SPE 124212 Well Treatment Fluids Prepared with Oilfield Produced Water

Leiming Li, SPE, Ksenia Eliseeva, SPE, Schlumberger; Vasily Eliseev, SPE; Oscar A. Bustos, SPE, Kevin England, SPE, Paul R. Howard, SPE, Curtis L. Boney, SPE, Michael D. Parris, SPE, and Syed A. Ali, SPE, Schlumberger

Copyright 2009, Society of Petroleum Engineers This paper was prepared for presentation at the 2009 SPE Annual Technical Conference and Exhibition held in New Orleans, Louisiana, USA, 47 October 2009. This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract Oilfield produced water usually comprises both the formation water and injected fluids from prior treatments. Produced water may be environmentally hazardous and usually contains bacteria, hydrocarbons, and high levels of dissolved salts. As such, the proper disposal of produced water is often expensive. Meanwhile, fresh water used to formulate oilfield treatment fluids is becoming more costly and more difficult to obtain. Operators, as well as service companies, have therefore shown a strong desire to use produced water in field operations to reduce costs. Consequently, a series of laboratory experiments have been performed to optimize the viscosity profile of fracturing fluids prepared with produced water. Preparation of polysaccharidebased fracturing fluids with produced water frequently resulted in fluids with poor viscosity profiles despite the fact that the produced water was pretreated with biocide. Furthermore, the problem could not be resolved by just adding more biocide. In a number of representative cases, the guar-based fracturing fluids, prepared with produced water and regular biocide, quickly lost their viscosity after hydration, possibly because of the degradation of the guar by the bacterial enzymes in the produced water. A new fluid stabilizer was recently invented to address the problem, and it was observed that the addition of the stabilizer dramatically extended the lifetime of the polysaccharide-based fracturing fluids prepared with produced water. The fluid stabilizer was simply added to produced water prior to mixing the polymer. The polysaccharide-based fluids prepared with the stabilizer-treated produced water showed stable viscosity profiles at both surface and bottomhole temperatures. The use of the fluid stabilizer has greatly enhanced the fluid performance and job efficiency since its initial introduction in the field in June 2008 and was implemented in about 80 successful fracturing and sand control jobs by the end of 2008. The invention and successful application of the fluid stabilizer have reduced the operating costs for the operators and service companies. At the same time, this new technology has also helped improve the environment by cutting the fresh water usage in the field. This paper will discuss the chemistry, experimental studies, and case histories. Background Oilfield produced water is a term used in the oil industry to describe the water that is produced along with the oil and/or gas, and it may contain formation water, flowback fluids, surface water, and water from any other sources. Produced water is in good contact with various environmental elements such as air, soil, formation, and contaminated water tanks, and it is therefore not surprising that produced water often contains high level of bacteria and/or bacterial enzymes as bacteria are ubiquitous in almost every habitat on Earth. Formation water usually consists of salty water that may be the ancient seawater trapped in the formation. On the other hand, produced water stored in tanks or ponds is often subjected to evaporation that can further increase the salt concentration in the water. Measured by volume, produced water is the largest waste generated during the production process, and the volume of produced water can be several times that of hydrocarbons produced (Stephenson, 1992). The potential benefit of using such produced water, if feasible, for oilfield operations is at least twofold. First, the cost related to the proper disposal of produced water can be reduced. Produced water usually contains high levels of salt and hardness as well as bacteria. Without proper treatment, produced water is environmentally hazardous. It can be, however, costly to clean up produced water following the local, state, or federal regulations. If produced water can be treated in situ and then used to prepare fracturing fluids, the operating cost is expected to decrease. Second, as large amount of fresh water is used for oilfield operations such as water flooding, subterranean fracturing, etc. (Gleick, 1994), reusing produced water can cut the consumption of fresh water that is becoming more costly and more difficult to obtain since neighboring residents and municipal and state governments are putting more restrictions on water availability from either surface or

