AU2005231200B2 - Clay stabilization in sub-surface formations - Google Patents
Clay stabilization in sub-surface formations Download PDFInfo
- Publication number
- AU2005231200B2 AU2005231200B2 AU2005231200A AU2005231200A AU2005231200B2 AU 2005231200 B2 AU2005231200 B2 AU 2005231200B2 AU 2005231200 A AU2005231200 A AU 2005231200A AU 2005231200 A AU2005231200 A AU 2005231200A AU 2005231200 B2 AU2005231200 B2 AU 2005231200B2
- Authority
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- Prior art keywords
- quaternary salt
- poly
- stimulation
- stimulation fluid
- clay
- Prior art date
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- 239000004927 clay Substances 0.000 title claims description 59
- 230000015572 biosynthetic process Effects 0.000 title claims description 47
- 238000005755 formation reaction Methods 0.000 title description 42
- 230000006641 stabilisation Effects 0.000 title description 17
- 238000011105 stabilization Methods 0.000 title description 17
- 239000012530 fluid Substances 0.000 claims description 80
- 230000000638 stimulation Effects 0.000 claims description 69
- 150000003839 salts Chemical group 0.000 claims description 62
- 229920000642 polymer Polymers 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- 239000003381 stabilizer Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 claims description 20
- 230000008961 swelling Effects 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 12
- 230000000087 stabilizing effect Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 6
- 239000003899 bactericide agent Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- MHJIKNDFXOZABF-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate;dimethyl sulfate Chemical compound COS(=O)(=O)OC.CN(C)CCOC(=O)C=C MHJIKNDFXOZABF-UHFFFAOYSA-N 0.000 claims description 3
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000035699 permeability Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- -1 NH4+ ions Chemical class 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- ACUGTEHQOFWBES-UHFFFAOYSA-M sodium hypophosphite monohydrate Chemical compound O.[Na+].[O-]P=O ACUGTEHQOFWBES-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
- C09K8/608—Polymer compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
- C09K8/575—Compositions based on water or polar solvents containing organic compounds
- C09K8/5751—Macromolecular compounds
- C09K8/5753—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Description
WO 2005/098199 PCT/US2005/009988 CLAY STABILIZATION IN SUB-SURFACE FORMATIONS FIELD OF THE INVENTION The present invention generally relates to compositions and methods of using same for clay stabilization in sub-surface formations. More specifically, the present invention relates to compositions that include a polymer that is capable of inhibiting clay swelling and methods of using same for clay stabilization, such as in oil and gas well treatment.
BACKGROUND OF THE INVENTION Hydraulic fracturing has been utilized for many years to stimulate the production of oil, gas or other formation fluids from subterranean formations. In hydraulic fracturing, a suitable fluid is introduced into the down-hole formation by way of a well bore under conditions of flow rate and pressure which are at least sufficient to create or extend a fracture into a desired portion of the formation. Various fluids have been utilized in hydraulic fracturing. Most fluids utilized today, however, are aqueous-based liquids.
The presence of clay in oil and gas producing formations poses a problem for production from wells completed in such formations. Ordinarily, such clays are inert in the formation and do not disrupt the flow of hydrocarbons. When disturbed, however, by aqueous-based fluids used in well stimulation for example, clay particles can swell and reduce formation permeability.
Clay swelling problems in the past have been addressed by preflushing with slugs of salt-containing water and using inorganic salts in the aqueous stimulation fluid. Quite often the salt of choice has heretofore been potassium chloride (KC1) which converts the clay to a less swellable form by cationic exchange with Na 30 ions present on the clay surfaces. Other salts include calcium chloride, ammonium chloride and the like, typically dissolved in an aqueous preflush and/or in the aqueous stimulation fluid used for the fornation treatment.
