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EVALUATION OF THE PERFORMANCE OF WASTE WATER UNITS OF A

NIGERIAN REFINERY: PHYSICAL AND BIOLOGICAL PARAMETERS

By

Opara, C.C; Mbazurike, C; Obot, E.I.


Department of Chemical Engineering,
University of Port Harcourt,
Port Harcourt, Nigeria

ABSTRACT

The waste water effluents from various wastewater generation and treatment units of
the Refinery were collected as samples and analyzed to determine their physical and
biological properties and thereby to assess the efficiency of treatment received in each
treatment units. The oil and grease content of the open channel was recorded as
significantly high with a value of 7.5mg/l suggesting a contamination to the
observation pond. The sedimentation tank reduced the amount of TDS from raw water
(process, caustic and sanitary wastewater) from 668 to 336mg/l. The predominant
microorganisms were staphylococcus spp. and E. coli.

INTRODUCTION
The Refining Company converts Nigeria crude oil into refined products such as
liquefied petroleum gas, gasoline, kerosene, aviation fuel, diesel fuel, fuel oils and
feedstocks for the petrochemical industry. Petroleum refinery activities start with
receipt of crude for storage at the refinery, include all petroleum handling and refining
operations, and they terminate with storage preparatory to removal of the refined
products from the refinery by tankers or pumping to depots by pipeline.
. If untreated wastewater is allowed to accumulate, the decomposition of the organic
materials it contains can lead to the production of large quantities of malodorous
gases. In addition, untreated wastewater usually contains numerous pathogenic, or
disease –causing, microorganisms that dwell in the human intestinal tract or that may
be present in certain industrial waste. Wastewater also contains nutrients, which can
stimulate the growth of aquatic plants in addition to toxic compounds1. Studies have
been carried out on the toxicity of oil, oil spill chemicals and industrial waste water (effluent)
on different aquatic organisms including those in Nigeria2.
___________________________
1
Ojuola, E.A.; Onuoha, G.C. (1981): The effect of liquid petroleum refinery effluent on
fingerlings of sarotherodon melanotheron (ruppel 1852) and oreochromis niloticus
(linnaeus 1757). FAO Corporate Document ARAC/87/WP/8 1987
2
Ajao et al (1981)

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For these reasons, the immediate and nuisance – free removal of waste water from its
source of generation followed by treatment and disposal is not only desirable but also
necessary in an industrialized society2. Methods or treatment equipments in which the
application of physical forces dominates are known as unit operations. Methods of
treatment in which the removal of contaminants is brought about by chemical or
biological reactions are known as unit processes. In primary treatment, physical
operations such as screening and sedimentation are used to remove the floating and
settleable solids found in wastewater. In secondary treatment, biological and chemical
processes are used to remove most of the organic matter2. It has been reported by that
the rotary biodisk, having a long residence time, would habour bacteria that have had
sufficient time to acclimatize to degrade phenol fast and at a higher concentration.

MATERIALS AND EQUIPMENT


PRELIMINARY TREATMENT FOR WASTEWATER SAMPLES
Wastewater from the Port Harcourt Company facilities is grouped and treated as
follows:
a. Process Wastewater:- This wastewater comes from the following units:
 Desalter in Crude Distillation unit.
 FCC Sour Water Stripping Section.
 Sour Water and Caustic Treatment Unit.
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It mainly contains oil and BOD elements. Oil is removed by an oil separator while
BOD elements are removed by BIO treatment system and change to BIO sludge2.

b. Oily Sewer Water:- The oily sewer water consists of rain water which has
fallen in possible oil contaminated pave areas and drain water from vessels,
pumps, tanks, etc. it mainly contains oil and suspended solids. Oil is removed
by Dissolved Air Floating (DAF) system, and changed to BIO sludge.

c. Ballast Water:- The ballast water from tankers mainly contains oil and
suspended solids.

d. Sanitary Wastewater:- It consists of toilet effluent which is run through


decantation pit and kitchen wastewater is run through a grease trap. It contains
BOD elements.

e. Chemical Wastewater:- This consists of laboratory wastewater, spent caustic


water from Sour Water and Caustic Treatment Unit and Demineralizer
effluent. The neutralized spent caustic water, which contains some phenol and
MEA solution, is combined with the process water.

1
Tchobanoglous, G. and Burton, F. L (1991): Chemical Unit Processes, Wastewater
rd
Engineering, Treatment, Disposal and Reuse”. 3 edition, McGraw Hill International Editions,
Singapore, pp.316-317.
2
Ajao, E. A.; Oyewo, E: O. and Orekoya, T. (1981). The Effect of Oil Formation Water on Some
Marine Organisms. 2pp. In Proceedings of An International Seminar on the Petroleum Industry and
The Nigerian Environment

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f. Clean Water system:- The following clean water which does not require
further treatment is discharged to the observation pond directly;

g. Dimersol Effluent:- This waste which comes from the Dimersol Unit contains
suspended solids.

