GENERAL CHARACTERISTICS AND TREATMENT OF PETROLEUM REFINERY WASTEWATER 1.

INTRODUCTION Petroleum, commonly known as crude oil is available naturally below surface of the earth and has become the most significant fuel and raw material for production of chemicals in present day world. Due to higher demand for hydrocarbons, the pressure on exploration, production and further processing of crude oil / natural gas is tremendous and so the prices of crude oil have touched sky level recently. The main activities of the petroleum industry are: o o o o Exploration of crude oil and natural gas; Production of crude and natural gas; Processing consists of refining crude for gasoline, diesel, lubricants and further production of other downstream chemicals by cracking; Marketing and distribution of gasoline, diesel, lubricants and other processed chemicals.

1.1 Petroleum refining process Crude oil is a mixture of thousands of different hydrocarbons (compounds of hydrogen and carbon). Processing of crude is done in oil refineries where more useful petroleum products such as gasoline, kerosene, diesel, LPG (liquefied petroleum gas) etc., are produced by a process known as fractional distillation. Products having lower boiling point leaves from top and higher boiling point products leave the fractioning column at the bottom. Therefore, light distillates are LPG, gasoline, naptha; middle distillates are kerosene, diesel and heavy distillates including residuum are fuel oil, lubricating oils, wax and tar. Oil refineries pollute our air, water, and land through about 100 chemicals that they emit every day. 1.2 Refining operations Petroleum refining processes and operations can be separated into five basic areas: 1. Crude oil Pre treatment Crude oil often contains water, inorganic salts, suspended solids, and water-soluble trace metals. As a first step in the refining process, to reduce corrosion, plugging, and fouling of equipment and to prevent poisoning the catalysts in processing units, these contaminants must be removed by desalting (dehydration). The two most typical methods of crude-oil desalting, chemical and electrostatic separation, use hot water as the extraction agent. 2. Fractionation (distillation) is the separation of crude oil in atmospheric and vacuum distillation towers into groups of hydrocarbon compounds of differing boiling-point ranges called "fractions" or "cuts." 3. Conversion processes change the size and/or structure of hydrocarbon molecules. These processes include: Decomposition (dividing) by thermal and catalytic cracking; Unification (combining) through alkylation and polymerization; and Alteration (rearranging) with isomerization and catalytic reforming.

4. Treatment processes are intended to prepare hydrocarbon streams for additional processing and to prepare finished products. Treatment may include the removal or separation of aromatics and naphthenes as well as impurities and undesirable contaminants. Treatment may involve chemical or physical separation such as dissolving, absorption, or precipitation using a variety and combination of processes including desalting, drying, hydrodesulfurizing, solvent refining, sweetening, solvent extraction, and solvent dewaxing. 5. Formulating and Blending is the process of mixing and combining hydrocarbon fractions, additives, and other components to produce finished products with specific performance properties. 6. Other Refining Operations include: light-ends recovery; sour-water stripping; solid waste and wastewater treatment; process-water treatment and cooling; storage and handling; product movement; hydrogen production; acid and tail-gas treatment; and sulfur recovery. Auxiliary operations and facilities include: steam and power generation; process and fire water systems; flares and relief systems; furnaces and heaters; pumps and valves; supply of steam, air, nitrogen, and other plant gases; alarms and sensors; noise and pollution controls; sampling, testing, and inspecting; and laboratory, control room, maintenance, and administrative facilities. Fig. 1: Process flow diagram - Petroleum refining

2. WASTEWATER IN PETROLEUM REFINERIES PROFILE 2.1 Water and Wastewater Petroleum refineries are complex systems of multiple operations that depend on the type of crude refined and the desired products. For these reasons, no two refineries are alike. Depending on the size, crude, products and complexity of operations, a petroleum refinery can be a large consumer of water, relative to other industries and users in a given region. Within a refinery, the water network is as unique to the refinery as its processes. Fig.2: Overall refinery water balance

Many of the processes in a petroleum refinery use water, however, not each process needs raw or treated water, and water can be cascaded or reused in many places. A large portion of the water used in a petroleum refinery can be continually recycled with in a refinery. There are losses to the atmosphere, including steam losses and cooling tower evaporation and drift. A smaller amount of water can also leave with the products. Certain processes require a continuous make-up of water to the operation such as steam generating systems or cooling water systems. 2.2 Wastewater generation and characteristics The sources of wastewater in a refinery can be categorized as follows: Process water (high TDS) Cooling water & Condensate (low TDS) Stormwater (low TDS) and Miscellaneous wastewater

Process water is defined as water that has been in intimate contact with hydrocarbons in the refinery. Water that is generated in the process units is represented by desalter effluent, sour water, tank bottom draws and spent caustic. Desalter effluent The wash water used in desalters is typically 5 to 8% of the crude throughput. 3