WO 2005/098199 PCT/US2005/009988 2 Clays dispersed throughout oil-producing formations may be described as stacked platelets with a net positive charge associated with the four short dimensional sides and a net negative charge associated with the two long dimensional faces. It is generally believed that the concept of surface charge may be used to understand the mechanisms involved in swelling inhibition. When the large negatively charged face or surface is exposed to an aqueous solution, it attracts cations from the solution. In order to inhibit the swelling phenomenon, minimization of the hydratable surface area of the clay is necessary. One way that this may be accomplished is by flocculating and decreasing the surface charge density, or by increasing the ionic strength of the aqueous phase, or both. By allowing cations with small charge-to-surface-area ratios to associate with the particle, the effective strength of the negatively charged, doubleface platelet layer surfaces will be diminished, allowing greater platelet-platelet interaction. Increasing the ionic strength of the solutions will also have the same effect.
In the case of potassium chloride, it is generally believed that the potential for clay swelling is shunted via a cation exchange of potassium ions for the more hydration-enticing native cations, such as sodium. It has been found that K+ is much better at creating electrostatic links between the negatively charged faces of the stacked clay platelets than the abundant Na+, thus allowing less osmotic migration of water to occur between the platelets. While a lower concentration of K+ ions relative to Na+ ions is needed to flocculate clays, NH4+ ions have been shown to be even better or equal to K+ ions in creating electrostatic links and reducing osmotic migration of water.
While salts may be effective in protecting the formation, several problems are generally associated with use of same. For example, the amount of material needed for preparing an effective fluid may be very high, and it is often difficult to dissolve such solid components in the treating fluids in the quantities required. In environmentally sensitive areas, there may be limits on the permissible amount of chloride. The presence of salts may also interact with other additive components of the aqueous stimulation fluid, such as, for example, viscosifying agents, the hydration of which is WO 2005/098199 PCT/US2005/009988 3 inhibited by such salts. Further, the duration of the stabilizing effect thereof generally cannot be tailored to meet the optimum duration for a given situation. Accordingly, there is a need for a down-hole clay stabilizing composition that is more inert to other down-hole fluid additives, lower in chloride ion and therefore more environmentally tolerable, which has enhanced clay stabilizing effectiveness compared to potassium chloride and other similar salts, and which may be tailored as to the duration of stabilizing effect.
SUMMARY OF THE INVENTION The present invention generally relates to compositions and methods of using same for clay stabilization in sub-surface formations, such as in oil and gas well treatment. The compositions include a polymer, such as a cationic polymer, that is capable of effectively inhibiting clay swelling in a down-hole formation, and can be used to treat and/or pretreat a sub-surface formation for well stimulation, such as fracturing, acid treating and the like. In an embodiment, the present invention provides a composition suitable as an additive for inhibiting clay swelling in a down-hole formation, a well stimulation fluid that includes such composition, and a method for stabilizing a clay-containing formation that employs such compositions as such well stimulation fluids.
The present invention generally relates to compositions that can be effectively utilized to stabilize clays in sub-surface formations. The compositions are added to the sub-surface formations in an effective amount such that clay swelling can be effectively inhibited. In this regard, the present invention can be effectively utilized to treat and/or pretreat a down-hole formation for well stimulation, such as fracturing, acid treating and the like.
In an embodiment, the present invention provides a composition for clay stabilization in a sub-surface formation. The composition comprises one or more polymers selected from the group consisting of poly(dimethylaminoethylmethacrylate quatemary salt), poly(dimethylaminoethylacrylate quaternary salt) and dimethylaminoethylmethacrylate quaternary salt-dimethylaminoethylacrylate WO 2005/098199 PCT/US2005/009988 4 quaternary salt copolymer, wherein the polymers have a molecular weight of about 1,000 to about 100,000.
In an embodiment, the polymers have a molecular weight of about 1,000 to about 10,000.
In an embodiment, the polymers are selected from the group consisting of poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt), poly(dimethylaminoethylacrylate dimethylsulfate quaternary salt) and dimethylaminoethylmethacrylate methyl chloride quaternary saltdimethylaminoethylacrylate methyl chloride quaternary salt copolymer.
In an embodiment, the composition comprises an aqueous solution of poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt).
In an embodiment, the composition further comprises one or more ingredients in addition to the polymer, wherein the ingredients including viscosifying agents, crosslinking agents, bactericides, breakers, ion control agents, foaming agents including a surfactant, a gas stabilizers and liquefied gas stabilizers and combinations thereof.
