustic strength for the naphtha/kerosine
settler. The quantity and drainage frequency of caustic from the
prewash and settler is listed in Table 2.
Before the study was conducted, the plant spent caustic, with
high pH (12) and COD (~50,000 ppm), was directed to oily
TABLE 2. Sources and quantity of caustic drainage
Caustic source

Strength, %

pH

temp., C

Monthly disposal

3 to 4

6 times

Naphtha settler

8 to 10

6.5

6 times

Kerosine prewash

3 to 4

4 times

Kerosine settler

8 to 10

2 times

ppm

ppm

16

13

26

382

2.5

9,331

14.19

11.86

26

875

1.1

55,209

Naphtha settler

15.68

12.46

30

4,129

1.6

6,026

Naphtha prewash

50.9

9.44

30

3,025

TABLE 5. BBDW and spent caustic neutralization

results
Sample source

pH

COD, ppm

Spent caustic soda (SCS) with oily layer

11.8

55,209

Spent caustic soda (SCS) after oil removal

11.8

4,600

Boiler blowdown water (BBDW)

11.66

88

98% BBDW + 2% SCS

11.76

180

7.0

190

TABLE 6. Final effluent water quality after

implementation
Sample No.

Parameter

NEQS limits

ARL values

40

30

Temperature, C (Max)

pH value

6 to 9

O&G, ppm (Max)

10

10

TSS, ppm

COD, ppm (Max)

150

140

BOD, ppm (Max)

80

40

TABLE 3. Lab scale BBDW H2SO4 treatment results

pH

ppm

LWK. prewash

98% BBDW + 2% SCS + 0.3% H2SO4

Qty, m3

Naphtha prewash

Sample source

% spent

Boiler blowdown water (BBDW) Blank

11.13

96

BBDW + 0.30 ml H2SO4

10.01

45

TSSs, ppm (Max)

200

80

BBDW + 0.40 ml H2SO4

8.60

15

TDSs, ppm (Max)

3,500

2,500

BBDW + 0.50 ml H2SO4

6.95

10

Phenols, ppm (Max)

0.1

0.05

HYDROCARBON PROCESSING NOVEMBER 2009

I 69

BONUSREPORT

WATER MANAGEMENT
12
2008 results
2007 results

10

NEQS limit min

NEQS limit max

pH

8
6
4
2
0

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

600
2008 results
2007 results
NEQS limit

New treatment pit installed to improve management of

oily and non-oily wastewater with high pH.

Desalter
cuff header

APIseparator

HBU-I
(distillation
unit)

Boiler house
Spent
caustic
treater

HBU-II
(distillation
unit)

400
300
200
100

Distillation
unit

Heavy crude
unit (HCU)

Treatment
pit

Reformer
Cooling
tower

APIseparator

Tanks
drain

TSSs, ppm

FIG. 2

COD, ppm

500

500
450
400
350
300
250
200
150
100
50
0

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
2008 results
2007 results
NEQS limit

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

C-sump
Legend
1. Red (non-oily wastewater
stream)
Two SRC
2. Black (oily wastewater
units (100
stream)
gpm each)

Renery
exit
FIG. 3

FIG. 4
DAF
unit (100
gpm each)

APIseparator

Revised refinery process wastewater management system

and new installations at ARL.

are listed, too. Laboratory scale studies concluded that 0.4 ml of

98% pure H2SO4 per liter of boiler blowdown water (BBDW) is
required to lower the pH < 9 as required by the National Environmental Quality Standard.
In the second phase, detailed analysis of spent caustic from the
treating plant was conducted and Table 4 summarizes the testing results. From the initial test results, it was observed that high
COD values were attributed to the oily layer from the spent caustic
discarded by the sweetening process. Therefore, by removing the
oily layer from the spent caustic, a reduction of 80% to 90% of
spent caustic COD was obtained. The remaining portion of spent
caustic was mixed with boiler blowdown water since the spent
caustic was only 2% of the total boiler blowdown water. Table 5
lists the boiler blowdown water and spent caustic neutralization.
70

I NOVEMBER 2009 HYDROCARBON PROCESSING

Refinery trends for COD, pH and TSSs at ARL before and

after new wastewater management initiatives.