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subsurface aquifers. Operators, as well as service companies, are therefore interested in using produced water to reduce operating costs and gain competitive edges. Many commercial fracturing fluids are aqueous-based fluids, crosslinked or uncrosslinked. The fluids can be made viscous enough to suspend and carry proppants downhole for fracturing operations. To form such a fluid, a polymeric gelling agent, such as a soluble polysaccharide can be used. Polysaccharides, such as guar and guar derivatives, are susceptible to bacterial damage. Bacteria can synthesize enzymes, such as cellulase (including hemicellulase), glycoside hydrolases, and amylase, that catalyze the breakdown of polysaccharides (Fodge, et al., 1996; Gupta, et al., 1995; Tjon Joe Pin, et al., 1993; Shell and Hitzman, 1992; Dawson, 1991). Biocide (bactericide) is often added as an additive to suppress or kill bacteria, thus preventing the degradation of the polymer fluid and the growth of a large biomass in the formation. Commonly used biocides in oilfield may include glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide (DBNPA), tetrakishydroxymethyl phosphonium sulfate (THPS), and quaternary ammonium compounds (QACs), to name a few (Paulus, 2005). Heavy metal biocides can also be used to kill bacteria or inhibit the growth of bacteria, including Hg compounds (Paulus, 2005), Sn compounds (Paulus, 2005), Cu compounds (Paulus, 2005), Ag compounds (Ring, et al., 2004), etc. The bacteriainhibiting or bacteria-killing mechanisms of heavy metal compounds may be different from case to case, but they often inhibit enzymes in bacteria, which may suppress or kill bacteria. Many enzymes have a number of SH groups (cysteine) to which heavy metal ions can easily attach, thus inhibiting the enzyme activity (Bettelheim and March, 1991). Many of these heavy metal biocides may cause environmental damages, such as heavy metal contamination and accumulation (Paulus, 2005). At the same time, there could be problems especially for inorganic heavy metal compounds if used as biocides in produced water. Produced water contains various kinds and concentrations of anions such as Cl-, CO32-, SO42-, S2-, etc., that could precipitate out heavy metal cations quickly, making such inorganic heavy metal biocides lose effectiveness. When fracturing fluids, for example, polysaccharide-based fracturing fluids, are prepared using clean water or brine, normal dosage of the common biocides is usually sufficiently protective (Paulus, 2005). This may not always be the case when produced water is used to make fracturing fluids, as produced water typically contains much higher concentrations of bacteria and/or bacterial enzymes. The biocides may be depleted quickly by overwhelming populations of bacteria and/or high concentrations of ions in produced water. At the same time, biocide is usually applied at low dose (sufficient for clean water) because of environmental and economical considerations and may not denature (disable) bacterial enzymes at all. These enzymes will then continue to decompose polysaccharides even after the bacteria can be killed or suppressed. A new fluid stabilizer was therefore invented (Li, et al., 2008) that can effectively remove the damaging bacteria and/or bacterial enzymes. The fluid stabilizer actually includes a number of metal compounds, either inorganic or organometallic compounds. The compounds can be used individually or in combination. The metal has an atomic weight between Zn and Ag, and some of the metal compounds are routinely used as the crosslinkers in the oilfield. The fluid stabilizer was found capable of denaturing enzymes that break down polysaccharide-based fracturing fluids. These enzymes include the cellulase/hemicellulase mixture, an enzyme breaker that is used in the oilfield to break down guar-based fracturing fluids. Experimental Procedure and Results Produced Water Analyses Produced water samples were collected without further treatment from a number of oilfield locations in North America. Water analyses were carried out to measure the ion species and concentrations. The typical produced water samples may contain the following cations (with the approximate concentration ranges indicated): Na: K: Mg: Ca: Fe: 9000 to 50 000 mg/l 0 to 2000 mg/l 0 to 2000 mg/l 0 to 16 000 mg/l 0 to 200 mg/l

Other cations may also exist, possibly with nontrivial concentrations. The anions in the typical produced water may consist of chloride, carbonate, bicarbonate, sulfate, sulfide, etc., with chloride usually the most abundant anion. The evaporation may significantly increase the ion concentrations in produced water left in open air. Produced water may also contain precipitations, suspensions, and hydrocarbons. The pH of produced water typically ranges from about 5 to about 8. Produced water usually contains bacteria, such as general heterotrophic bacteria (GHB), acid-producing bacteria (APB), and sulfate-reducing bacteria (SRB). The species and concentrations of bacteria change over time, affected by many complexities such as the competition among bacteria. Table 1 gives an example of the bacteria concentration change over time in a typical oilfield produced water sample not treated with biocide. The produced water contained 12 300 mg/l Na, 47 mg/l K, 24 mg/l Mg, 522 mg/l Ca, 19 001 mg/l chloride, 660 mg/l bicarbonate, and less than 200 mg/l sulfate. Table 1 suggests that there could be bacteria in produced water, and the bacteria concentrations could change with time. Fluid Stabilizer 1 Fluid stabilizer 1 is an organometallic compound. Three fluids were prepared using deionized (DI) water. Fluid 1 was boratecrosslinked guar gel with a guar loading of 0.3% (weight percentage, same below unless otherwise indicated). The borate-