In an embodiment, the composition is in a form selected from the group consisting of a solution, an emulsion and a powder.
In another embodiment, the present invention provides a stimulation fluid. The stimulation fluid comprises an aqueous solution of one or more polymers selected from the group consisting of poly(dimethylaminoethylmethacrylate quaternary salt), poly(dimethylaminoethylacrylate quaternary salt) and dimethylaminoethylmethacrylate quaternary salt-dimethylaminoethylacrylate quaternary salt copolymer, wherein the polymers have a molecular weight of about 1,000 to about 100,000.
In an embodiment, the stimulation fluid comprises an aqueous solution of poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt).
00 0 In an embodiment, the simulation fluid comprises up to about four gallons of the poly O (dimethylaminoethylmethacrylate methyl chloride quaternary Z salt) solution per 1,000 gallons of stimulation fluid.
In an embodiment, the stimulation fluid comprises Sabout one to about two gallons of the poly C- (dimethylaminoethylmethacrylate methyl chloride quaternary
T
salt)solution per 1,000 gallons of stimulation fluid.
SIn an embodiment, the stimulation fluid further C-I comprises one or more components such as viscosifying agents, crosslinking agents, bactericides, breakers, ion control agents, foaming agents including a surfactant, gas stabilizers and liquefied gas stabilizers, combinations thereof and the like.
In yet another embodiment, the present invention provides a method of stabilizing a clay-containing formation during a sub-surface well stimulation process.
The method includes providing a stimulation fluid comprising an aqueous solution of one or more polymers selected from the group consisting of poly (dimethylaminoethylmethacrylate quaternary salt), (dimethylaminoethylacrylate quaternary salt) and dimethylaminoethylmethacrylate quaternary salt-dimethylaminoethylacrylate quaternary salt copolymer, wherein the polymers have a number average molecular weight of about 1,000 to about 100,000; and (ii) contacting the formation with the stimulation fluid.
In an embodiment, the stimulation fluid N:%Bnsbw\CsaeserPoten61ODDO199P61724.AUSpedsP61724.AU Speafiatio 2008-11-17.doc 19/11/08 00 0 comprises an aqueous solution of poly (dimethylaminoethylmethacrylate methyl chloride quaternary 0 salt).
5 In an embodiment, the stimulation fluid comprises up to about four gallons of the poly S(dimethylaminoethylmethacrylate methyl chloride quaternary Ce salt) solution per 1,000 gallons of stimulation fluid.
C-
C io In an embodiment, the stimulation fluid does not Scontain an added salt.
In an embodiment, the stimulation fluid comprises about one to about two gallons of the poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt) solution per 1,000 gallons of stimulation fluid.
In an embodiment, the stimulation fluid further includes one or more components such as viscosifying agents, crosslinking agents, bactericides, breakers, ion control agents, foaming agents including a surfactant, gas stabilizers and liquefied gas stabilizers and combinations thereof.
In another aspect of the present invention, there is provided a method of stabilizing a clay-containing formation during a sub-surface well stimulation process, the method comprising the steps of: i) providing a stimulation fluid comprising an aqueous solution of one or more polymers selected from the group consisting of poly(dimethylaminoethylmethacrylate quaternary salt), poly(dimehtylaminoethylacrylate quaternary salt, and dimethylaminomethyacrylate quaternary salt-dimethylaminoethylacrylate quaternary salt co- N:%BrsbaneCses\Patent61 ODOO6199W61724.AASpoe P61724.AU Spec fAtio 2008-11-17.dDc 19/1108 6A oo polymer, wherein the polymers have a molecular weight that is sufficiently low to inhibit clay swelling; and 0 i) contacting the formation with the stimulation Z fluid.
In an embodiment the stimulation fluid does not Scontain added salt.
An advantage of the present invention is to C i0 provide improved compositions for clay stabilization.
C-i Another advantage of the present invention is to provide improved clay stabilizers that can be utilized in stimulation fluids.
Yet another advantage of the present invention provides improved compositions that include a low molecular weight polymer for effective clay stabilization without the addition of a salt or the like.
Yet still another advantage of the present invention provides improved stimulation fluids and methods of using same to provide clay stabilization in a subsurface formation.
