Guar Gum Graft Copolymers with Applications in Hydraulic Fracturing Fluids

Transcription

1 Guar Gum Graft Copolymers with Applications in ydraulic Fracturing Fluids William. Daly, Ahmad Bahamdan, Sreelatha S. Balamurugan Macromolecular Studies Group, Department of Chemistry, Louisiana State University, Baton Rouge, LA USA Dedicated To The Memory of James E. McGrath

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8 ydraulic Fracturing Fluids ydraulic fracturing fluids are needed: To obtain sufficiently high fluid viscosity at down-hole temperature to create a fracture in the reservoir. To transport the proppant particles through the fracture formation and prevent proppant settling. 3 Upon hydrolysis, gel fragments must be removed from the formation Existing Developments : surfactants, copolymers, and hydrophobically modified polysaccharides (MPS). 3-Naval Goel, Subhash N. Shah, Wei-Li Yuan, and Edger A. Rear, Journal of Applied Polymer Science, 2001, 82,

9 Mechanism f Fracture Formation Packer igh viscosity fluids Formation start fracturing

10 bjectives Is to develop a hydrophobically modified polysaccharides (MPS) used to achieve greater well productivity and less damaging completion and stimulation fluids. Why MPS The mechanism for aggregation of nonionic MPS is similar to that for surfactant micellisation. As a result of this network formation, MPS are expected to be very efficient viscosifiers of aqueous media. The viscosity increases with increasing hydrophobe incorporation and alkyl chain length provided that the hydrophobe incorporation is not so high that the polymer becomes insoluble. Using such aggregated polymers can overcome the problems of pore clogging because the active molecular weight and hydrodynamic volume are much smaller than those of a non-hydrophobic polymer with comparable viscosity. The MPS can be broken and cleaned from the formation by the oil during production.

11 Guar Gum is derived from endosperm of the guar plant (Cyamopsis tetragonoloba) Guar gum is a naturally occurring galactomannan polysaccharide composed of galactan and mannan units combined through glycosidic linkages Galactose Mannose Guar Gum - a galactomannan The structure of guar gum is a linear chain of β-d-mannopyranosyl units linked (1 4) with single member α-d-galactopyranosyl units occurring as side branches. The ratio of galactose to mannose usually ranges from 1:2 to 1:4.

12 Guar Gum Source Cyamopsis tetragonoloba seed envelop, the seeds, the split seed and the grounded seed and different products of guar gum

13 Guar Gum is very high molecular weight Polysaccharide Applications: Emulsifier, thickener, and stabilizer in a wide range of foods, cosmetics, and pharmaceuticals. Used extensively in the oil industry as a thickener for hydraulic fracturing of rock formations to enhance oil recovery (ER). 2 RI response GPC of Guar Gum volume/ml 1- Behari, K., Kumar, R. Tripathi, M., and Pandey, P. K., Macromol. Chem. Phys., 2001, 202, Rymond Jasinski, David Redwine, and Gene Rose, Journal of Polymer Science:Part B: Polymer Physics, 1996, 34, GPC in water Mn = Mw = Polydispersity = 1.15 Polystyrene standard

14 Guar Gum The galactose branches occur on every other mannose unit. 1 Mw around Applications: Emulsifier, thickener, and stabilizer in a wide range of foods, cosmetics, and pharmaceuticals. Used extensively in the oil industry as a thickener for hydraulic fracturing of rock formations to enhance oil recovery (ER). 2 * C 2 D-galactose branches joined by α-(1 6) bonds 2 C 2 C D-mannose units linked by β-(1 4) linkage * 1- Behari, K., Kumar, R. Tripathi, M., and Pandey, P. K., Macromol. Chem. Phys., 2001, 202, Rymond Jasinski, David Redwine, and Gene Rose, Journal of Polymer Science:Part B: Polymer Physics, 1996, 34,

15 ydrophobically Modified Guar Gum Young et al. compared MBG (has 1-2(w/w)% C 16 alkyl chains randomly distributed) with native guar, hydroxybutyl guar (BG) and hydroxypropyl guar (PG) in solution and in the presence of an ionic surfactant sodium dodecyl-sulphate (SDS). They reported that MBG shows improved rheological properties over the others. Young, N.W.G., Williams, P.A., Meadows, J, and Allen, E., Society of Petroleum Engineering, SPE 39700, 1998,

16 Grafting of Guar Gum Kunj Behari 1 and coworkers reported the graft of methylacrylamide (MAM) onto guar gum, using a potassium chromate/malonic acid redox pair. P. Chowdhury 5 et al reported the graft of methyl methacrylate (MMA) onto guar gum utilizing ceric ammonium sulfate/dextrose redox pair (CAS/DM). Kavita Taunk 6 et al reported the grafting of acrylic acid (AA) onto guar gum using potassium peroxy-diphosphate (PDP)/silver nitrate redox system. The grafting of polyacrylonitrile onto guar gum utilizing potassium persulfate/ascorbic acid redox system was also reported. 7 5-Chowdhury, P., Samui, S., Kundu, T., and Nandi, M.M., Journal of Applied Polymer Science, 2001, 82, Taunk, Kavita and Behari, Kunj, Journal of Applied Polymer Science, 2000, 77, Bajpai, U.D.N., Mishra, Veena., and Rai, Sandeep, Journal of Applied Polymer Science, 1993, 47,

