College of Engineering

The Seventh Annual U.A.E. University Research Conference ENG- 186

Refinery Wastewater Treatment: A true Technological Challenge
Farid Benyahia, Department of Chemical and Petroleum Engineering, E-mail:
farid.benyahia@uaeu.ac.ae
Mohamed Abdulkarim and Ahmed Embaby, Department of Chemical and Petroleum Engineering
Madduri Rao, Department of Chemistry
U.A.E. University, Al-Ain, P.O. Box: 17555, U.A.E.
Abstract
Crude oil and condensate refineries generate a large amount of wastewater that has both
process and non-process origins. Depending on the type of crude oil, composition of
condensate and treatment processes, the characteristics of refinery wastewater vary
according to a complex pattern. The design and operation of modern refinery wastewater
treatment plants are challenging and are essentially technology driven. In this
investigation, the sources of wastewater pollutants have been traced to specific sources and
operations, and suitable treatment technologies identified. Modern powerful tools such
image analysis have been employed to characterize oil droplet sizes in oily wastewater and
immobilized cell technology considered in biological reactor design for wide spectrum
chemical pollutant degradation. A biomass extraction method was developed to harvest
Pseudomonas P. and Baccili S. cells from a commercial biological product and acclimate
them to a source of carbon rich in phenol, prior to immobilizing them in a suitable gel.

1. INTRODUCTION
The petroleum refining industry converts crude oil into more than 2500 refined products, including liquefied
petroleum gas, gasoline, kerosene, aviation fuel, diesel fuel, fuel oils, lubricating oils, and feedstocks for the
petrochemical industry. Typically, petroleum refining activities start with receipt of crude oil for storage at
the refinery, include all petroleum handling and refining operations, and they terminate with storage prior to
shipping the refined products from the refinery.

The petroleum refining industry employs a wide variety of physical and chemical treatment processes. A
refinery processing flow scheme is largely determined by the composition of the crude oil feedstock and the
chosen final petroleum products. Typical processing and auxiliary units in refineries are presented below [1]:

1. Separation processes
a. Atmospheric distillation b. Vacuum distillation c. Light ends recovery (gas processing)
2. Petroleum conversion processes
a. Cracking (thermal and catalytic) b. Reforming c. Alkylation d. Polymerization e. Isomerization
f. Coking g. Visbreaking
3. Petroleum treating processes
a. Hydrodesulfurization b. Hydrotreating c. Chemical sweetening d. Acid gas removal
e. Deasphalting
4. Feedstock and product handling
a. Storage b. Blending c. Loading d. Unloading
5. Auxiliary facilities
a. Boilers b. Wastewater treatment c. Hydrogen production d. Sulfur recovery plant

Large volumes of water are employed in refining processes, especially for cooling systems, distillation,
hydrotreating, and desalting. Tank drains, equipment flushing, surface water runoff and sanitary wastewaters
are also generated. It is therefore clear that refinery wastewater can be broadly categorized as process or non-
process wastewater. In most modern refineries, these different wastewaters are channeled in separate sewer
systems. At least two different independent sewers exist in most petroleum refineries: one that handles storm
water and surface runoff and another that handles all process water and water produced from utilities units.
However, in most efficient refineries, process water sewers are usually split in more than one sewer
depending on the nature of wastewater, thus reducing the load on the wastewater treatment plants, increasing


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The Seventh Annual U.A.E. University Research Conference ENG - 187
the efficiency of each treatment unit and broadening the possibilities of wastewater reuse in different refining
units. Clearly, there is no universal approach to handling and treating refinery wastewater streams.