Additional features and advantages of the present invention are described in and will be apparent from the following Detailed Description of the Presently Preferred Embodiments.
DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED
EMBODIMENTS
The present invention generally relates to compositions and methods of using same for clay stabilization in sub-surface formations, such as in oil and gas well treatment. The compositions include a N: BrisbaneCases PatenlO610.61999kP6l724.AJSpecstP~l 724.AU Specicatsor 2008-11-17.doc 19/11/08 6B 00 polymer, such as a cationic polymer, that is capable of effectively inhibiting clay swelling in a down-hole O formation, and can be used to treat and/or pretreat a sub- Z surface formation for well stimulation, such as N:BribaneCasesXPatentM10OO-61999XP61724 AU SpecsP6l724 AU Specification 2008-11-17.ooc 19/11/08 WO 2005/098199 PCT/US2005/009988 fracturing, acid treating and the like. In an embodiment, the present invention provides a composition suitable as an additive for inhibiting clay swelling in a down-hole formation, a well stimulation fluid that includes such composition, and a method for stabilizing a clay-containing formation that employs such compositions as such well stimulation fluids.
Hydrocarbon producing formations typically contain some amount of clay.
When exposed to water based treating fluids, these clays will absorb water, swell and block pore space. This can reduce permeability or swell, break loose and migrate through the formation to later cause damage in another location. Temporary clay stabilizers, such as salts, can be small enough in size to move into the pore throats of the formation matrix, but the effect is only temporary. With respect to high molecular weight polymers, they are physically too large in size to effectively move into the pore spaces of low permeability formations and actually plate out on the formation matrix surface. The present invention provides a composition comprising one or more polymers which are small enough to effectively enter the small pore throats of low permeability formations and further which can provide long term protection.
Further; the present invention can provide less material handling at comparable costs, in comparison to the use of typical inorganic salt treatments. Another general advantage of the present invention concerns the duration of the clay stabilizing effect.
At times it is desirable to avoid a stabilization of clay by the use of an organic inhibitor that permanently adheres to the clay particle. Such adherence may make the clay surface oil wet. An oil wet surface is undesirable when the formation is producing oil to the borehole, since the pressure needed to move oil past an oil wet surface is greater than the pressure needed to move oil past a water wet surface. Therefore, less oil is produced per unit time on an oil wetted surface versus a water wetted surface. The present invention permits the duration of clay stabilization to be tailored to given situations.
In an embodiment, the polymer compositions include polymers prepared by polymerization of the quaternary ammonium salts of dimethylaminoethylmethacrylate, WO 2005/098199 PCT/US2005/009988 8 dimethylaminoethyl acrylate and mixtures thereof. The polymers have a molecular weight that is sufficiently low to inhibit clay swelling. For example, the molecular weight can range from about 1,000 to about 100,000, preferably about 1,000 to about 10,000. The composition may, but does not necessarily include a salt, such as KC1,
NH
4 CI, NaCI, TMAC and the like.
"Quaternary ammonium salts", quaternary salt" and "quat" means the salt resulting from reaction of the tertiary nitrogen atom of dimethylaminoethylmethacrylate, dimethylaminoethyl acrylate with a quaternizing agent or acid. Representative quaternary salts include dimethyl sulfate quaternary salts, benzyl chloride quaternary salts, methyl chloride quaternary salts, and the like.
Representative acid salts include hydrochloric acid salt, sulfuric acid salt, and the like.
Preferred polymers include dimethylaminoethylmethacrylate methyl chloride quaternary salt (DMAEM-MCQ), dimethylaminoethylacrylate dimethylsulfate quaternary salt (DMAEA-MSO 4 Q) and dimethylaminoethylmethacrylatedimethylaminoethyl-acrylate copolymer (DMAEM- DMAEA). A more preferred polymer is dimethylaminoethylmethacrylate methyl chloride quaternary salt, alone or in combination with other suitable polymer materials, ingredients and the like.