Desalter effluent Contaminant Chemical oxygen demand (COD) Free hydrocarbons Suspended solids Phenol Benzene Sulphides Ammonia Expected concentration (mg/l) 400 to 1000 Up to 1000 Up to 500 10 to 100 5 to 15 Up to 100 Up to 100

In some refineries, the desalter effluent is pre-treated before sending it to the wastewater treatment plant. Fig. 3:Desalter effluent stripper

In typical desalter effluent pretreatment system, the desalter effluent is sent to a floating roof tank (floating roof in order to control VOC emissions) which typically has a residence time of a day or so in order to provide equalization, upset buffering etc. The brine is allowed to settle and separate. The oil is skimmed off and sent to refinery slops and the water phase is sent to the wastewater plant. The bottom solids from the tank is sent to the sludge treatment plant or the coker unit if the refinery has such a suit. Sour water Steam is used in many processes in refineries as a stripping medium in distillation and as a diluent to reduce the hydrocarbon partial pressure in catalytic cracking and other applications. The steam is condensed as an aqueous phase and is removed as sour water. Since this steam condenses in the presence of hydrocarbons, which contain hydrogen sulphide (H2S) and ammonia (NH3), these compounds are absorbed into the water at levels that typically require treatment. 4

Sour water producers Unit Crude Vacuum Catalytic cracker Delayed coker Visbreaker Hydrotreaters Hydrocracker Sulphur plant Producer Atmospheric tower overhead drum Tower hotwell Fractionator overhead drum Fractionator overhead drum and blowdown drum Fractionator overhead drum and blowdown drum Wash water separator Wash water separator Tail gas treater

Stripping of sour water Sour water is typically stripped off H2S and NH3 before sending it to a wastewater treatment facility. All the sour water produced in the refinery is flashed in a drum and any separated oil is sent to refinery slops. The vapours from this drum are sent to the flare. The sour water from the drum is then sent to a storage tank which provides the required surge in the system. The sour water is then passed through a feed/bottoms exchanger where it is heated up and then sent to the stripper. Steam is used in the reboiler to heat up the bottoms and provide the vapour traffic in the tower. The separated vapors containing H2S and NH3 are typically sent to a sulphur plant. The stripped water is routed via the feed/bottoms exchanger and a trim cooler for reuse in the refinery. Any excess water that cannot be reused would be sent to a wastewater treatment plant. Fig. 4: Sour water stripper configuration

Refineries that include process units such as catalytic crackers and delayed cokers produce more sour water than a less complex refinery. The sour water from these sources also contains phenols and cyanides, and should be segregated from the remaining sour water produced in the refinery. Dedicated sour water strippers may be used to process this water, and the stripped sour water from this stripper should be preferentially reused as wash water for the desalters. This will result in the extraction of a substantial portion (up to 90%) of the phenol contained in this sour water and result in a lowering of the load of phenol to the wastewater treatment system.

Expected concentration (mg/l) Contaminant Chemical oxygen demand (COD) Free hydrocarbons Suspended solids Phenol Benzene Sulphides Ammonia 390 to 8250 135 to 6550 100 to 1000 Sour water 500 to 2000 Stripped sour water 600 to 1200 < 10 < 10 Up to 200 0 < 10 < 100

Where necessary, the stripped sour water should be cooled prior to discharge to wastewater treatment, to avoid subjecting the biological treatment system to excessive temperatures. Tank bottom draws Typically, the categories of tanks that may require water draws in refineries include: crude tanks gasoline tanks and slop tanks.

The incoming crude to refineries normally contains water and sediments (mud) that are picked up when the oil is extracted from the wellsthis is referred to as bottom sediment and water (BS&W). When the crude is stored in large tanks, the BS&W settles to the bottom and must be periodically removed to prevent a buildup of this material which would otherwise result in a loss of storage capacity. Water draws are normally sent to either the wastewater treatment or to a separate tank where the solids are separated from the oil and water. The crude tank located inside a berm for secondary containment, is equipped with a valved drain line that is sent to a sump located outside the berm. The operator uses the valve to drain the BS&W periodically using the interface level indicator to ensure that hydrocarbons do not get inadvertently drained out. Some crude tanks use probes, which use high frequency electromagnetic measurement to detect the interface. Fig. 5: Crude tank water draw

The amount of water that is drained from gasoline tanks is relatively small compared to the amount of water from crude tanks. Crude tank bottom sediment and water contaminants Contaminant Chemical oxygen demand (COD) Free hydrocarbons Suspended solids Sulphides Expected concentration (mg/l) 400 to 1000 Up to 1000 Up to 500 Up to 100

