Al-Khwarizmi!! Engineering!!! Journal Al-Khwarizmi Engineering Journal, Vol. 6, No. 1, PP 24 - 30 (2010) Components and Treatments of Oilfield Produced Water Ayad A. Al-Haleem* Hamed H.Abdulah** Essam Abdul-Jalil Saeed*** * , ** Department of Geology/ College of Science/ University of Baghdad * Email: ayadah62@yahoo.com *** Technology Institute –Baghdad (Received 21 June 2009: accepted 29 December 2009) Abstract In this study, a review of variety of processes that are used in the treatment produced water prior to reuse or to responsible disposal are presented with their environmental issues and economical benefits. Samples of produced water from five locations in Rumaila oilfield/in south of Iraq were taken and analyzed for their contents of brine, some heavy metals, total suspended solids and oil and grease. Moreover, two samples of water were treated using reverse osmosis technique which showed its ability to treat such contaminated water. The results showed that the environmental impact of produced water arises from its chemical composition; i.e., its salt content, its heavy metals, and hydrocarbon contents. Keywords: Produced water, environment, heavy metals, components 1. Introduction Produced water is water trapped in underground reservoir rocks and is brought to surface along with crude oil and gas. Besides elevated concentration of heavy metals such as barium, uranium, cadmium, chromium, strontium and lead, produced water contains dispersed oil droplets and dissolved organic compounds and significant amount of anion such as carbonate, bromide sulfate. The largest volume of waste in the upstream petroleum industry is produced water. The total volume of produced water in the united states is roughly 21 billion/year [1]. Sources of this water may include flow from above or below or within the hydrocarbon zone, or flow from injected fluids and additives resulting from production activities [2]. Produced water is usually very salty and may contain suspended and dissolved solids, residual hydrocarbons, numerous organic species, heavy metals, naturally occurring radioactive and chemicals used in hydrocarbon extraction [3,4]. The major components of produced water vary according to the type of production activity associated with these types which includes oil production, gas production and coal bed methan (CBM) production. For example, produced waters from gas production are relatively more toxic than produced waters from oil production due to the higher contents of flow molecular – weight aromatic hydrocarbons such as benzene, toluene, and xylene [5,6]. Untreated produced water causes number of problems; these problems are:  Excess sodicity which cause clay deflection.  Excess soluble salts which can cause plants to dehydrate and die.  Reduced oxygen level enough to damage aquatic species [2].  Injection formation plugging due to suspended solids, which results in injection pressure increase and decrease in the produced water injection flow rate.  Scale problem which causes well bore clogging and fluid flow prevention [7,8,9].  Environmental impact due to chemical additive like corrosion inhibitor and H2S scavenger [10]. This page was created using Nitro PDF trial software. To purchase, go to http://www.nitropdf.com/ http://www.nitropdf.com/ Ayad A. Al-Haleem!!! Al-Khwarizmi Engineering Journal, Vol.6, No.1, PP 24-30 (2010) 25 A large number of methods were used as treatment technologies [11-21] such as heat treating, gas flotation, chemical separation, filtration, and biological degradation. Many methods are available to remove the dissolved hydrocarbons such as adsorption, volatilization, oxidation, ultraviolet, irradiation, precipitation, and biological processes [22,23,24]. Several methods are available to remove the suspended solids (like cuttings, sand and clay particles) and there methods are filtration, coagulation, gravity separation, and biological treatment [25,26,27,28]. The dissolved solids which include salt, hardness ions and heavy metals can be treated by processes like ion exchange, precipitation, evaporation, distillation and bio treatment [22,29,30,31]. Table (1) summarizes the reviewing of different technologies according to their environmental and cost issues. Table 1, Different Produced Water Treatment Technologies with Their Cost and Environmental Issues. Treatment Method Cost Environ- mental Effect Biological Treatment Low operating costs None- very low Gravity Separation 1. Plate Separators Low operating costs Very low 2. Hydrocyclones Low operating costs Very low 3. Decanting centrifuge Low operating costs Very low Gas Flotation + Gravity Separation + Chemical Addition Moderate operating costs Low Membrane Filtration (Microfiltration, Nanofiltration and Reverse Osmosis Low operating costs Low Carbon Adsorption Moderate operating costs Moderate Air stripping Low operating costs Moderate Ultra-Violet Light Low operating costs Moderate Chemical Oxidation (Ozone and/or hydrogen peroxide oxidation) Moderate operating costs Moderate Precipitation Low operating costs Moderate (Flocculating Polymers, biocides, reverse emulsion breakers, and corrosion inhibitors) High costs Moderate - High 2. Experimental Work Samples of produced water from five locations at Rumaila oilfield (south of Iraq) were collected and analyzed chemically for their brine composition and concentration of some heavy metals. Also the parameters such as Tss oil and grease, and PH are measured. More over, two samples of contaminated water were treated using micro filtration and reverse osmosis membranes. The analysis and treatment were done at Al- Mansour state company. Experimental apparatus Reverse Osmosis Reverse osmosis (commonly abbreviated as R.O) is a physical process which allows dissolved salts to be removed by forcing water to pass through a semi permeable membrane. The permeate, or product water passes through the membrane, while the dissolved salts, particles and the organic matter which are unable to pass through the membrane are conveyed to the drain as a concentrate or rejected water. The heart f an R.O declinator is the osmotic membrane. The R.O systems use spiral wound aromatic polyamide membranes capable to treat the salinity of