Additional ingredients can include, for example, viscosifying agents, crosslinking agents, bactericides, breakers, ion control agents, foaming agents including surfactamats, gas stabilizers and liquified gas stabilizers, combinations thereof and the like. In an embodiment, the dimethylaminoethylmethacrylate methyl chloride quaternary salt composition is in an aqueous solution form. However, it should be appreciated that the composition of the present invention can include a solution, an emulsion, a powder and the like.
As previously discussed, the present invention relates to a stimulation fluid that includes a polymer composition in solution form as discussed above. The polymer composition can be added to the stimulation fluid in any suitable concentration. In an embodiment, the stimulation fluid comprises an polymer solution at a concentration of about four gallons of the aqueous polymer composition in solution per 1,000 gallons of WO 2005/098199 PCT/US2005/009988 9 stimulation fluid or less, preferably from about one gallon of the aqueous polymer composition in solution per 1,000 gallons of stimulation fluid to about two gallons of the aqueous polymer composition in solution per 1,000 gallons of stimulation fluid.
The polymer composition includes at least one of the polymers of this invention, preferably dimethylaminoethylmeth-acrylate methyl chloride quaternary salt, alone or in addition to other ingredients including additional other polyelectrolytes, copolymers thereof, and the like. In an embodiment, the stimulation fluid does not include a salt or other similar type of clay swelling inhibition agent.
The stimulation fluid can be made in any suitable manner. In an embodiment, the stimulation fluid is preferably prepared by admixing a quantity of the clay stabilizing composition of the present invention and a polymeric viscosifying agent with an aqueous fluid. Alternatively, the stimulation fluid may be prepared by blending together the various components, such as the cationic polyelectrolyte and the viscosifier, in the desired proportion in any combination or order.
In an embodiment, the viscosifying agent includes a soluble polysaccharide.
Representative examples pf soluble polysaccharides include galactomannan gums (guar), glucomannan gums, cellulose derivatives, and the like. In an embodiment, the stimulation fluid includes a viscosifying agent in a concentration of about 100 to about 600 pounds per 1,000 gallons of the aqueous stimulation fluid.
The stimulation fluid can carry conventional suspended proppants, such as glass beads, which are forced into the fracture or fractures to keep the broken formation from closing completely once the pressure is released. However, the use of such proppants is not necessary to achieve the clay stabilization obtained by the present simulation fluid.
The stimulation fluid also can include a crosslinking agent for the viscosifying agent as well as other suitable additives. For example, the fluid can contain bactericides, breakers, iron control agents, foaming agents such as surfactants, gases or liquefied gases stabilizers, and the like. The preparation of such fluids and the various additives are well known in the art. The selection of the particular stimulating fluid WO 2005/098199 PCT/US2005/009988 constituents and amounts thereof such as the viscosifying agent, crosslinking agent, breakers, stabilizers can be made in any suitable manner.
The clay swelling inhibitor composition, or components thereof, are admixed with an aqueous stimulation fluid in an amount sufficient to substantially stabilize the formation against permeability damage as the result of contact with the aqueous stimulation fluid. In this regard, the clay swelling inhibitor composition can be made in a liquid state, in contradistinction to potassium chloride and similar salts which are crystalline solids, and the present composition may be readily admixed with the stimulation fluid at any time prior to contact of the fluid with the formation.
Alternatively, the present composition may be admixed with constituents of the liquid viscosifying agent and stored as a ready-to-use stimulation fluid additive concentrate.
The clay swelling inhibitor additive is effective in treating a down hole formation when transported in a carrier fluid, such as a well-stimulation fluid having either an acid, alkaline or neutral pH. The stimulation fluid of the present invention can have a pH in the range of from about 0 to about 11 without any significant negative effects upon the activity thereof, although preferably the pH of the stimulation fluid is within the more moderate range of from about a pH of 0 to about a pH of according to an embodiment of the present invention.
It should be appreciated that the present invention can be made and used in any suitable manner, can include any suitable materials and be modified in any suitable manner. Examples of various and suitable materials, such as stimulation fluid additives, of the present invention can be found in U.S. Patent Nos. 5,342,530; 5,152,906; and 5,099,923, the disclosures of which are herein incorporated by reference.
An illustrative example of the present invention according to an embodiment is provided below without limitation.