17 Carboxylation of Guar Gum C 2 2 C 2 C ClC 2 C Na SCA Na, 70 o C C 2 C 2 C 2 C 2 C Guar Gum, g (meq) Na, g (eq) SCA, g (eq) Weight gain (g) D.S. by titration Efficiency 60 (0.37) 12 (0.3) 35 (0.3) % 70 (0.43) 9.92 (0.25) 24 (0.21) % 140 (0.87) 28 (0.7) (0.58) %

18 Conversion to Poly(oxyalkylene)amide grafts C 2 C 2 C 2 C 2 C 3 C S C 3 DMS, 60 o C C 2 C 2 C C 3 2 C 2 C C 2 C 2 C N C 3 C X C -C 2 C 2 C x 3 Polyoxyalkyleneamines DMS, 95 o C 2 C 2 C

19 Polyoxyalkyleneamines used in this study Name of Polyoxyalkylene amine Structure Ratio P/E (y/x) Approximate Molecular Weight Jeffamine M-715 XTJ-506 (M-1000) Surfonamine L-300 XTJ-505 (M-600) Surfonamine MNPA-1000 Surfonamine-B30 (ML-300) C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 2/ C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 3/ C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 8/ C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 9/1 600 C C [C 2 C(C 3 )] C 2 C(C 3 )-N C 3 (C 2 ) 12 C 2 C(C3)- C 2 C(C 3 )-N 2-325

20 Brookfield viscosity of 0.48% solutions of CMGGW-45- M BMCMGGW-45, BMCMGGW-45- M1000, up BMCMGGW-45- M1000, down Log Viscosity, cp Log RPM

21 Brookfield viscosity of Carboxymethyl Guar compared to the grafted derivatives at room temperature, 0.48% solutions Sample p Viscosity, at 20 RPM (cp) CMG GW CMGGW-45-M CMGGW-45-M CMGGW-45-MNPA CMGGW-45-L BMCMGGW-45-B

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23 Synthesis of alkyne terminated Guar gum x y Synthesis of Temperature Responsive Biohybrid Guar- Based Grafted Copolymers by Click Chemistry Morgan Tizzotti, Caroline Creuzet, Marie-Pierre Labeau, Thierry amaide, Fernande Boisson, Eric Drockenmuller, Aurelia Charlot,, and Etienne Fleury Macromolecules 2010, 43, Br 60 0 C Isopropanol, 5% Na R R R R R R R x R R y R = or Alkyne substituited Guar

24 Azidation of Surfonic surfactant 5 addition at 0 0 C Solvent -TF 24 hrs R.T stirring C 3 S Cl Triethyl amine 5 S C 3 solvent DMF 60 0 C 24 hrs NaN 3 5 N 3 Formation of the azide terminated surfactant was confirmed by 1 NMR

25 Formation of Azide terminated surfactant was confirmed by 1 NMR C 2 N 3 Azide terminated surfactant -Mesyl derivative of the surfactant Surfonic surfactant

26 Clicking Guar gum to surfactants x y + Degree of substitution Azide terminated surfactant N 3 Alkyne substituited Guar CuS sodium ascorbate, water N hour (room temp) R R N 3 8 R R R R N R R = C 2 R x N N y R N R = C 2 N N Clicked Guar gum with surfactant

27 Zirconium Salt Promoted Guar Crosslinking

28 Proposed Covalent Bonding Mechanism for Crosslinking

29 Crosslinked Gel Strength

30 Viscosity values of zirconium-crosslinked BMCMGGW-45 control sample compared to its grafted derivatives as a function of shear rate (4.8g/L, p >10, 0.5ml Zr crosslinking agent, 25 C) BMCMGGW- 45 control 40lb/1000gal BMCMGGW- 45-M600 40lb/1000gal Log Viscosity, cp BMCMGGW- 45-M lb/1000gal BMCMGGW- 45- MNPA1000, 40lb/1000gal BMCMGGW- 45-B30, 40lb/1000gal BMCMGGW- 45-L300, 40lb/1000gal log Shear Rate, s-1

31 Average viscosity of Gelled CMG control sample and its derivatives (37.7/s, 4.8g/L, p >10, 0.5ml of Zr crosslinking agent). Sample name BMCMGGW45 Control Initial Viscosity at R.T., cp Avg. Viscosit y at 65 C, cp SD Avg. Viscosity at 90 C, cp SD BMCMGGW45-M BMCMGGW45- M BMCMGGW45-L BMCMGGW45- MNPA BMCMGGW45-B

32 Viscosity values of zirconium-crosslinked CMPG control sample compared to its grafted derivatives as a function of shear rate (4.8g/L, p >10, 0.5ml Zr crosslinking agent, 25 C).