The quantity of wastewaters generated and their characteristics depend on the process configuration. As a
general guide, approximately 3.55 cubic meters (m
3
) of wastewater per ton of crude are generated when
cooling water is recycled. Refineries generate polluted wastewaters, containing biochemical oxygen demand
(BOD) and chemical oxygen demand (COD) levels of approximately 150250 milligrams per liter (mg/l) and
300600 mg/l, respectively; phenol levels of 20200 mg/l; oil levels of 100300 mg/l in desalter water and
up to 5,000 mg/l in tank bottoms; benzene levels of 1100 mg/l; benzo(a)pyrene levels of less than 1 to 100
mg/l; heavy metals levels of 0.1100 mg/l for chrome and 0.210 mg/l for lead; and other pollutants.
Refineries also generate solid wastes and sludges (ranging from 3 to 5 kg per ton of crude processed), 80% of
which may be considered hazardous because of the presence of toxic organics and heavy metals [2].

Given the complex and diverse nature of refinery wastewater pollutants, a combination of treatment methods
is often the norm before discharge. Therefore separation of wastewater streams, such as storm water, cooling
water, process water, sanitary, sewage, etc., is essential for minimizing treatment requirements.
2. OILY WASTEWATER TREATMENT TECHNOLOGIES
Knowledge the oil droplet size distribution in refinery wastewater is paramount to understanding the
wastewater behavior in an oil/water separator [3,4]. This size distribution is crucial for determining the
proper oil/water separation system and its efficiency.
Oil and grease present in the wastewater generated in the oil processing industries can be removed by various
established or novel techniques. Many researchers tried to divide the oil droplets size spectrum and then
propose an appropriate treatment technique for each section. The diagrams shown in Figure 1 represents such
classifications.




Fig. 1: Oily water treatment techniques as a function of oil droplet sizes [5].

On a general basis, and in order to obtain an effluent that meets the current EPA (fairly stringent) effluent
discharge guidelines, a refinery wastewater treatment plant should contain at least the units depicted in
Figure 2. It should be stated that the configuration shown in Figure 2 is very basic and by no means
definitive or complete.
















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The Seventh Annual U.A.E. University Research Conference ENG - 188






Fig. 2: Typical refinery oily wastewater treatment stages [6].

If a complete wastewater treatment plant that comprises the three treatment stages, namely primary,
secondary and tertiary, is in operation, then we can achieve an effluent that can be recycled and if a reverse
osmosis unit is supplemented, the treated wastewater can be reused in processing units. Removal efficiencies
can reach 90-99 % of all wastewater parameters; COD, BOD, O&G, BTEX, SS, NH
3
, Heavy metals [7].

Since this project is in association with TAKREER (end user), and the objectives aim at developing
wastewater treatment technologies that would enable recycling wastewater, a brief description of the refinery
and its current wastewater system will be presented in the next sections.
3. RUWAIS REFINERY OVERVIEW
3.1 History and Processes
Ruwais Industrial Complex was officially inaugurated in 1982. Soon after commissioning the original
120,000 barrels per day (bpd) Hydro skimming refinery in June 1981, plans were drawn up to add a 27,000
bpd Hydro cracker complex that was started in 1985. To consolidate operations, the General Utilities Plant,
set up in 1982 to provide electricity and water for the area, was merged with the Refinery in 1986. A central
Sulphur Handling and Granulation Plant was established in 1991 to handle all the liquid Sulphur recovered
in the GASCO and ADGAS Natural Gas Liquefaction facilities. After its expansion in early 2001, the
granulation capacity, at 7,650 tons per day, has become one of the largest in the world.

Two 140,000 bpd condensate-processing trains were commissioned in year 2000-2002 to process condensate
produced in the on-shore gas fields of Abu Dhabi. Currently these are two of the largest such condensate
splitters in the world. Meanwhile, support facilities such as berths, power generation and water production
facilities continued to be expanded to meet the growing needs of the industrial area.

Today the range of refined products includes Liquefied Petroleum Gas, Premium Unleaded Gasoline (98
Octane), Special Unleaded Gasoline (95 Octane), Naphtha grades, Jet-A1 and Kerosene grades, Gas Oil
grades, Straight run Residue, Bunker grades 180 and 380 cst and Granulated Sulphur.
3.2 Wastewater Treatment Plant
The wastewater treatment facility in the Ruwais refinery belongs to the "Oil Movement Department". Figure
3 shows a schematic diagram of the complete water treatment plant and associated ancillary equipment.