The heavy-crude-unit desalter oil-water emulsion was tested. The

problems from this wastewater stream were sourced to the presence
of a surfactant in the crude oil received from the Chanda oil field.
The surfactant aided in creating in a strong oil/water emulsion.4
Testing. Laboratory-scale experimentation results were evaluated
and used to develop optimization plans for the ARL facility. From
the testing results, a neutralization pit with a total capacity of 0.1
million gallons (Fig. 2) would be installed. Boiler blowdown water
would be collected in the first half of the pit. Temperature at the
collection pit ranged from 80C to 90C. The wastewater was
allowed to cool and settle in the first two pits for two hours. The
spent caustic was collected in a vessel from which it was pumped
to the third half of the pit at a rate of 1 tpd. Sulfuric acid was
added in the third half of the pit to neutralize the pH to 8. After
neutralization, the water was settled in the third and fourth half
of the pit before disposal.
At the HCU, the surfactant-rich Chanda crude oil was diverted
to a light-sweet crude pool. With this change, operations of the
desalter oil and water separator improved. Fig. 3 shows the scheme
adopted for treating boiler blowdown water and spent caustic.
The revised treatment program was very successful and
enabled 100% compliance to the National Environmental Qual-

WATER MANAGEMENT
ity Standards for pH, TSSs, O&G and COD. Moreover, the
total efficiency of wastewater treatment increased. Fig. 4 shows
the improvements in wastewater pH and COD with the water
management changes for the last two years.
The boiler blowdown water, with high pH and TSSs, and
plant spent caustic with high pH and COD levels were treated
via an onsite neutralization pit. Whereas, the operational controls
applied at heavy-crude-unit desalter controlled oil-and-water
emulsion formation. Spent caustic that was earlier drained into
the oily drain was diverted to non-oily drain after removing oil.
The neutralization treatment was successful in many ways:
National Environmental Quality Standards limits were met
for pH, O&G, COD and TSSs.
The strong oil/water emulsion was broken by removing the
high pH spent caustic from the oily drain.
Efficiency of API separators increased with reduced loading
on the treatment plants.
Quality of ARL wastewater after the new treatment program
is summarized in Table 6. Applying an in-house initiative can
identify cost-effective solutions that can be implemented in a
short time and reusing spare equipment. HP
1
2
3
4

LITERATURE CITED
Pakistan Environmental Protection Council, National Environmental
Quality Standards, December 28, 1999.
The Gazette of Pakistan, Pakistan Environmental Protection Act 1997,
December 16, 1997.
Ahmed, I., Merox catalyst impregnation, Merox Operating Manual.
Kirmani, Z. U., A. Khurshid, N. Alam, N. Ahmed and S. Gul, Crude
incompatibility problems at heavy crude unit desalter, Hydrocarbon Asia,
July/August 2007, pp. 6870.

BONUSREPORT

Mansoor Shafique is the assistant general manager in operations, at Attock Refinery Ltd. He has 34 years of experience in plant
operations and has done two master startups. His main interests are
plant optimization and value addition with minimum investment.
He holds a BE degree in chemical engineering from the University
of the Punjab.

Zia Uddin Kirmani is the manager of health, safety, environment and quality at Attock Refinery Ltd. He has more than 20
years of diversified experience in petroleum refining, fertilizer and
paper industries. He has authored seven research publications in
environment, petroleum and chemical fields. Mr. Kirmani holds
master degrees in chemistry and business administration.

Amir Khurshid is the senior chemist for environment and

quality at Attock Refinery Ltd. He has more than nine years of diversified experience in the field of quality control and environment.
Mr. Khurshid holds an MS degree in chemistry from Quaid-i-Azam
University, Islamabad.

Naveed Alam is the senior chemist at Attock Refinery Ltd.

He has more than 11 years of diversified experience in the field of
quality control and environment. Mr. Alam holds an MS degree in
chemistry from Peshawar University.

Naveed Ahmed is a senior engineer in operations at Attock

Refinery Ltd. He has 10 years of experience in plant operations
and troubleshooting. Mr. Ahmed holds a BE degree in chemical
engineering from Punjab University, Lahore.

Select 162 at www.HydrocarbonProcessing.com/RS

HYDROCARBON PROCESSING NOVEMBER 2009

I 71