Spent caustic Spent caustic is formed due to the extraction of acidic components from intermediate hydrocarbon streams. This includes residual H2S, phenols, organic acids, hydrogen cyanide and carbon dioxide. These acidic compounds are absorbed into the reagent, and the resulting spent caustic solution cannot be regenerated. As a result, these absorbed acidic compounds contained in the caustic solution must be purged intermittently or continuously from the caustic treating system, and replaced by fresh caustic. The caustic solution will drop out as separate aqueous phase in intermediate or product storage tanks. Subsequent drawdown and discharge from the tanks will be required. This discharge usually occurs to the sewer, frequently on a batch basis and can cause problems in the wastewater treatment plant. Sulphidic spent caustic can be treated in the wastewater treatment plant as long as it is added in a controlled manner. Phenolic spent caustic (from catalytic cracker, coker and kerosene/jet fuel treater) should be segregated from the sulphidic spent caustic and disposed off-site. Spent caustic stream Benzene Characteristic sulfonation scrubbing Alkalinity (mg/L) BOD (mg/L) COD (mg/L) pH Phenols (mg/L) NaOH (wt %) Na2SO4 (wt %) Sulphates (mg/L) Sulphides (mg/L) Sulphites (mg/L) 33,800 53,600 112,000 13.2 8.3 1 1.5-2.5 3,760 7,100 18,400 18,400 67,600 9-12 5,500 0.2-0.5 2,440 4,720 40,800 46,250 256 3,230 12.8 50 2 209,330 8,440 50,350 12.7 22.2 3,060 Orthophenylphenol washing Alkylate washing Polymerization

Total solids(mg/L) 90,300

Cooling water blowdown In distillation columns, the crude is heated up and vapourized in a fuel (fuel oil, natural gas or refinery fuel gas) fired heater. Various fractions are separated by condensing and cooling the products that are withdrawn from the tower. From an overall heat balance point of view, the heat that is put into the system by burning fuel and/or the introduction of steam has to be removed or rejected. This is accomplished in various ways, including: heat exchange with boiler feedwater to generate steam; heat exchange with other process streams; rejection of heat using air coolers; and rejection of heat to cooling water.

In a cooling tower system, part of the circulating water is removed as blowdown to prevent the buildup of dissolved solids in the system. The quantity of blowdown required depends on the quality of the make-up water, and the number of cycles of concentration that the cooling tower is operated at (typically 4 to 7). Cooling tower blowdown is typically sent to wastewater treatment in refineries via the sewer. This is because in many cases the pressure on the process side of heat exchangers is higher than the cooling water pressure, and any leaks in a heat exchanger would result in the contamination of the cooling water with hydrocarbons. This practice imposes a hydraulic load on the wastewater treatment system. Cooling tower blowdown Contaminant Chemical oxygen demand (COD) Free hydrocarbons Suspended solids Dissolved solids Expected concentration (mg/l) 150 <5 Up to 200 Up to 700

Condensate blowdown

In a refinery condensate losses are from:

Blowdown from the plant boiler system Blowdown from the various steam generators that are located in the process units and Unrecovered condensate from steam traps, steam tracing etc.

Any condensate lost to the sewer increases the temperature of the wastewater and thus imposes a heat load at wastewater treatment. Stormwater and sewerage Stormwater from within the refinery process areas is potentially contaminated and typically needs to be treated prior to discharge. Non-process area stormwater may be discharged without prior treatment if allowed by local regulation. Sewerage refers to wastewater that is discharged from kitchens, employee locker rooms and washrooms. Miscellaneous discharges The raw water treatment in a refinery creates wastewater and sludges that require disposal. Typical refinery laboratories analyse both hydrocarbon and water samples. In addition to this, laboratory wastewater also contains discharges from sinks in the laboratory and discharges from bottle washing systems in the laboratory.

3. EFFLUENT TREATMENT The technology used for refinery wastewater systems is site-specific and depends largely on influent conditions and the level of treatment required which is governed by local regulations. Fig. 6: Typical refinery wastewater treatment

In a refinery wastewater treatment system, two steps of oil removal are typically required to achieve the necessary removal of free oil from the collected wastewater prior to feeding it to a biological system. This oil removal is achieved by using an API separator followed by a dissolved air flotation (DAF) or induced air flotation (IAF) unit. The wastewater from the secondary oil/water separation unit is sent to the equalization system that is used to dampen out variations in flow and concentration in the refinery wastewater. The wastewater is then routed to the aeration tank/clarifier which constitutes the biological system. The effluent from the clarifier is then sent to tertiary treatment (if necessary) prior to discharge. 3.1 Wastewater segregation Given that there is a shortage of available raw water in many locations, and the fact that a typical refinery produces anywhere from 10 to 50 gallons of wastewater per barrel of crude processed, the reuse of treated refinery wastewater is increasingly coming into focus. In a segregated system the refinery wastewater system would consist of two parallel trains with the same unit operations, except that the low TDS train would not include an API separator because the suspended solids loading of the inlet wastewater tends to be quite low. Fig. 7: Segregated wastestreams treatment

