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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
Figure 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.
Tertiary
Carbon Adsorbtion Ultrafiltration
Treatment
Final Treated
Effluent
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, NH3, 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.
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.
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
Oily WW from SY
sewer
(Condensate plant)
Accidentally Oily
WW AY sewer
Existing above D
ground lines
Oily Sewer Mixing Basin
WW from (47 F10) Final Mixing & F
Dilution Pit SEA
Hydroskimmer
47F20
Oily Sewer from
tank farm
sweetening Units E
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).
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.
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.
C D
E F
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.
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