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crosslinked guar gels such as fluid 1 typically had a pH of about 8.6 at room temperature (RT) and atmospheric pressure. Fluid 2 was the same as fluid 1 but with the addition of about 0.009% of the cellulase/hemicellulase enzyme mixture (a common oilfield enzyme breaker) after the gel was prepared. To make fluid 3, 0.009% of the same cellulase/hemicellulase enzyme mixture was added to DI water, followed by the addition of about 0.01% of fluid stabilizer 1. The solution was fully mixed and then used to make the borate-crosslinked guar gel similar to fluid 1. The viscosity of the three fluids was all measured at 52C (125F) with a Fann50-type viscometer following the API RP 39 schedule. As shown in Fig. 1, the viscosity of fluid 1 stayed above about 600 cP (at the shear rate of 100/s) for over 2 hours as expected. Fluid 2, the gel with the enzyme breaker, quickly lost its viscosity since the enzyme breaker broke down the guar polymer chains. Fluid 3 behaved nearly the same as fluid 1, strongly suggesting that the cellulase/hemicellulase enzymes had been disabled by fluid stabilizer 1. Bacteria could synthesize cellulase (including hemicellulase) enzymes to digest (and therefore damage) polysaccharides. With the presence of the fluid stabilizer, the bacterial enzymes were denatured, and polysaccharides such as guar polymers were therefore protected. Fluid Stabilizer 2 Fluid stabilizer 2 is also an organometallic compound. Two fluids were prepared and compared with each other. Fluid 1 was borate-crosslinked guar gel with a guar loading of 0.42% prepared with untreated produced water from Vernal, Utah. The produced water contained 15 900 mg/l Na, 36 mg/l K, 36 mg/l Mg, 738 mg/l Ca, 24 106 mg/l chloride, 954 mg/l bicarbonate, 80 mg/l carbonate, and less than 200 mg/l sulfate. To prepare fluid 2, the same produced water was treated with 0.013% of fluid stabilizer 2, and then used to make the borate-crosslinked guar gel similar to fluid 1. The viscosity of the two fluids was measured at 93C (200F) with a Fann50-type viscometer following the API RP 39 schedule. As shown in Fig. 2, the viscosity of fluid 2 stayed above about 300 cP (at the shear rate of 100/s) for over 2 hours. Fluid 1, on the contrary, quickly lost its viscosity, possibly since the bacterial enzymes broke down the guar polymer chains. After the measurement, the fluid was cooled down to RT and taken out of the viscometer. Fluid 1 was water-like, while fluid 2 still looked like a viscous gel. The study again suggested that the bacterial enzymes could be disabled by the fluid stabilizer. To test if the instability of the guar fracturing fluid had been caused by the high concentrations of ions in the produced water, salts such as NaCl and CaCl2 were added to DI water to such an extent that the cation and anion concentrations in the water were similar to those in the produced water sample. Obviously, there were no bacteria or enzymes in this artificially made water. The borate-crosslinked guar gel was then similarly prepared with the water. The viscosity of the gel was comparable to that of the borate-crosslinked guar gel prepared with the fluid stabilizer-treated produced water, suggesting that it was not the ions that caused the damage to the fluid. In another test, the produced water was boiled and then cooled down to RT, and the borate-crosslinked guar gel was similarly prepared. Its viscosity, again, was similar to that of the gel prepared with the fluid stabilizer-treated produced water. It is reasonable to expect that most, if not all, bacteria and enzymes were killed/denatured during the boiling, thus leaving the guar gel intact during the test period. This test clearly showed that the guar gel was mainly damaged by bacteria and bacterial enzymes. At the same time, the comparison among the above tests suggested that the fluid stabilizer could effectively disable the bacterial enzymes. Fluid Stabilizer 3 Fluid stabilizer 3 is an inorganic compound. Two fluids were prepared and compared with each other. Fluid 1 was boratecrosslinked guar gel with a guar loading of 0.3% prepared with untreated produced water from oilfield at Bakersfield, California. A normal dose of biocide, or 24 ppm of DBNPA, was added to the produced water before making fluid 1. The produced water contained 11 300 mg/l Na, 503 mg/l K, 277 mg/l Mg, 818 mg/l Ca, 19 887 mg/l chloride, 445 mg/l bicarbonate, and 400 to 800 mg/l sulfate. To prepare fluid 2, the same produced water was treated with 0.014% of fluid stabilizer 3 along with 24 ppm of DBNPA, and then used to make the borate-crosslinked guar gel similar to fluid 1. The viscosity of the two fluids was measured at 54C (130F) with a Fann50-type viscometer following the API RP 39 schedule. As shown in Fig. 3, the viscosity of fluid 2 stayed above about 150 cP (at the shear rate of 100/s) for over 2 hours. Fluid 1, on the contrary, quickly lost its viscosity, possibly since the bacterial enzymes broke down the guar polymer chains. After the measurement, fluid 1 looked like a broken gel at RT, while fluid 2 was still a viscous gel. The study suggested that the bacterial enzymes could be effectively disabled by the fluid stabilizer, but not by the normal dose of common biocides (such as DBNPA) used in the oilfield. Case Histories Case History 1: The 31-well Fracturing Project The project consisted of 31 individual wells in Elk Hills, California. All of the wells were completed in multistage fracturing treatments with half of them using the abrasive perforating and fracturing technology. Average perforation depth was 914 to 1372 m (3,000 to 4,500 ft) (TVD) and 1219 to 3658 m (4,000 to 12,000 ft) (MD), with bottomhole temperatures of 54C (130F). Average fracturing treatment size was 41 000 to 68 000 kg (90,000 to 150,000 lb) of proppant per stage. The total water requirement for the project was about 23 850 m3 (150,000 bbl). The treatments were pumped at 3.2 to 6.4 m3/min (20 to 40 bbl/min) with proppant concentrations up to 1200 kg/m3 (10 ppa) through 140 to 178 mm (5.5 to 7 in.) casing. The recycled fracturing flowback water (produced water) was treated with fluid stabilizer 3, at a typical dose of about 70 to 270 ppm, for about 20 minutes, and the treated produced water was then used to prepare crosslinked guar-based fracturing fluid.