33 Average viscosity of Gelled CMPG control sample and its derivatives (37.7/s, 4.8g/L, p >10, 0.5ml of Zr crosslinking agent). Sample name Initial Viscosity at R.T. Avg. Viscosity at 65 C SD Avg. Viscosity at 90 C SD BM12CMPG Control BM12CMPG-M BM12CMPG-M715* BM12CMPG-M BM12CMPG-L300* BM12CMPG- MNPA BM12CMPG-B30*

34 Polyoxyalkyleneamines used in this study Name of Polyoxyalkylene amine Structure Ratio P/E (y/x) Approximate Molecular Weight Jeffamine M-715 XTJ-506 (M-1000) Surfonamine L-300 XTJ-505 (M-600) Surfonamine MNPA-1000 Surfonamine-B30 (ML-300) C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 2/ C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 3/ C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 8/ C 3 -[C 2 -C2] x -[C 2 - C(C3)] y -N 2 9/1 600 C C [C 2 C(C 3 )] C 2 C(C 3 )-N C 3 (C 2 ) 12 C 2 C(C3)- C 2 C(C 3 )-N 2-325

35 Brookfield viscosity of 0.48% solutions of CMGGW-45- M BMCMGGW-45, BMCMGGW-45- M1000, up BMCMGGW-45- M1000, down Log Viscosity, cp Log RPM

36 Brookfield viscosity of Carboxymethyl Guar compared to the grafted derivatives at room temperature, 0.48% solutions Sample p Viscosity, at 20 RPM (cp) CMG GW CMGGW-45-M CMGGW-45-M CMGGW-45-MNPA CMGGW-45-L BMCMGGW-45-B

37 Zirconium Salt Promoted Guar Crosslinking

38 Proposed Covalent Bonding Mechanism for Crosslinking

39 Crosslinked Gel Strength

40 Viscosity values of zirconium-crosslinked BMCMGGW-45 control sample compared to its grafted derivatives as a function of shear rate (4.8g/L, p >10, 0.5ml Zr crosslinking agent, 25 C) BMCMGGW- 45 control 40lb/1000gal BMCMGGW- 45-M600 40lb/1000gal Log Viscosity, cp BMCMGGW- 45-M lb/1000gal BMCMGGW- 45- MNPA1000, 40lb/1000gal BMCMGGW- 45-B30, 40lb/1000gal BMCMGGW- 45-L300, 40lb/1000gal log Shear Rate, s-1

41 Average viscosity of Gelled CMG control sample and its derivatives (37.7/s, 4.8g/L, p >10, 0.5ml of Zr crosslinking agent). Sample name BMCMGGW45 Control Initial Viscosity at R.T., cp Avg. Viscosit y at 65 C, cp SD Avg. Viscosity at 90 C, cp SD BMCMGGW45-M BMCMGGW45- M BMCMGGW45-L BMCMGGW45- MNPA BMCMGGW45-B

42 Viscosity values of zirconium-crosslinked CMPG control sample compared to its grafted derivatives as a function of shear rate (4.8g/L, p >10, 0.5ml Zr crosslinking agent, 25 C).

43 Average viscosity of Gelled CMPG control sample and its derivatives (37.7/s, 4.8g/L, p >10, 0.5ml of Zr crosslinking agent). Sample name Initial Viscosity at R.T. Avg. Viscosity at 65 C SD Avg. Viscosity at 90 C SD BM12CMPG Control BM12CMPG-M BM12CMPG-M715* BM12CMPG-M BM12CMPG-L300* BM12CMPG- MNPA BM12CMPG-B30*

44 Gel Viscosity Behavior at 90 and 120 C at 150 psi Control, CMGGW-45 CMGGW-45 B-30 Adduct (40 Gel)

45 Gel Viscosity Behavior CMGP-B-30 at 90 and 120 C at 150 psi

46 Chain Breakers Acid Breakers Acids depolymerize various polysaccharides by hydrolysis of glycosidic linkage as long as the formation matrix does not have sensitivity to acidic solutions Enzyme Breakers Selective enzymes target anhydroglucose linkages promote a chain cleavage. Limitations: Excessive heat, Temperature, p s and high salinity denature enzymes.

47 CMGGW-45 control sample broken by the enzyme (left), and extracted with toluene (right). Toluene layer

48 CMPGuar Derivative Gel Broken Enzymatically after extraction with toluene.

49 Guar Derivative Gels Broken Enzymatically after extraction with toluene.

50 Fragments from Enzymatic ydrrolysis

51 Conclusions Novel guar gum derivatives can be synthesized from commercially available polyoxyalkyleneamine compounds and guar gum derivatives. omogeneous aqueous solutions of the new derivatives could be prepared. The viscosities of these solutions are approximately ten times less than the viscosities of the parent materials at comparable concentrations. All of the derivatives could be crosslinked successfully using a zirconium lactate crosslinking agent. The resultant gels exhibited properties comparable to or greater than those of gels formed from the guar gum precursors at a concentration of 40lb/1000gal (4.8 g/l) which is typical for field applications Enzymatic hydrolysis yielded fragments with surfactant character, which should facilitate removal from formation