This level of segregation and treatment is not common practice in refineries but is sometimes considered in water-scarce areas. 3.2 Primary treatment The primary treatment for refinery wastewater is a physical operation, usually gravity separation, to remove the floating and the settleable materials in the wastewater. In a typical refinery wastewater treatment system, the primary treatment step consists of an oil/water separator where oil, water and solids are separated. This is followed by a secondary oil/water/solids separation step in which a DAF or an IAF unit is used. 3.3 Equalization system The objective of the equalization system is to minimize or reduce the fluctuations caused due to either sudden change of flow or composition in the wastewater treatment plant. Flow equalization provides dampening of the flow variations, thereby reducing potential spikes in flow and loads to the downstream units; it also reduces the size of the downstream units and the cost of the overall refinery wastewater system. Concentration equalization provides dampening of contaminants, thereby preventing the shock loading of the downstream units such as biological systems. In a biologicallybased system, performance is limited by the capacity of the microorganisms to adapt to the changing conditions of variation in flow and composition. 3.4 Secondary treatment Biological treatment is the most widely used wastewater treatment technology for removal of dissolved organic compounds in the oil refining industry and maybe either suspended growth process or attached growth process. Micro organisms use organic constituents as food for their growth and clump together to form the active biomass. The most commonly practiced suspended growth process used in the treatment of refinery wastewater is the activated sludge process. Performance of Typical Activated Sludge Systems Type of waste Sludge loading (lb BOD/day/lb sludge) 0.6 0.3-0.4 0.1-0.2 0.65-0.76 Detention time (hours) 4-5 3-4 18-22 8-10 Percentage of BOD reduction 90-95 90-95 88-92 95-97 Comment

Refinery Refinery Refinery Petrochemical

99% phenol removal 98% phenol removal Minimal sludge production Sludge bulks for long period

The PACT process has great potential for controlling whole-effluent toxicity in refinery wastewater. It involves the addition of powdered activated carbon (PAC) to the activated sludge process for enhanced performance. For applications where further tertiary treatment such as reverse osmosis will be used, MBR can be attractive versus the alternative option of using media filtration and microfiltration after biological treatment. In some cases when a refinery site is required to meet tight ammonia or nitrogen limits, the biological treatment system could include either a nitrification (by the use of nitrifying bacteria) or a combined nitrification/denitrification step.

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3.5 Tertiary treatment Tertiary treatment needs to be considered if the refinery needs to meet stringent limits for different contaminants such as: total suspended solids (TSS); chemical oxygen demand (COD); dissolved and suspended metals; and trace organics such polyaromatic hydrocarbons (PAHs)

Filtration Effluent from the biological treatment system typically contains about 25 to 80 mg/l of suspended solids depending on the operating conditions in the clarifier. Refineries at many locations need to meet limits as low as 15 mg/l on a consistent basis. In these instances, one option is for the effluent from the clarifier to be filtered using sand filters. Membrane filtration processes are becoming popular and include options such as microfiltration or ultrafiltration; microfiltration or ultrafiltration, with reverse osmosis; microfiltration or ultrafiltration with nanofiltration; and ion exchange softening

Microfiltration and ultrafiltration will both produce a very clear filtrate with <1 mg/L suspended solids. Reverse osmosis (RO) can remove the dissolved salts and metals found in the refinery effluent, potentially producing a product water suitable for reuse at the refinery. Because of the hydrophobic nature of the membrane materials, they are highly susceptible to organic fouling by oil and grease. For this reason most MF and UF manufacturers have a typical specification of <1 mg/l oil and grease. In order to remove dissolved and emulsified oil and grease, granular activated carbon (GAC) pretreatment is typically used. One major application of NF is water softening before further treatment such as reverse osmosis or ion exchange. Activated carbon Removal of dissolved organic constituents from the refinery wastewater can be done by carbon adsorption. Chemical oxidation Chemical oxidation in a refinery may be used for reduction of residual COD, non-biodegradable compounds, and trace organic compounds. It is not common to have a chemical oxidation system in a refinery wastewater treatment plant. Ion exchange Ion exchange softening is another viable option for the removal of the dissolved inorganic compounds found in the refinery effluent. Water re-use and recycling is made possible after tertiary treatment to bring the wastewater constituents to an acceptable level. 11

3.6 Treatment of sludges In a refinery wastewater treatment plant, sludge is typically produced from the following unit operations: API separatorbottom sludge; dissolved gas flotation (DGF) and induced gas flotation (IGF) systemsfloat and bottom sludge; biological treatmentwaste biological sludge