The wastewater treatment plant receives oily wastewater streams from the following three refinery sewer
channels:
Existing Refinery Oily Water Sewer System
New Oily Sewer System
New Accidental Oily Sewer System







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Fig. 3: Ruwais refinery wastewater treatment flow diagram.

These sewer channels are fed with wastewater from several sources: crude and condensate refining units,
flare systems, crude oil storage tanks, laboratory drains and sanitary drains. In the latter source, the drains are
fitted with septic tanks to retain solids and the liquid is directed to the sewer. The solids are collected
periodically for treatment and disposal.

The sewer channels network eventually converge into the mixing sump (247 F1) in the waste water treatment
plant. The oily water sump (mixing sump 247 F1) consists of three separate sections, each being provided
with a proper inlet pit. The three sections are connected together by bottom slide gates and receive the
wastewater according to the following sources and entry point:

(1) The wastewater streams from the new refinery (Condensate splitting unit) oily wastewater system,
namely:
Accidental oily wastewater streams (AY) originate from the condensate unit and enter the sump
247-F001C.
Oily wastewater streams (SY) originate from the condensate unit and enter the sump 247-F001B.
Wastewater from the new flares and tank farm areas also enter the sump 247 F001B via the SY
system.
(2) The wastewater streams from the existing refinery oily wastewater system, namely:
Existing Hydroskimmer Unit oily wastewater stream
Existing Hydrocracker Unit oily wastewater stream
Existing tank farm oily wastewater stream
Sanitary and laboratory wastewater stream

The streams described above are collected in the existing API separator (currently not in operation in its
original function but used for another purpose) inlet pit (47 F 10) and then flow to 247 F001A.
The mixing sump (247 F001) includes an oil settling compartment (247 F001E) that collects slop oil which is
in turn pumped into tank 247 F003.

The wastewater with residual oil from mixing sump (247 F001 A/B/C) is then pumped into the CPI separator
(247 V1) where oil separation via coalescing plates occurs. The effluent water flows to water settling tank
(247 F002) and the separated oil is recovered and routed to the slop oil settling tank (247 F003).


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Water from the settling tank (247 F002) is directed to two large tanks called "ballast tanks", working
alternatively according to the liquid level (F01A/B), then proceeds to the mechanical flotators (V04 A/B) and
finally to the final dilution pit (47 F20) that precedes discharge into the marine environment. The mechanical
flotators aforementioned are not functional and used simply as a transition stage. The settling tank and ballast
tanks have oil skimming weirs that discharge slop oil when a certain liquid level is reached.

In the final dilution pit (47 F 20), dilution of discharge water with used cooling sea water occurs in the ratio
of around 1:60. Wastewater streams that do not flow through the wastewater treatment unit (in this context,
the CPI) are channeled directly to the final dilution pit (47 F 20). These streams are essentially pH adjusted
spent caustic streams from LPG and Kerosene sweetening units, as well as spent caustic solutions from the
condensate splitting unit.

This brief description of the Ruwais refinery wastewater treatment facility indicates that only mechanical
treatment followed by high dilution with seawater is employed before discharge into the marine
environment. The refinery laboratory conducts routine analysis on samples of treated waste water after the
water settling tanks (247 F01A) and possibly in other unspecified locations to ensure discharge compliance
limits.
4. OBJECTIVES OF STUDY
The objectives of this work include:
Characterization of wastewater generated at the Ruwais refinery,
Evaluation of the current treatment process performance
Design, development and evaluation of alternative treatment processes compatible with project
resources.
Laboratory scale tests on the most promising treatment process with a view to improve the current
process and enable recycling of wastewater for uses required by the end user, namely TAKREER.