The wastewater treatment equipment consists of water clarifying system and sludge
treatment system. The wastewater system is divided into the following two (2)
categories: 1) Process water, sanitary water and caustic spent water are treated by
biological treatment; 2) Oily rain water and ballast water are treated by dissolved air
floating treatment.

BIOLOGICAL TREATMENT SYSTEM


Process water, sanitary water and caustic waste water are treated by this method.
Caustic wastewater is firstly neutralized in the neutralization pit at process area before
entering into the wastewater pit. In the wastewater pit, the process water, sanitary
water and caustic spent water are mixed by aeration and are equalized. The equalized
wastewater is pumped up to the rotating biological contactors or rotary bio disks. At
the inlet of trough, nutrient is always injected for normal operation. In a case of
carryover of suspended solids from sedimentation tank, alum is also injected to
promote the settling speed of fine bio sludge in the sedimentation basin. The treated
water from the RBD is sent by gravity to sedimentation basin. The treated water in the
sedimentation basin is stored in the observation pit

In its simplest form, a rotating biological contactor consists of a series of disc or


media blocks mounted on a shaft which is driven so that the media rotates at right
angles to the flow of sewage. The discs or media blocks are normally made of plastic
(polythene, PVC, expanded polystyrene) and are contained in a trough or tank so that
about 40% of their area is immersed. The biological growth that becomes attached to
the media assimilates the organic materials in the waste water. Aeration is provided
by the rotating action which exposes the media to the air after contacting them with
the wastewater. The degree of wastewater treatment is related to the amount of
surface area, characteristics or quality and volume of the inflowing wastewater.

DISSOLVED AIR FLOATING (DAF) SYSTEM


Oily rain water and ballast water are treated by an oil separator enter into the oily
sewer water pit. The mixed raw water is pumped up to the DAF tank through a
measuring tank and coagulation tank. In the coagulation tank, alum, caustic soda and
a polymer (B) are injected and mixed. The air floatation separator makes use of
minute bubbles (colloids) which are produced when dissolved pressurized air is
released in the water due to pressure reduction. The pressure of pressure drum is 4 -
4.5 kg/cm2 (G). In order to promote separation efficiency, chemicals are injected to
the water to promote coagulation of suspended solids before floatation separation
takes place.

DETERMINATION OF PHYSICAL PARAMETERS

Temperature and pH were measured simultaneously using Hanna Temperature


Compensated pH meter model HI98128. Total suspended solids (mg/l) were
determined by HACH photometric method. To determine dissolved solids a 100ml

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beaker was washed with chromic acid to remove greases. The beaker was then
washed with water, dried at 1200C, cooled in a desiccator to room temperature and
weighed (WI). 25ml of filtered sample was introduced into the beaker and left to dry
in the oven. The beaker and content were left to cool in a desicator to room
temperature and weighed (W2). The dissolved solid content was obtained as:
W 2  W 1 *106
DissolvedSolids (mg / I ) 
Vol .ofSample

OIL (HYDROCARBON CONTENT)

200ml of sample was placed in a separating flask and 40ml of CCL4 was added and
the flask shaken. Then gas was release and he system left so that two layers of liquid
got formed. The upper (solvent) layer was separated into an already weighed 100ml
beaker (WA), through a filter paper containing anhydrous salt, NaSO 3 (to absorb any
water) and dried at 500C. It is cooled in a desicator and weighed again (WB). Oil
content was obtained as:

(Weight B  Weight A)*106


Oil Content (mg/L) 
Volume of Sample (L)

DETERMINATION OF BIOLOGICAL PARAMETERS

Identification of isolates
Isolates were identified by standard microbiological and biochemical test procedures
according to Bergey’s Manual3. Basic microbiological tests undertaken included:
gram-staining test, motility test and test for the presence of endospore, while
biochemical tests included catalase, oxidase, indole, citrate utilization, methyl-red,
Voges – proskauer, kligler iron agar, carbohydrate fermentation, coagulase and starch
hydrolysis tests. The BOD5 was obtained by incubation the sample a 20oC for 5 days
and monitoring the decreases in oxygen concentration as dissolved oxygen using
Hanna DO meter (Hanna Instruments, UK)