Fig. 8: Sludge generation in wastewater treatment system

API sludge, after further dewatering and de-oiling, can be sent either to off-site disposal or to the coker unit in the refinery. The sludge from the DGF is normally sent to the same system that treats the API sludge. The float from the DGF/IAF typically contains emulsions and the chemicals (flocculants and coagulants). The float is sent to a tank where emulsion-breaker chemicals are added (if necessary) and the fluid is recirculated and heated up to break the emulsions. The material in the tank is then sent to disposal. The biological sludge is sent to a gravity thickener or DAF thickener, where water is separated from the sludge and returned to WWT. The sludge from the thickener is sent to an aerobic digester where air is added to digest the sludge. This step is essentially a volume reduction step to lessen the load on the downstream filter. In some cases the sludge from the thickener is sent directly to the filter. Several types of filters such as belt filter presses, plate and frame filters etc can be used. This treated sludge is then disposed by land farming or landfills or off-site disposal.

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Fig. 9: An alternative sample wastewaster treatment scheme, mainly for oil and organics removal

Fig. 10: Diagram of a wastewater treatment process for reuse at oil refineries

Fig. 11: diagram of an advanced refinery wastewater treatment system considering membrane bioreactors for secondary treatment and reverse osmosis or reverse electrodialysis as tertiary treatment

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3.7 Zero Liquid Discharge: The recycling/reuse options result in the need to discharge a concentrated brine stream that comes from the reverse osmosis/nanofiltration reject. In a ZLD system the brine that is usually discharged from a wastewater reuse system is further treated to extract more water and separate the dissolved solids that are left as solid crystals for disposal. The water that is removed is sent back to the refinery for recycle. Application of ZLD in refineries is very rare, in part because the energy requirements are very high. The possible use of this approach needs to be evaluated on a site-specific basis. Fig. 10: ZLD scheme

4. MINIMUM NATIONAL STANDARDS (MINAS) As per the Environment (Protection) Rules, 1986, India, the standards for discharge of petroleum refinery effluents are as follows: Concentration not to exceed, mg\L S. No. 1 2 3 4 5 6 7 8 9 10 Parameter pH Oil & Grease BOD 3 days, 27oC COD Suspended Solids Phenols Sulphides CN Ammonia as N TKN (except for pH) 6.0-8.5 5.0 15.0 125.0 20.0 0.35 0.5 0.20 15.0 40.0

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Concentration not to exceed, mg\L S. No. 11 12 13 14 15 16 17 18 19 20 21 Parameter P Cr (Hexavalent) Cr (Total) Pb Hg Zn Ni Cu V Benzene Benzo (a) Pyrene (except for pH) 3.0 0.1 2.0 0.1 0.01 5.0 1.0 1.0 0.2 0.1 0.2

Notes:(i) Concentration limits shall be complied with at the outlet, discharging effluent (excluding discharge from sea water cooling systems) to receiving environment (surface water Bodies, marine systems or public sewers). In case of application of treated effluent directly for irrigation/horticulture purposes (within or outside the premises of refinery), make-up water for cooling systems, fire fighting, etc., the concentration limits shall also be complied with at the outlet before taking the effluent for such application. However, any use in the process such as use of sour water in desalter is excluded for the purpose of compliance. (ii) In case of circulating seawater cooling, the blow-down from cooling systems shall be monitored for pH and oil & grease (also hexavalent & total chromium, if chromate treatment is given to cooling water) and shall conform to the concentration limits for these parameters. In case of reuse of treated effluent as cooling water make-up, all the parameters (as applicable for treated effluent) shall be monitored and conform to the prescribed standards. (iii) In case of once through cooling with seawater, the oil & grease content in the effluent from cooling water shall not exceed 1.0 mg/l.

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5. CASE STUDIES 5.1 DESIGN FOR WASTEWATER TREATMENT PLANT FOR KRPC Kaduna Refining and Petrochemicals Company (KRPC) is an Oil Refinery Complex in Kaduna, Nigeria. The plant refines two different types of crude oil, heavy crude of 50,000 barrels per day and light crude of 60,000 making a total plant capacity of 110,000 barrels per day; therefore the plant has two atmospheric and two vacuum distillation units. In addition to this, the refinery complex has other process units for conversion such as cracking, hydrotreating , reforming units etc. The following table shows the capacity of the units in the refinery.

Almost all the units mentioned above use tons of water during processing and in turn generate tons of waste water per day. In addition to the production units mentioned above, a lot of waste water is produced in other units such as feed/intermediate product storage, crude oil desalting, utilities plant as well as domestic/sanitary wastes. The amount of waste water produced from each unit as well as the composition and concentration of pollutants in the effluent was estimated using the rates given by Wang et al (2006). The following table summarises the flowrates, composition and concentration from this units.

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This can further be summarized to get the total effluent flow rate and concentration of pollutants in this in the effluent.