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By using produced water, the following savings were realized for this project: KCl brine savings: USD 1,540,500 Fuel (for transporting water) savings: USD 34,000 Total savings: USD 1,574,500 Additionally, the time required for water hauling was reduced by 1344 hours or by 6 times. In other words, the average time saved was about 2 days per well. The total savings were around 10% of the project cost for stimulation without affecting the production performance. Case History 2: The 97-well Sand Control Project The project consisted of 97 individual wells in Elk Hills, California. Average perforation depth was 610 to 914 m (2,000 to 3,000 ft), with bottomhole temperatures of 54C (130F). Average fracturing treatment size was 11 000 to 14 000 kg (25,000 to 30,000 lb) of proppant. The total water requirement for the project was about 11 290 m3 (71,000 bbl). The treatments were pumped at 2.4 to 4.0 m3/min (15 to 25 bbl/min) with proppant concentrations up to 1080 kg/m3 (9 ppa) through 73 to 89 mm (2.9 to 3.5 in.) tubing. The produced water was similarly treated with fluid stabilizer 3. By using produced water, the following savings were realized for this project: KCl brine savings: USD 857,000 Fuel (for transporting water) savings: USD 16,000 Total savings: USD 873,000 Additionally, the time required for water hauling was reduced by 639 hours or by 4 times. The total savings were around 18% of the project cost without affecting the production performance. Potential of the Fluid Stabilizer for Produced Water By the end of 2008, this new produced water stabilizing technology was implemented in about 80 successful fracturing and sand control jobs. The success story in Bakersfield, California has triggered a wave of requests from operators to apply this technology in other parts of North America. We are optimistic that the produced water fluid stabilizer will make much more contribution to the energy production and environmental protection in the days to come. Conclusions The new fluid stabilizer can effectively disable the damaging mechanisms of the bacteria and bacterial enzymes in produced water, making it feasible to use the fluid stabilizer-treated produced water to prepare polysaccharide-based fracturing fluids. Treating produced water with the fluid stabilizer has been shown to be a successful water conservation approach and an attractive solution to lower operating costs. Acknowledgments The authors would like to thank the management of Schlumberger for permission to present this paper. References Bettelheim, F.A. and March J. 1991. Introduction to General, Organic and Biochemistry, third edition. Fort Worth: Saunders College Publishing. Dawson, J.C. 1991. Low Temperature Degradation of Galactomannans. US Patent No. 5,067,566. Fodge, D.W., Anderson, D.M., and Pettey, T.M. 1996. Hemicellulase Active at Extremes of Ph and Temperature and Utilizing the Enzyme in Oil Wells. US Patent No. 5,551,515. Gleick, P.H. 1994. Water and Energy. Annu Rev Energy Environ 19: 267-299. Gupta, D.V.S., Prasek, B.B., and Horn, R.D. 1995. Enzyme Breakers for Breaking Fracturing Fluids and Methods of Making and Use Thereof. US Patent No. 5,441,109. Li, L., Howard, P.R., Parris, M.D., Lungwitz, B., Boney, C.L., England, K.W., Hutchins, R.D., and Li, J. 2008. Treatment and Reuse of Oilfield Produced Water. US Patent Application No. 20080287323. Paulus W. ed. 2005, Directory of Microbiocides for the Protection of Materials: A Handbook. The Netherlands: Springer. Ring, T.A., Smolkov, T., and Gamarra, M.A. 2004. Method and Apparatus for Preventing Bacteria and Algae Growth in Water. US Patent No. 6,824,794. Shell, F.J. and Hitzman, D.O. 1992. Enzymatic Decomposition of Drilling Mud. US Patent No. 5,165,477. Stephenson M.T. 1992. A Survey of Produced Water Studies. In Produced Water: Technological/Environmental Issues and Solutions, ed. Ray J.P. and Engelhart F.R., Chap. 1, 1-12. New York: Plenum Press. Tjon Joe Pin, R.M., Brannon, H.D., and Rickards, A.R. 1993. Method of Dissolving Organic Filter Cake Obtained from Polysaccharide Based Fluids Used in Production Operations and Completions of Oil and Gas Wells. US Patent No. 5,247,995.

