US20030017953A1 - Thermal extenders for well fluid applications involving synthetic polymers - Google Patents
Thermal extenders for well fluid applications involving synthetic polymers Download PDFInfo
- Publication number
- US20030017953A1 US20030017953A1 US09/901,444 US90144401A US2003017953A1 US 20030017953 A1 US20030017953 A1 US 20030017953A1 US 90144401 A US90144401 A US 90144401A US 2003017953 A1 US2003017953 A1 US 2003017953A1
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- US
- United States
- Prior art keywords
- fluid
- well
- well fluid
- amine
- synthetic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000012530 fluid Substances 0.000 title claims abstract description 86
- 229920001059 synthetic polymer Polymers 0.000 title claims abstract description 43
- 239000004606 Fillers/Extenders Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 230000001965 increasing effect Effects 0.000 claims abstract description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 45
- 229960004418 trolamine Drugs 0.000 claims description 44
- 150000001412 amines Chemical class 0.000 claims description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 claims 4
- -1 primary amine compound Chemical class 0.000 abstract description 41
- 229920000642 polymer Polymers 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 9
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000005755 formation reaction Methods 0.000 description 24
- 239000012267 brine Substances 0.000 description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 238000005553 drilling Methods 0.000 description 14
- 229910001622 calcium bromide Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000006187 pill Substances 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003077 lignite Substances 0.000 description 6
- 229940123973 Oxygen scavenger Drugs 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- MGOFVQZCOQYWML-UHFFFAOYSA-N C.C.CCCOC Chemical compound C.C.CCCOC MGOFVQZCOQYWML-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HGIXFHANEYAZMP-UHFFFAOYSA-N aminomethyl propane-1-sulfonate Chemical compound CCCS(=O)(=O)OCN HGIXFHANEYAZMP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940059251 calcium bromide Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XTNMKCFFSXJRQE-UHFFFAOYSA-N n-ethenylethenamine Chemical compound C=CNC=C XTNMKCFFSXJRQE-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000003180 well treatment fluid Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- C09K8/62—Compositions for forming crevices or fractures
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
Definitions
- the invention relates generally to the exploitation of hydrocarbon-containing formations. More specifically, the invention relates to the fields of fluid rheology, thickeners, viscosifiers, viscoelastic fluids, drilling fluids, well fracturing fluids, well treatment fluids and fluid control pills.
- well fluid When drilling or completing wells in earth formations, various fluids typically are used in the well for a variety of reasons.
- the fluid often is aqueous.
- well fluid Common uses for well fluids include: lubrication and cooling of drill bit cutting surfaces while drilling generally or drilling-in (i.e., drilling in a targeted petroliferous formation), transportation of “cuttings” (pieces of formation dislodged by the cutting action of the teeth on a drill bit) to the surface, controlling formation pressure to prevent blowouts, maintaining well stability, suspending solids in the well, minimizing fluid loss into and stabilizing the formation through which the well is being drilled, fracturing the formation in the vicinity of the well, displacing the fluid within the well with another fluid, cleaning the well, testing the well, implacing a packer fluid, abandoning the well or preparing the well for abandonment, and otherwise treating the well or the formation.
- Brines such as CaBr 2
- CaBr 2 commonly are used
- a brine-based well fluid also may include corrosion inhibitors, lubricants, pH control additives, surfactants, solvents, and/or weighting agents, among other additives.
- Some typical brine-based well fluid viscosifying additives include synthetic polymers and oligomers such as poly(ethylene glycol) (PEG), poly(diallyl amine), poly(acrylamide), poly(aminomethylpropylsulfonate [AMPS]), poly(acrylonitrile), poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl amine), poly(vinyl sulfonate), poly(styryl sulfonate), poly(acrylate), poly(methyl acrylate), poly(methacrylate), poly(methyl methacrylate), poly(vinylpyrrolidone), poly(vinyl lactam) and co-, ter-, and quater-polymers of the following co-monomers: ethylene, butadiene, isoprene, styrene, divinylbenzene, divinyl amine, 1,4-pentadiene-3-one (divinyl ketone), 1,6-hept
- the wellbore is drilled to penetrate the hydrocarbon bearing zone using conventional techniques.
- a casing generally is set in the wellbore to a point just above the hydrocarbon bearing zone.
- the hydrocarbon bearing zone then may be re-drilled, for example, using an expandable under-reamer that increases the diameter of the wellbore.
- Under-reaming usually is performed using special “clean” drilling fluids.
- Typical drilling fluids used in under-reaming are expensive, aqueous, dense brines that are viscosified with a gelling and/or cross-linked polymer to aid in the removal of formation cuttings.