The project involves visits to the refinery to collect process data and wastewater samples for analyses. At
some stage, wastewater treatment process simulation would play a major role in the advancement of the
project, using real plant data from the Ruwais refinery wastewater unit and physical/chemical characteristics
of its wastewater. Superpro Designer has been selected as the best simulation tool to conduct the simulation
work owing to its rich library of biological process and cost models.
5. EXPERIMENTAL
5.1 Sampling & wastewater characterization
During two consecutive visits to the refinery premises in June 2005, wastewater samples from the
wastewater treatment unit (247) were collected. Sampling points are shown in Figure 3 (points A to E). Most
of the samples were collected again in a second visit to check the consistency of parameters measured and to
verify the stability of the treatment process. Table 1 summarizes the parameters measured. At this stage no
BOD/COD measurements were made as these would have required immediate processing and that was not
possible at the time of sampling.

Table 1: Wastewater analysis parameters.
Sample location Code Unit A B C F F D E
Design Flow Rate m
3
/hr 175.5 177
Average Flow Rate m
3
/hr 129
Min m
3
/hr 155 155 155
Flow Rate
Max m
3
/hr 290 290 290
Min mg/l 488 49 33 < 0.2 < 0.2 37.7
TPH
Max mg/l 3714 339 124 12.8 622
Min mg/l 466 253 89
Oil & Grease
Max mg/l 3428 576
Naphthalene g/l 306 334 220 < 0.22 < 0.22 29.6 218
Acenaphthylene g/l 0.18 ND 1.20 ND ND ND < 0.18
Acenaphthene g/l 21.2 7.4 0.8 < 0.05 < 0.05 0.30 2.60
Flourene g/l 1.80 114 88.2 0.07 ND 4.10 0.40


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Phenanthrene g/l 236 164 1.8 0.20 < 0.08 4.20 0.40
Anthracene g/l 0.40 < 0.05 0.20 < 0.05 < 0.05 < .05 0.20
Fluoranthene g/l 34 12.0 88.4 < 0.09 ND 3.20 20.6
Pyrene g/l 6.60 6.40 46.6 0.10 < 0.05 0.80 < 0.05
Benzo(a)anthracene g/l 19.8 17.4 11.4 < 0.05 ND 0.30 < 0.05
Chrycene g/l ND 41.2 32.4 ND ND 0.40 ND
Benzo(b)flouranthene g/l ND 0.20 4.00 < 0.10 < 0.10 0.10 < 0.1
Benzo(k)flouranthene g/l < .08 0.20 1.60 ND ND < .08 ND
Benzo(a)pyrene g/l 0.60 0.20 0.40 ND ND < .05 ND
Dibenzo(a,h)anthracene g/l 0.20 ND ND ND ND 0.20 ND
Benzo(g,h,i)perylene g/l 0.80 0.80 2.80 ND ND ND ND
Indeno(1,2,3-cd)pyrene g/l 0.40 ND 2.00 ND ND ND ND
2,4-Dinitrophenol mg/l ND ND ND ND ND ND ND
2-Methyl-4,5-dinitrophenol mg/l 0.02 0.02 0.10 ND ND ND 8.98
2,4,6-Trichlorophenol mg/l ND ND ND ND ND ND ND
2,4-Dichlorophenol mg/l ND ND ND ND ND ND ND
2,4,5-Trichlorophenol mg/l ND ND ND ND ND ND ND
Phenol mg/l 0.20 0.19 0.24 ND ND 0.17 5.75
m,p-Cresol * mg/l 0.24 0.24 0.23 ND ND 0.12 2.95
o-Cresol + 2-cyclohexyl-4,6-dinitrophenol* mg/l ND ND ND ND ND ND ND
2,3,4,6-Tetrachlorophenol mg/l 0.18 0.11 0.32 ND ND 0.18 0.38
4-Chloro-3-cresol mg/l 0.06 0.06 0.10 ND ND 0.07 0.23
2,4-Dimethylphenol mg/l ND 0.04 0.14 ND ND 0.06 ND
o-Chlorophenol mg/l ND ND ND ND ND ND ND
2,6-Dichlorophenol mg/l ND ND ND ND ND ND ND
o-Nitrophenol mg/l 0.14 0.11 0.10 ND ND 0.07 0.09
p-Nitrophenol mg/l ND ND ND ND ND ND ND
Pentachlorophenol mg/l 0.06 0.05 0.07 ND ND ND 0.10
Al mg/l 0.89 0.28 0.09 0.02 0.02 0.05 0.85
As mg/l ND ND ND ND ND ND ND
Cd mg/l ND ND ND ND ND ND ND
Co mg/l ND ND ND ND ND ND 1.05
Cr mg/l 0.03 0.01 ND ND ND ND 0.01
Fe mg/l 11.7 3.42 0.68 ND ND 0.97 0.33
Mn mg/l 0.20 0.09 0.02 ND ND 0.03 <0.013
Pb mg/l 0.03 ND ND ND ND ND ND
V mg/l 0.01 <0.004 ND ND ND ND ND
Zn mg/l 1.66 0.53 0.25 0.003 0.003 0.07 0.05
Total Sulphur (as SO4) mg/l 75.0 83.2 53.2 3567 3550 142 333
Hg mg/l ND ND ND ND ND ND ND
Min 9.25 9.82 10.6 5.69 7.75 10.3 10.2
pH
Max 10.8 10.2
Min mg/l 0.76 0.72 2.60 0.34 0.54 0.98 0.90
NH4
+