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Table 1. The concentration change over time in the untreated produced water of the three types of bacteria: general heterotrophic bacteria (GHB), acid-producing bacteria (APB), and sulfate-reducing bacteria (SRB). Time 0 7 days 21 days GHB 4.5 105/ml > 1.4 107/ml > 1.4 107/ml APB 4.5 105/ml 2.5 105/ml 2.5 104/ml SRB 7.0 104/ml 1.1 107/ml 2.5 106/ml

2000 Fluid 1 1800 1600 Viscosity at 100 s-1 (cP) 1400 1200 1000 800 600 400 200 0 0 20 40 60 Time (min) 80 100 Fluid 2 Fluid 3 T (degC)

60

50

30

20

10

0 120

Fig. 1Viscosity at 52C for fluid 1 (the borate-crosslinked guar gel), fluid 2 (the borate-crosslinked guar gel with the cellulase/hemicellulase enzyme breaker), and fluid 3 (water premixed with the cellulase/hemicellulase enzyme breaker and fluid stabilizer 1 and then used to make the borate-crosslinked guar gel), respectively.

Temperature (degC)

40

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1200 Fluid 1 1000 Viscosity at 100 s-1 (cP) 80 Temperature (degC) Temperature (degC) 800 60 600 40 Fluid 2 T (degC) 100

400

200

20

0 0 20 40 60 Time (min) 80 100

0 120

Fig. 2Viscosity at 93C for fluid 1 (the borate-crosslinked guar gel prepared with untreated produced water) and fluid 2 (the borate-crosslinked guar gel prepared with fluid stabilizer 2-treated produced water), respectively.

500

60

400 Viscosity at 100 s-1 (cP)

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40 300 30 200 20 100 Fluid 1 0 0 20 40 60 Time (min) 80 100 Fluid 2 T (degC) 0 120

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Fig. 3Viscosity at 54C for fluid 1 (the borate-crosslinked guar gel prepared with untreated produced water) and fluid 2 (the borate-crosslinked guar gel prepared with fluid stabilizer 3-treated produced water), respectively.