WO 2005/098199 PCT/US2005/009988 11 Table I: Synthesis of Polydimethylaminoethylmethacrylate-methyl chloride quaternary salt Solution (DMAEM-MCQ Solution) Step Wt% in DMAEM-MCQ Solution grams Formulation 1 Dimethylaminoethylmethacrylate methyl chloride quaternary salt (75wt% 316.8 31.68 aq) (DMAEM-MCQ) 2 D.I. Water 318.92 31.89 3 Sodium Hypophosphite hydrate (solid) 3.56 0.356 4 Vazo 67 0.64 0.064 Methanol 193 19.3 6 D.I. Water 167.08 16.71 7 Total grams 1,000 100.0 A DMAEM-MCQ Solution was made according to an embodiment of the present invention as shown in Table I above and further described in detail below. To a 2-liter 4-neck round bottom flask equipped with an overhead stirrer, a nitrogen (N 2 inlet tube, a Dean-Stark trap, an overhead condenser, and a temperature regulator probe installed was added DMAEM-MCQ, water, and sodium hypophosphite with stirring (Material steps 1-3, amounts described above). Stirring of the materials was conducted at room temp, an N 2 purge was started at 500 milliliters/minute for minutes, and the material mix was heated to 70 0 C. Vazo 67 was then added to the mixture, stirring was continued, and the N 2 purge tube was raised just above the surface of the liquid in the flask (to reduce entrained vapor loss). Within approximately minutes, an exotherm was noted to 74°C. The temperature decreased to 70 0 C and stirring was continued for approximately 8 hours.
A mass balance was then run on the product (clear, syrup). Approximately 8 grams of material was lost to vaporization. This was assumed to be D.I. water and thus 8 grams of D.I. water was added to the flask and contents stirred. At this point the product was clear, but many bubbles were entrained. Steps 5 and 6 were then WO 2005/098199 PCT/US2005/009988 12 conducted where methanol and a final water addition were carried out (see Table I above). Addition of these materials was performed very slowly with stirring. The product appeared hazy for a brief period and then cleared up_ The viscosity, specific gravity and pH were measured for the DMAEM-MCQ Solution made according to an embodiment of the present invention as described above. The following Table II provides the viscosity, specific gravity, and pH data as measured: Table II Material pH Spec gravity Viscosity (cps) LV Spindle 20 0 C 1, DMAEM-MCQ 4.42 1.0552 85.4cps Solution (42.7 dial, 2x factor) A number of experiments have been conducted that demonstrate the beneficial effects of the present invention. The experiments and results thereof are described below according to an embodiment of the present invention without limitation.
The experiments were conducted to compare the clay stabilization properties of a composition made pursuant to an embodiment of the present invention to commercially available clay stabilization products. As indicated in Table III below, three products were evaluated during this study, namely Products A-C. Product A is a polyepichlorohydrin-trimethylamine quaternary salt that has a molecular weight of about 1,000. This product is commercially available. Product B is a commercially available DMAEMA-methylsulfate quaternary salt that has a molecular weight of about 800,000. Product C is a clay stabilization composition made pursuant to an embodiment of the present invention. More specifically, Product C includes a dimethylaminoethylmethacrylate methyl chloride quatemary salt that has a molecular weight of about 4,000.
The clay stabilization properties of each of Products A-C were evaluated by measuring the permeability in millidarcies (md) of a Bandexa Sandstone core after being treated by a standard 3.5% sodium chloride brine to establish a baseline for the WO 2005/098199 PCT/US2005/009988 13 test. The permeability was measured initially or before addition of the product clay stabilizer. The permeability was then again measured after the core had been treated with a product clay stabilizer and then flushed with ten pore volumes of deionized water. Each of the product stabilizers were added at various dosage levels measured in "gpt" where one gpt represents one gallon of product clay stabilizer added to 1,000 gallons of treatment or carrier fluid.
Any decrease in permeability between the before and after measurements indicates that clay swelling has occurred. As shown in Table m below, the product clay stabilizer according to an embodiment of the present invention outperformed product clay stabilizers that are commercially available.