seawater as TDS. The Concentration materials used, particularly for the parts in contact with the water, have proven resistance to corrosion (stainless steel, PVC and poly ethylene). R.O. units are fitted with an automatic system for control of the influent and effluent water pressure and of motor absorption and also equipped with flow meters and conductivity meters. The operation data are 380V, 50Hz, three phase flow rate 300 to 6000 L/hr(liter/hour). This page was created using Nitro PDF trial software. To purchase, go to http://www.nitropdf.com/ http://www.nitropdf.com/ Ayad A. Al-Haleem!!! Al-Khwarizmi Engineering Journal, Vol.6, No.1, PP 24-30 (2010) 26 Microfiltration Filtration is a physical process used to reduce turbidity. The impurities trapped by the filtering cartridge are removed by a backwashing procedure powered by an impeller with calibrated holes installed inside the stainless steel cartridge which is able to spray jets of water across the entire surface of the cartridge and propel the trapped deposits to the drain. The materials used for construction are non toxic and of high quality; these filters allow a degree of filtration of 100 microns to 300 and are able to work at an operation pressure of 10 bar. PH-meter The specifications of an electric meter modelS 595-PH are:  Standard measuring range 0-14 PH.  Indicator: digital, liquid crystal (LCD), 3 1/2 digit, h = 1/2".  Current output 4-20 mA DC on load < 700 ohm. 3. Field Observations It is important to mention that according to field investigations in the oilfield under study, procedure water coming from oil wells is four to seven times the volume of oil produced. These volumes represent huge amount of contaminated water that require economical and environmentally friendly methods of treatment to be reused or disposed off safely. Also, there are about tens of wells that have been used as disposal wells for produced water after a restricted water treatment. Discharging processes were done in Al- Dammam formations which have very low pressure property. Although this disposal option was not desirable due to many environmental concepts, the injection continued until the disposal wells were in capable of receiving more water. 4. Results and Discussion The water analysis of Rumaila oilfield is summarized in table (2). Although, the waters were taken from five locations, no significant differences are shown in the results since they related to the same oilfield. As known, the properties or constituents of produced water vary according to geological formation, to the type of hydrocarbon being produced and to the enhanced operations which are conducted. It can be seen in higher concentrations of solids, heavy metals like barium, strontium, calcium and bicarbonate ions have the potential to precipitate as scale. Table 2, Constituents of Produced Water at Five Locations of Rumaila Oilfield. Constitu- ent Produced Water (mg/L) Loca- tion 1 Loca- tion 2 Loca- tion 3 Loca- tion 4 Loca- tion 5 Sodium 35000 25000 28000 19700 22000 Potassium 720 450 410 250 220 Magnesium 390 810 670 520 480 Barium 280 190 180 220 200 Strontium 720 580 630 590 500 Sulfate 80 100 190 110 130 Chloride 65000 66000 67100 62000 61000 Calcium 5500 4400 4100 4000 4700 Cadmium 30 25 26 29 21 Chromium 110 90 95 90 100 Copper 100 85 90 75 95 Lead 280 210 220 160 150 Nickel 190 170 180 130 140 Zinc 150 88 99 110 120 HCO3 650 600 610 700 630 PH 8.2 8.5 8.6 8.4 8.1 TSS 8000 7500 8100 7600 7900 Oil and Grease 600 650 670 640 710 The scale can clog flow lines from oily sludge's that must be removed and form emulsion that are difficult to break [9]. However, the high concentrations of some heavy metals can cause many production problems for example the presence of different charge ions such as barium and sulfated calcium and sulfates iron and oxygen can cause deposits at discharge sites. Table (3) shows typical concentrations of pollutants in two treated produced water samples. This page was created using Nitro PDF trial software. To purchase, go to http://www.nitropdf.com/ http://www.nitropdf.com/ Ayad A. Al-Haleem!!! Al-Khwarizmi Engineering Journal, Vol.6, No.1, PP 24-30 (2010) 27 These data represent good results that have been achieved with this available technology by reverse osmosis membranes. Table 3, Results Using Reverse Osmosis And Micro Filtration. Constituent Untreated (mg/L) Untreated (mg/L) Treated (mg/L) Sodium 35000 28000 100 Potassium 720 410 10 Magnesium 390 670 ND Barium 280 180 10 Strontium 720 630 15 Sulfate 80 190 ND Chloride 65000 67100 150 Calcium 5500 4100 70 Cadmium 30 26 ND Chromium 110 95 ND Copper 100 90 ND Lead 280 220 15 Nickel 190 180 ND Zinc 150 99 ND HCO3 650 610 10 PH 8.2 8.6 7.4 TSS 8000 8100 350 Oil and Grease 600 670 10 The obtained water quality is suitable for many different usages such as re-injection processes for enhanced oil recovery or irrigation and other human purposes. In the present treatment system, the removal efficiency can be enhanced with an increase in the treatment stages which depend on the required water quality. Precipitation was detected at a number of micro filters and membranes which can be attributed to presence of oil, grease and lead contents in water respectively. It was necessary to remove these precipitations by chemical washing for example. 5. Conclusions  Field observations confirmed that produced water is responsible for many problems like corrosion, scale, microbial growth and dirty equipment.  Practices such as discharge to surrounding, storage on the surface in open tanks, re-using with a restricted treatment can arise many oilfield problems.  Chemical analysis of the produced water from other drilling locations is required to cover the wide range differences in the chemical and physical properties of water. Notation CBM Coal Bed Methan BTEX Benzene-Toluene-Ethyl benzene-xylene TDS Total Dissolved Solids TSS Total Suspended Solids H2S Hydrogen Sulfide PAHs Polycyclic Aromatic Hydrocarbons Acknowledgment The authors would like to thank engineer Mohamed A. Al-Haleem (from Al-Mansour state company) for his invaluable help in water treatment and in the interpretation of water characterization. 6. 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