- the high permeability of the target formation may allow large quantities of the drilling fluid to be lost into the formation.
- fluid loss control is highly desirable to prevent damaging the formation in, for example, completion, drilling, drill-in, displacement, hydraulic fracturing, work-over, packer fluid implacement or maintenance, well treating, or testing operations.
- Techniques that have been developed to control fluid loss include the use of fluid loss “pills.”
- Significant research has been directed to determining suitable materials for the fluid loss pills, as well as controlling and improving the properties of the fluid loss pills.
- fluid loss pills work by enhancing filter-cake buildup on the face of the formation to inhibit fluid flow into the formation from the wellbore.
- the present invention relates to a method for increasing the thermal and pressure stability of viscosifying agents, particularly synthetic polymers, used in a well fluid which comprises mixing a miscible tertiary amine compound into the fluid.
- the present invention relates to a method for increasing the thermal and pressure stability of viscosifying agents, and particularly synthetic polymers, in a well fluid which comprises mixing a miscible secondary amine compound into the fluid.
- the present invention relates to a method for increasing the thermal and pressure stability of viscosifying agents, and particularly synthetic polymers, in a well fluid which comprises mixing a miscible primary amine compound into the fluid.
- the present invention relates to a thermally stable viscosifying system for well fluids which comprises a synthetic polymer, a solvent, and a tertiary amine miscible in the solvent.
- the present invention relates to a thermally stable viscosifying system for well fluids, which comprises a synthetic polymer, a solvent, and a secondary amine miscible in the solvent.
- the present invention relates to a thermally stable viscosifying system for well fluids, which comprises a synthetic polymer, a solvent, and a primary amine miscible in the solvent.
- the present invention relates to a novel composition for increasing the thermal durability of synthetic polymers used in downhole applications. Further, the present invention relates to increasing the thermal and pressure stability of viscosified well fluids by including an effective amount of an amine into a synthetic polymer system. “Effective” simply means an amount sufficient to raise the temperature stability of the synthetic polymer system by a measurable amount.
- the present invention relates to compositions for the creation of, and methods of using fluid loss control pills and similar fluids that can sustain stress conditions for extended periods of time without significant fluid loss or loss of desirable Theological properties.
- the stress conditions may include, for example, exposure to high shear in pumping and placement, exposure to oxidizing breakers (including oxygen dissolved in the fluid), exposure to brines having high divalent cation content, high temperature, high differential pressure, low pH, extended time, and a combination of two or more of such stress conditions.
- These pills and fluids are advantageously applied in or in connection with drilling, drill-in, displacement, completion, hydraulic fracturing, work-over, packer fluid implacement or maintenance, well treating, testing, or abandonment.
- one embodiment of the invention is related to the effect of triethanol amine (TEA) on a conventional synthetic polymer well fluid system, such as a system containing polyethylene glycol (PEG).
- PEG is a water soluble polymer that may be generated from a condensation reaction between ethylene glycol monomers.
- the general structure of a single repeat unit of PEG is shown below:
- Triethanol amine has the following structure:
- the effects of high temperatures for long periods of time on the fluid control abilities of synthetic polymers were measured on a TEA-containing composition. Specifically, 10.0 grams per lab barrel (g/Lbbl) of high molecular weight PEG (MW ⁇ 400,000 g/mol) and 7.0 g/Lbbl of low molecular weight PEG (MW ⁇ 800 g/mol) were added slowly to an agitated brine solution.
- the term “lab barrel” is used as a unit of volume—a lab barrel is equivalent to about 350 milliliters. (A lab barrel of water weighs about 350 grams, just as a regular barrel of water weighs the same number of pounds, about 350. This is the formal origin of the term “lab barrel.”
- the particular embodiments describe a particular order of addition for the chemical components, such a description is not intended to limit the scope of the invention in any fashion.
- the brine solution comprises 0.888 Lbbl of a 19.2 pounds per gallon (ppg) density ZnBr 2 /CaBr 2 in water.
- the 19.2 pounds per gallon ZnBr 2 /CaBr 2 brine solution is roughly 52.8% by weight ZnBr 2 , 22.8% CaBr 2 , with the balance being water.
- 15.0 g/Lbbl amount of an oxygen scavenger sodium thiosulfate pentahydrate in this embodiment
- TEA 85% TEA in water
- 5.0 g/Lbbl of gilsonite was added as a dry reagent into the brine.
- Gilsonite is a natural, resinous hydrocarbon which is often used as an additive in well fluids because of its corrosion inhibiting properties.
- 5.0 g/Lbbl of lignite was added to the brine as a dry reagent.