Treatment process design The plant is designed to have different units; starting with a primary treatment unit where difference in density as well as action of gravity will be used in an oil water separator to recover most of the free oil which can easily float and be skimmed off. The oil water separator can also remove about fifty percent of suspended solids, so the effluent from this unit have less loading of suspended solids, and most of the residual oil present will be in emulsion. To remove the emulsified oil and other suspended solids, a secondary treatment unit is needed. This will use rising bubbles of air to take off both solids and oil which float on the aeration basin and be skimmed off. A tertiary treatment unit is needed to remove the phenols and other dissolved hydrocarbons by the action of micro-organism in a biological treatment unit. Effluent from the biological treatment units will be filtered and polished in a dual media filters by using sand and activated carbon to give an effluent of a very low turbidity. However, in order to re-use the water the dissolved salts should be removed by desalination systems. Reverse osmosis is currently employed in sea water treatment plants for salt removal, hence similar systems can be used in desalinating the effluent from the filtration unit to give a clear permeate which is free of any dissolved salts and can be re-used in the refinery. Concentrated brine from the desalination unit can be passed through multi-stage evaporator and to remove more water vapour so that the salt can be crystallised and recovered in solids. Like most waste water treatment plants, there is a problem of solids handling due to the enormous amount of sludge generated. In this design, the gravity separation, air flotation and biological treatment units are expected to produce a lot of sludge which in addition to suspended solids, will also contain oil and biological substances. Therefore a solid-handling unit will be required to dewater the sludge and dry the cake which can be used for land filling and for agricultural purposes. The sludge handling units mix all the sludge and pass it to an anaerobic digestion unit where biogas is produced and can be used in heating and evaporating residual water from the cake in the cake dryer after the cake has been dewatered in a centrifuge.

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5.2 EFFLUENT TREATMENT FOR TOXICITY REMOVAL IN BAY AREA Some American refineries have used GAC to achieve compliance with NPDES permit requirements for toxicity. There are five major refineries in the San Francisco Bay Area as of 2003. Because of the stringent toxicity requirements for direct discharge to the Bay, four of the major refineries have installed GAC systems to polish secondary treatment plant effluent prior to discharge (Chevron Texaco, Valero, Tesoro, and Shell Equilon). The one exception is the ConocoPhilips Refinery in Rodeo, which has a PACT system for organics and toxicity removal. These GAC systems are designed mainly to reduce toxicity rather than COD. The toxicity of treated refinery effluent is believed to be caused mainly by naphthenic acid. The spent GAC from the refineries is regenerated offsite by a contractor. The cost of GAC treatment in these refineries has been lower than anticipated because COD removal is not critical for meeting toxicity requirements, and thus the GAC beds can last much longer between regenerations. The iron coprecipitation process has been used successfully in several San Francisco Bay Area refineries to remove selenium to below 50 ppb in treated effluent. Based on bench- and pilot-scale tests in a refinery, a ferric chloride dosage of 50 mg/L as Fe was necessary to achieve the required 50 ppb selenium at all times. The iron coprecipitation system in the Shell Equilon Refinery generates a large amount of iron sludge for disposal. An outside contractor uses an onsite belt filter press system to dewater the iron sludge before its offsite disposal as hazardous waste in California. One of the Bay Area refineries has installed a second above-ground biological treatment system to treat waste streams with higher benzene concentrations. The existing biotreater is pond-based with DAF clarifiers. Figure shows a block flow diagram of the revised effluent treatment system. The process train includes conventional refinery treatment processes, two different biological treatment systems, an iron coprecipitation system for selenium removal, and GAC for toxicity reduction and is therefore a complex one.

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5.3 RUWAIS REFINERY OVERVIEW The wastewater treatment facility in the Ruwais refinery belongs to the "Oil Movement Department". Figure 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 Figure 13: 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:

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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 247F001B. 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). 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.

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Wastewater analysis parameters Sample location Code Design Flow Rate Average Flow Rate Min Flow Rate Max m3/hr Min TPH Max mg/l Min Oil & Grease Max mg/l Naphthalene Acenaphthylene Acenaphthene Flourene Phenanthrene g/l g/l g/l g/l g/l 3428 306 0.18 21.2 1.80 236 334 ND 7.4 114 164 220 1.20 0.8 88.2 1.8 < 0.22 ND < 0.05 0.07 0.20 < 0.05 < 0.09 0.10 < 0.05 ND < 0.10 ND ND < 0.22 ND < 0.05 ND < 0.08 < 0.05 ND < 0.05 ND ND < 0.10 ND ND 29.6 ND 0.30 4.10 4.20 576 218 < 0.18 2.60 0.40 0.40 mg/l 3714 466 339 253 124 89 12.8 622 mg/l 290 488 290 49 290 33 < 0.2 < 0.2 37.7 Unit m3/hr m3/hr m3/hr A 175.5 129 155 155 155 B 177 C F F D E