Max mg/l 4.96 3.96
Min mg/l 28.9 72.2 22.7 43.1 36.6 12.6 68.7
TSS
Max mg/l 372 106
TDS mg/l 3272 6726 484 52430 51160 2060 13590
Min mg/l 82.2 76.0 41.0 3350 3250 127 11.1
SO4
Max mg/l 60 41.7
Min g/l ND ND ND ND ND 21 ND
S
-2
(g/l)
Max g/l 65 50 560 900


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In Table 1, one can see the design and average flowrates of wastewater at certain locations (see Figure 3) in
addition to Total Petroleum Hydrocarbon (TPH), oil and grease, Polyaromatic hydrocarbons (PAH), phenols,
heavy metals, sulfates, ammonia (as ammonium), Total Suspended solids (TSS), Total Dissolved Solids
(TDS), sulfides (as S
-2
) and stream pH.

The appearance of oil droplets in wastewater was studied by transmission light microscopy and shown in
Table 4.

Table 4: Appearance of oil droplets in wastewater samples from various streams.
A B

C D


E F


The oil droplet sizes were estimated using Image Analysis.
The characterization of wastewater will be completed once BOD and COD measurements will be conducted
as these are standard parameters reported in the literature (as opposed to TPH).
One of the important aspects of treatment technologies considered in this work is biological treatment using
immobilized cell technology. Cell immobilization has many advantages over free cells processes: high
volumetric cell density, protection of biomass from load and shock load, possible protection of biomass
against heavy metals and of course flexibility in biomass management. These aspects have not been
sufficiently investigated in the literature despite the fact the some aspects of immobilized cell technology has
been reported (eg: PVA immobilized cells employed in the treatment of phenols at Negishi refinery, Japan).
In the next section, a brief description of the preliminary work on biological treatment will be presented.
5.2 Biomass extraction for biological treatment
A major unit that is missing in Ruwais refinery wastewater treatment plant is a biological treatment stage. In
order to be able to reuse the treated wastewater, the dissolved oils, hydrocarbons and other constituents that
sum up to the COD level must be removed. Biological treatment has proven to be the most economical and
reliable tool after preliminary oil/water separation. Amongst hydrocarbons present in refinery wastewater,
phenol is one of the main dissolved components and it is also one of the toughest hydrocarbons to degrade
biologically. The bacterium Pseudomonas Putida has been reported to have multiple applications; in
particular, it is known for its capacity to degrade phenolic compounds [8] and other aromatic substances
[9,10]. This micro-organism will be one of a few to be considered in biological treatment processes.