RESULTS AND DISCUSSION


The heaviest focus for pollution prevention activities in refineries has been in the area
of general operating and maintenance practices and procedures, with much of the
emphasis placed on reducing losses of hydrocarbons and solids to the wastewater
systems. Loss of hydrocarbons results in both lost product and revenue, and loss of
solids increases sludge formation and incurs additional disposal costs4.
The wastewater treatment equipment consists of clarifying system and sludge
treatment system. Our concern is the water clarifying and treatment section. Form the
diagram it could be sent that the wastewater treatment system is divide into the
following two (2) categories: 1) process water, sanitary water and caustic spent water
are treated by biological treatment, 2) oily rain water and ballast water are treated by
dissolve air floating (DAF) system.
_____________________________
3
Altas, M. R.; Bartha R.(1993): Microbial Ecology Fundamentals and Applications Third Edition. The
Benjamin/Cummings Publishing Company, Inc. New York, p.383-385.
4
Jacobs Consultancy (2002): Water Pollution Prevention Opportunities in Petroleum Refineries
Ecology Production No 02-07-012; Washington State Department of Ecology.

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The oil content in the effluent stream from wastewater pit has been reduced from
10mg/I (process water) to 8mg/I., although the wastewater pit receives and mixes
process wastewater, caustic wastewater and sanitary waste water. The aim is to skim
as much oil as possible from the influents so that microbial activity in the RBC would
not be hindered.

The microorganisms in the RBC feed on hydrocarbon substrate thereby reducing the
contaminants. The influent stream to the RBC has the following measured parameters,
oil (8mg/I), TDS (624mg/I). BOD (21.46mg/I) reduced tremendously to oil
(205mg/I), TDS (396mg/I), and BOD (13.37mg/). It means that the microorganisms
found in the RBC which include staphylococcus spp and E. coli had approximately
right environment for microbial activity which include manually added nutrient such
as phosphorous.

From the profile of Figure 4.1., the oil content of the open channel is tremendously
high (7.5mg/I). This wastewater from the open channel is not treated because it is
designed to contain clean water such as blown down and condensate, etc. the oil
content is high because of channeling wrong drainage into it; as a result it
contaminates the observation pond with excessive oil content.

The DAF is a physical method treatment unit that uses pressurized dissolve air to
remove dissolved solids as scum a combination of oily and ballast wastewater. The
TDS increased from 285mg/I to 308mg/I while the oil content dropped from 9.5mg/I
to 6mg/I.

The treated wastewater has a high TDS content of 336mg/I although, it did not go
above the regulation limit. It has an oil content of 4mg/I which can be reduced further
if that from the DAF treatment system is reduced.

The observation pond collects treated wastewater from both the biological and DAF
systems. As the name implies, it stores the treated wastewater for observation before
been discharged to surrounding surface water (streams, rivers). Its oil content is
slightly higher than that of treated wastewater.

CONCLUSION AND RECOMMENDATION

CONCLUSION
The Port Harcourt Refining Company wastewater has been characterized in terms of
physical, chemical and biological parameters. The concentrations which these
parameters depended on certain factors that affect their availability and abundance.
Some microorganisms expected to be found in the type of effluent were absent. For
instance, Pseudomonas spp, an important and common microorganism found in this
type of effluent were absent. A contributing factor to this may be the non availability
of essential nutrients for their survival. In all these, the measured parameters meet the
FEPA standards.

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RECOMMENDATIONS
Although the measured parameters meet regulatory standards, there are short falls that
need to be corrected.

The temperature of the process wastewater can be reduced significantly on –site by


passing it throught heat exchangers before it gets to the Wastewater Treatment Unit
(WWT).

The RBC should be checked regularly to feed the microorganisms with nutrient and
replace or clean clogged disks for effective air penetration.

A physical treatment unit should be in place just for the open channel to remove any
excess oil and suspended solids. Powdered activated carbon (PAC) should be used to
further treat the effluent wastewater before it is discharged to the river.

REFERENCES
1
Tchobanoglous, G. and Burton, F. L (1991): Chemical Unit Processes,
Wastewater Engineering, Treatment, Disposal and Reuse”. 3 rd edition,
McGraw Hill International Editions, Singapore, pp.316-317.
2
Ajao, E. A.; Oyewo, E: O. and Orekoya, T. (1981). The Effect of Oil
Formation Water on Some Marine Organisms. 2pp. In Proceedings of An
International Seminar on the Petroleum Industry and The Nigerian
Environment
3
Altas, M. R.; Bartha R.(1993): Microbial Ecology Fundamentals and
Applications Third Edition. The Benjamin/Cummings Publishing Company,
Inc. New York, p.383-385.
4
Jacobs Consultancy (2002): Water Pollution Prevention Opportunities in
Petroleum Refineries Ecology Production No 02-07-012; Washington State
Department of Ecology.

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Film of microorganisms

Air Flow Air Flow

Air & Water Mixture Vacuum

Fig 1.1 schematic Diagram of Rotating Biological Contactor

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