Table III Clay Stabilizer Test Product Permeability Dosage (gpt) Permeability After (md) Before (md) A 4.2 1 A 3.2 10 3.3 B 58 5 46 B 2.8 1 1.6 C 65 2 68 C 4.0 2 3.8 C 2.6 1 1.7 It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art.
Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims.
13A 0 In the claims which follow and in the preceding description of the invention, except where the context 0 requires otherwise due to express language or necessary Z implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but Snot to preclude the presence or addition of further C- features in various embodiments of the invention.
C o10 It is to be understood that, if any prior art Spublication is referred to herein, such reference does not eCq constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
N:%BrisbaneCase3%Ptenl6100D-999P81 724AUSpecisP6724.AU Specfcsteoi 2008-11-17.dcb 1I110
Claims (8)
1. A method of stabilizing a clay-containing O formation during a sub-surface well stimulation process, Z the method comprising the steps of: providing a stimulation fluid comprising an Saqueous solution of one or more polymers selected from the pC group consisting of poly(dimethylaminoethylmethacrylate T quaternary salt), poly(dimethylaminoethylacrylate C o10 quaternary salt) and dimethylaminoethylmethacrylate Squaternary salt-dimethylaminoethylacrylate quaternary salt Cq copolymer, wherein the polymers have a number average molecular weight of about 1,000 to about 100,000; and (ii) contacting the formation with the stimulation fluid.
2. The method of Claim 1 wherein the polymers have a number average molecular weight of about 1,000 to about 10,000.
3. The method of either claim 1 or 2 wherein the polymers are selected from the group consisting of poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt), poly(dimethylaminoethylacrylate dimethylsulfate quaternary salt) and dimethylaminoethylmethacrylate methyl chloride quaternary salt-dimethylaminoethylacrylate dimethyl methyl chloride quaternary salt copolymer.
4. The method of any one of Claims 1-3 wherein the stimulation fluid comprises an aqueous solution of poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt). The method of claim 4 wherein the stimulation fluid comprises up to about four gallons of the N:dsb CasesPatent OOO61999kP61724 ALASpecisP61724.AU Specification 2008-11-17.doc 19/11108 poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt) solution per 1,000 gallons of stimulation O fluid. z
6. The method of claim 4 wherein the stimulation fluid comprises about one to about two gallons of the poly(dimethylaminoethylmethacrylate methyl chloride quaternary salt) solution per 1,000 gallons of stimulation fluid. CK1
7. The method of any one of Claims 1-6 wherein the C, stimulation fluid further comprises one or more components selected from the group consisting of viscosifying agents, crosslinking agents, bactericides, breakers, ion control agents, foaming agents, gas stabilizers and liquefied gas stabilizers and combinations thereof.
8. The method of any one of claims 1 to 7, wherein the stimulation fluid does not contain added salt.
9. A method of stabilizing a clay-containing formation during a sub-surface well stimulation process, the method comprising the steps of: i) providing a stimulation fluid comprising an aqueous solution of one or more polymers selected from the group consisting of poly(dimethylaminoethylmethacrylate quaternary salt), poly(dimehtylaminoethylacrylate quaternary salt, and dimethylaminomethyacrylate quaternary salt-dimethylaminoethylacrylate quaternary salt co- polymer, wherein the polymers have a molecular weight that is sufficiently low to inhibit clay swelling; and ii) contacting the formation with the stimulation fluid. N:%BrisbaneCaseaPetent%61 00061999%P61 724.ALSpecisP61 724.AU Specifiction 2038-l1-17.doc 19/11/08 00 16 The method of claim 9, wherein the stimulation o fluid does not contain added salt. N %BrisbaneCases Pstentk61 00041 999%I 61724.ALASpeisP61 724.AU Speciicaion 2008-11-1 7.dc 19/11/08
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| US10/812,337 | 2004-03-29 | ||