Following this track, an experimental procedure for extraction of Pseudomonas Putida and another Bacilli
Subtilis strains from a commercial biological product (Amnite P300, Cleveland Biotech Ltd, UK) in the form
of bran cereal with these two strains immobilized within it, was designed and executed. The extraction
process involved mixing and blending the cereal with a buffer solution of 0.22% sodium hexametaphosphate.
After that, the resulting blend was decanted and successive centrifugation steps were implemented to obtain


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the bacterial cake as a precipitate. This bacterial yield was grown in 100 ml bottles on an orbital shaker with
a recipe of mineral nutrients and dextrose as the main source of carbon in order to increase the biomass
population. This was subsequently followed by bacterial harvesting and starting a new stage of bacterial
growth and adaptation to phenol (as alternative source of carbon) in an increasing concentration manner.
The biomass acclimated to phenol rich hydrocarbon sources will be immobilized in PVA hydrogels and
employed in a series of experiments to test biological degradation of hydrocarbon pollutants in refinery
wastewater rich in phenolic compounds.
CONCLUSION
The existing wastewater treatment facility at Ruwais refinery consists of separating immiscible hydrocarbons
and settleable material from water that is ultimately diluted with sea water and discharged into the marine
environment.

Wastewater characterization has shown the presence of polyaromatic compounds, phenols and cobalt in the
treated stream that is currently diluted by sea water and discharged into the sea. The dilution does not
degrade or eliminate these, thus making a strong case for the design and implementation of further treatment
processes that should include biological reactors.

The current volume of discharged water into the sea, excluding the new load from the new units, amounts to
approximately 1.5 million cubic meters per annum. This substantial amount can be usefully recycled for
various applications. In order to achieve this goal, the existing treatment process must undergo significant
upgrades and must include biological treatment unit and physical adsorption units.
ACKNOWLEDGEMENT
We would like to extend our thanks to:
Technical Cooperation Department, Japan Cooperation Center, Petroleum
Environment & Product Technology Department, Nippon Oil Research Institute Co., Ltd.
The Japanese Government (the Ministry of Economy, Trading and Industry)
for their financial contribution to this project.
We would like to thank TAKREER for their technical support and access to Ruwais refinery.
We would like to thank the UAE University for its financial and administrative support in this project.
REFERENCES
[1] C. E. Burklin, et al., Revision Of Emission Factors For Petroleum Refining, EPA-450/3-77-030, U.
S. Environmental Protection Agency, Research Triangle Park, NC, October 1977.
[2] Pollution Prevention and Abatement Handbook, WORLD BANK GROUP, Effective July 1998.
[3] Romano, F. Oil and Water Dont Mix: The Application of Oil-Water Separation Technologies in
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[4] Flanigan, D.A., et al. Droplet Size Analysis: A New Tool for Improving Oilfield Separation. SPE
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[5] Ryan, J. Process Selection for Oil Separation. Effluent and Water Treatment Journal. Vol 26,
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[6] P.L. Dold Current practice for treatment of petroleum Refinery Wastewater and Toxics Removal
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[7] Buckles, J., A. Kuljian, K. Olmstead, and S. Hester. 2004. Full-Scale Treatment of a Petroleum
Industrys Wastewater Using an Immersed Membrane Biological Reactor, presented at WEFTEC
2004, October 2-6, 2004.
[8] Hughes, S. and Cooper, D. Biodegradation of phenol using the self-cycling fermentation process.
Biotechnology & Bioengineering, July 1996, vol. 51, no.1, p. 112-119.
[9] Eaton, R.W. and Seliefonov, S.A. Biotransformation of 6,6-Dimethylfulvene by Pseudomonas
putida. Applied Environmental Microbiology, March 1996, vol. 62, no. 3, p. 756-760.
[10] Park, Hee-Sung; Lim, Sung-Jin; Chang, Young Keun; Livingston, Andrew G. and Kim, Hak-Sung.
Degradation of chloronitrobenzenes by coculture of Pseudomonas putida and a Rhodococcus sp.
Applied Environmental Microbiology, March 1999, vol. 65, no. 3, p. 1083-1091.