Anthracene

g/l

0.40

< 0.05

0.20

< .05

0.20

Fluoranthene

g/l

34

12.0

88.4

3.20

20.6

Pyrene

g/l

6.60

6.40

46.6

0.80

< 0.05

Benzo(a)anthracene Chrycene Benzo(b)flouranthene Benzo(k)flouranthene Benzo(a)pyrene

g/l g/l g/l g/l g/l

19.8 ND ND < .08 0.60

17.4 41.2 0.20 0.20 0.20 23

11.4 32.4 4.00 1.60 0.40

0.30 0.40 0.10 < .08 < .05

< 0.05 ND < 0.1 ND ND

Dibenzo(a,h)anthracene Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene 2,4-Dinitrophenol 2-Methyl-4,5-dinitrophenol 2,4,6-Trichlorophenol 2,4-Dichlorophenol 2,4,5-Trichlorophenol Phenol m,p-Cresol * o-Cresol + 2-cyclohexyl4,6-dinitrophenol* 2,3,4,6-Tetrachlorophenol 4-Chloro-3-cresol 2,4-Dimethylphenol o-Chlorophenol 2,6-Dichlorophenol o-Nitrophenol p-Nitrophenol Pentachlorophenol Al As Cd Co Cr Fe Mn Pb

g/l g/l g/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l

0.20 0.80 0.40 ND 0.02 ND ND ND 0.20 0.24 ND 0.18 0.06 ND ND ND 0.14 ND 0.06 0.89 ND ND ND 0.03 11.7 0.20 0.03

ND 0.80 ND ND 0.02 ND ND ND 0.19 0.24 ND 0.11 0.06 0.04 ND ND 0.11 ND 0.05 0.28 ND ND ND 0.01 3.42 0.09 ND

ND 2.80 2.00 ND 0.10 ND ND ND 0.24 0.23 ND 0.32 0.10 0.14 ND ND 0.10 ND 0.07 0.09 ND ND ND ND 0.68 0.02 ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.02 ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.02 ND ND ND ND ND ND ND

0.20 ND ND ND ND ND ND ND 0.17 0.12 ND 0.18 0.07 0.06 ND ND 0.07 ND ND 0.05 ND ND ND ND 0.97 0.03 ND

ND ND ND ND 8.98 ND ND ND 5.75 2.95 ND 0.38 0.23 ND ND ND 0.09 ND 0.10 0.85 ND ND 1.05 0.01 0.33 <0.013 ND

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V Zn Total Sulphur (as SO4) Hg Min pH Max Min NH4+

mg/l mg/l mg/l mg/l

0.01 1.66 75.0 ND 9.25 10.8

<0.004 ND 0.53 83.2 ND 9.82 10.2 0.72 3.96 72.2 106 6726 76.0 41.7 ND 50 ND 560 484 41.0 22.7 2.60 0.25 53.2 ND 10.6

ND 0.003 3567 ND 5.69

ND 0.003 3550 ND 7.75

ND 0.07 142 ND 10.3

ND 0.05 333 ND 10.2

mg/l

0.76 4.96 28.9 372 3272 82.2 60 ND 65

0.34

0.54

0.98

0.90

Max mg/l Min TSS Max mg/l TDS Min SO4 Max mg/l Min S-2 (g/l) Max g/l g/l mg/l mg/l mg/l

43.1

36.6

12.6

68.7

52430 51160 2060 3350 3250 127

13590 11.1

ND

ND

21 900

ND

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.

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5.4 BHARAT PETROLEUM - MUMBAI REFINERY Bharat Petroleums Mumbai Refinery (BPMR) currently processes about 12 Million Metric Tons of crude oil per annum. BPMR has processed 61 different types of crude in five decades of its operations, making it one of the most flexible Refineries in the country. Waste Water Treatment Plant The effluent treatment plant is designed to process the effluent from various units like CDU, FPU, FCCU, DHDS, CCU, Aromatics etc.. This facility is designed to process 240 M3/hr of effluent containing pollutants like oil sulphides, phenolics, BOD and suspended solids. Here, the process effluent is given a Powdered Activated Carbon Treatment (PACT), which is a highly effective process to meet the stringent Minimal National Standards (MINAS). Tertiary Treatment Plant (TTP) In TTP, the WWTP (MINAS) effluent is processed further, to recover desired quality of water for recycle to DM plant- thus conserving raw water. TTP is designed for processing 1000 m3/d of effluent with 70 % recovery. The unit consists of a pretreatment section followed by a suite of Reverse Osmosis (RO) membranes. Permeate from the RO membrane is diverted to DM plant for further processing thereby reducing the raw water requirement for the Refinery. Water management Treated effluent water recycling and re-use and rain water harvesting Re-circulating sea cooling tower systems instead of once through sea cooling water system, thereby minimizing the sea cooling requirement and effluent discharge to the sea.