| US10/812,337 US20050215439A1 (en) | 2004-03-29 | 2004-03-29 | Clay stabilization in sub-surface formations |
| PCT/US2005/009988 WO2005098199A2 (en) | 2004-03-29 | 2005-03-24 | Clay stabilization in sub-surface formations |
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| US7398824B1 (en) * | 2003-09-25 | 2008-07-15 | Bj Services Company | Method for inhibiting or controlling inorganic scale formations with copolymers of acrylamide and quaternary ammonium salts |
| US8703655B2 (en) * | 2007-06-15 | 2014-04-22 | Baker Hughes Incorporated | Dispersing sulfide scales in oil and gas production systems |
| US20090308599A1 (en) * | 2008-06-13 | 2009-12-17 | Halliburton Energy Services, Inc. | Method of enhancing treatment fluid placement in shale, clay, and/or coal bed formations |
| US20130126169A1 (en) | 2011-11-23 | 2013-05-23 | Saudi Arabian Oil Company | Tight Gas Stimulation by In-Situ Nitrogen Generation |
| CA2997969C (en) | 2012-01-17 | 2019-12-03 | Mohammed Nasser Al-Dahlan | Non-acidic-exothermic sandstone stimulation fluids |
| CA2870879C (en) | 2012-05-29 | 2020-04-07 | Saudi Arabian Oil Company | Enhanced oil recovery by in-situ steam generation |
| CN103539902B (en) * | 2012-07-11 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method of high temperature resistant contraction-expansion system for promoting stratum clay modification |
| CA2943635C (en) | 2014-04-17 | 2019-03-12 | Saudi Arabian Oil Company | Method for enhanced fracture cleanup using redox treatment |
| US10308862B2 (en) | 2014-04-17 | 2019-06-04 | Saudi Arabian Oil Company | Compositions and methods for enhanced fracture cleanup using redox treatment |
| EP3132001B1 (en) | 2014-04-17 | 2020-11-11 | Saudi Arabian Oil Company | Chemically-induced pulsed fracturing method |
| US10053614B2 (en) | 2014-04-17 | 2018-08-21 | Saudi Arabian Oil Company | Compositions for enhanced fracture cleanup using redox treatment |
| WO2016096502A1 (en) | 2014-12-17 | 2016-06-23 | Basf Se | Method of using cationic polymers comprising imidazolium groups for permanent clay stabilization |
| CN108350728B (en) | 2015-11-05 | 2021-02-19 | 沙特阿拉伯石油公司 | Method and equipment for performing space-oriented chemically-induced pulse fracturing in reservoir |
| US11739616B1 (en) | 2022-06-02 | 2023-08-29 | Saudi Arabian Oil Company | Forming perforation tunnels in a subterranean formation |
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| US4147627A (en) * | 1977-02-07 | 1979-04-03 | American Cyanamid Company | Process for scale control using mixtures of polycationic and polyanionic polymers |
| US4463810A (en) * | 1981-09-23 | 1984-08-07 | The Dow Chemical Company | Process for fracturing subterranean formations |
| US4563292A (en) * | 1984-08-02 | 1986-01-07 | Halliburton Company | Methods for stabilizing fines contained in subterranean formations |
| US4536305A (en) * | 1984-09-21 | 1985-08-20 | Halliburton Company | Methods for stabilizing swelling clays or migrating fines in subterranean formations |
| US4588508A (en) * | 1984-11-13 | 1986-05-13 | Nalco Cehmical Company | Bimodal cationics for water clarification |
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| US5099923A (en) * | 1991-02-25 | 1992-03-31 | Nalco Chemical Company | Clay stabilizing method for oil and gas well treatment |
| US5256252A (en) * | 1992-07-15 | 1993-10-26 | Nalco Chemical Company | Method for controlling pitch deposits using lipase and cationic polymer |
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| US6787506B2 (en) * | 2002-04-03 | 2004-09-07 | Nalco Energy Services, L.P. | Use of dispersion polymers as friction reducers in aqueous fracturing fluids |
| US6831042B2 (en) * | 2002-06-17 | 2004-12-14 | Nalco Company | Use of anionic dispersion polymers as viscosity modifiers in aqueous drilling fluids |
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| US20050215439A1 (en) | 2005-09-29 |
| WO2005098199A2 (en) | 2005-10-20 |
| EP1730384A2 (en) | 2006-12-13 |
| AU2005231200A1 (en) | 2005-10-20 |
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