5.5 BHARAT PETROLEUM - KOCHI REFINERY Kochi Refinery presently has a crude oil processing capacity of 9.5 MMTPA (Million Tons per Annum) in its two Crude Distillation units (CDU-1 and CDU-2). Kochi Refinery is the first organization in Kerala to receive the ISO 14001 certification. Effluent Treatment Plants (ETP) takes care of the liquid effluent from the process units and other off site areas. The design of the effluent water treatment system is such that the water discharged from the treatment unit is well within the quality levels prescribed by the State Pollution Control Board and the national standards (MINAS). Kochi Refinery is the first industrial unit in Kerala permitted by the State Pollution Control Board, to discharge treated water into inland rivers. The 3 MLD ETP consists of: Tilted Plate Interceptor( TPI) Dissolved Air Flotation ( DAF) Bio tower Aeration Tank Secondary Clarifier Filters Sludge Handling Equipment Chemical Dosing & Handling System VOC Control System 26

An ecological park has been developed within the company premises in 2004-05 by planting 4000 saplings of different species of trees, flowering plants, herbal trees, etc. Now the ecological park and the treated effluent waterbed attract different birds including seasonal migratory birds. Implementation of rain water harvesting schemes inside the refinery is another project for environmental protection. Water collected from this facility is routed to cooling towers as make up water. A new effluent treatment plant costing Rs.50 crore will be completed by October 2010. 5.6 IOC, HALDIA REFINERY - 30 MLD WWTP Indian Oil currently controls ten of Indias twenty refineries. The group refining capacity is 60.2 MMTPA or 1.2 million barrels per day gives it the largest share among refining companies in India. It accounts for 33.8% share of national refining capacity. This is biggest recycling plant using Reverse Osmosis Technology in any refinery in India. The plant comprised of:

Oil Skimmer (API) Dissolved Air Floatation (DAF) Bio-Tower Filtration High rate contact type clarifier Reverse Osmosis plant

5.7 IOC, PANIPAT REFINERY Indian Oil commissioned a 600 m3/hr (14.4 MLD) Wastewater treatment plant for its Panipat refinery in 1996. The plant comprised of:

Tilted Plate Interceptor (TPI) Dissolved Air Floatation (DAF) Bio-Tower Aeration Clarifier Filtration Pressure Sand Filter Dual Media filter Gravity Thickener Centrifuge 27

5.8 HPCL, MUMBAI REFINERY Hindustan Petroleum Corporation Ltd. (HPCL) commands 20% market share of the Indian petroleum industry. It operates 2 major refineries, one in Mumbai of 5.5 MMTPA and the other in Vishakapatnam of capacity 7.5 MMTPA. In order to comply with pollution control boards proposed future liquid effluent norms and HPCLs commitment to a greener environment, the company went in for a complete overhaul of its effluent handling facility, replacing prior-existing ETP-I & ETP-II with a new integrated ETP using latest technologies in 2009. The plant included:

Non-metallic API Separators Tilted Plate Interceptor ( TPI) Dissolved Air Flotation (DAF) Sequential Batch Reactor (SBR) Membrane Bioreactor (MBR) Sludge Handling Equipment Chemical Dosing & Handling System Sludge Bioremidation Reverse Osmosis (RO) System Volatile Organic Control (VOC) System

5.9 CPCL, MANALI TERTIARY TREATMENT PLANT Chennai Petrochemicals Corporation Ltd. (CPCL), formerly known as Madras Refineries Ltd. (MRL), has a 2.5 MGD (9.6 MLD) Reverse Osmosis Plant. At the time, the plant was reputed as Asias first large scale sewage to water recovery plant. The plant comprised of:

Biological Treatment Aeration Tank, Bio-Clarifier Hydro-treator, Pressurized Solution feed (PSF), DMF, Cartridge Filters Ammonia Striper and recarbonation system RO System

The entire plant was automated requiring minimum manual intervention. The plant was successfully commissioned in 1994.

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6. REFERENCES 1. OSHA technical manual - section IV: chapter 2 Petroleum refining process www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html 1/ 2. IPIECA Operations Best Practice Series: Petroleum refining water/wastewater use and management, 2010 3. Treatment of Oilfield and Refinery Wastes, Joseph M. Wong and Yung-Tse Hung, Taylor & Francis Group, LLC, 2006 4. EPA Office of Compliance Sector Notebook Project: Profile of the Petroleum Refining Industry, September 1995 5. Refinery Wastewater Treatment: A true Technological Challenge, Farid Benyahia 6. Official websites of Bharat petroleum Hindustan Dorr Oliver Ltd.

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