- 30.0 g/Lbbl of calcium carbonate (CaCO 3 ) was added. It should be noted that all of the additional chemicals added to the TEA/PEG/brine system discussed above were added only to approximate a “typical” well fluid. It is explicitly within the scope of the invention that a variety of other well fluid additives may be present in addition to the amine/synthetic polymer/brine system described above.
- the fluid loss properties of the compositions described in the following embodiments were determined as follows. Fluid loss tests of durations ranging from 30 seconds to 48 hours were performed in an API standard high pressure high temperature (HPHT) apparatus (Ref.: API 13-BI with one modification: substituting an Aloxite or ceramic disk for paper).
- HPHT high pressure high temperature
- the testing temperature used in obtaining the below readings was predetermined, such as, for example, in accordance with a bottom-hole temperature at which the fluid will be used in the field.
- the HPHT apparatus was operated at 250 to 600 psig differential pressure, using, for example, a 50-2000 milliDarcy Aloxite disc (HPHT cell). In general, the HPHT cell is loaded into the HPHT apparatus, which is then pressurized and heated to a predetermined temperature. A discharge valve located on the HPHT apparatus is then opened, and a filtrate volume is measured as a function of time.
- the composition was placed in a HPHT cell and heated for 45 minutes at 250° F.
- a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for 6 hours.
- the tables reproduced in the specification therefore, merely extract the relevant data, rather than reproducing the data in toto.
- the composition was placed in a HPHT cell and heated for 45 minutes at 250° F.
- a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for approximately 6 hours.
- the effectiveness of the TEA on a system having higher PEG concentration than the first embodiment was determined.
- 15.0 g/Lbbl of high molecular weight PEG (MW ⁇ 400,000) and 7.0 g/Lbbl of low molecular weight PEG were added to 0.888 Lbbl of a 19.2 ZnBr 2 /CaCl 2 in water.
- the 19.2 pounds per gallon ZnBr 2 /CaBr 2 water mixture is roughly 52.8% by weight ZnBr 2 , 22.8% CaBr 2 , with the balance being water.
- the oxygen scavenger, lignite, gilsonite, TEA, and calcium carbonate were added in the same amounts and in the same manner as in the first embodiment described above.
- the composition was placed in a HPHT cell and heated for 45 minutes at 250° F.
- a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for approximately 6 hours.
- the effect of increased TEA concentration was determined.
- 15.0 g/Lbbl of high molecular weight PEG and 7 g/Lbbl of low molecular weight PEG were added to 0.676 Lbbl of 19.2 ppg ZnBr 2 /CaBr 2 in water.
- 80.0 g/Lbbl of TEA was added.
- the oxygen scavenger, the lignite, the gilsonite, and the calcium carbonate were added in the same amounts and in the same manner as in the first and second embodiments.
- the composition was placed in a HPHT cell and heated for 45 minutes at 250° F.
- a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid lost was then recorded over approximately 10 to 15 minute intervals for approximately 3 hours.
- a fourth embodiment the effect of TEA on mixed polymer systems was determined.
- 15.0 g/Lbbl of high molecular weight PEG and 7.0 g/Lbbl of low molecular weight PEG were added to 0.648 Lbbl of 19.2 ZnBr 2 /CaBr 2 in water.
- 3.0 g/Lbbl of a polymer sold under the trade name HE-300 and 3.0 g/Lbbl of a polymer sold under the trade name of HE-400 were added. Both HE-300 and HE-400 are sold by Drilling Specialties, Inc. of Bartlesville, Okla. 74004.
- HE-300 and HE-400 polymers are a family of synthetic, divalent-cation-tolerant, high temperature polymers that work in brine and freshwater environments for many applications. In addition, they may be crosslinked, so that they form rigid gels in a petroleum bearing reservoir for conformance control of unwanted water or gas production.
- HE-300 and HE-400 polymers When drilling or completing with clear brine fluids, HE-300 and HE-400 polymers have been used to viscosify brines at temperatures as high as 240° C. and will remain stable in solution without precipitation. 87.0 g/Lbbl of TEA was then added to this mixture. 5.0 g/Lbbl of both lignite and gilsonite were then added to the mixture. In addition, 10.0 g/Lbbl of magnesium oxide and 30.0 g/Lbbl of calcium carbonate were added as dry reagents.
- the composition was placed in a HPHT cell and heated for 45 minutes at 250° F.
- a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed in the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for approximately 16 hours.
- a suitable system for increasing polymer stability may comprise 0.1% by weight to 99% by weight synthetic polymer and 0.1% by weight to 99% by weight TEA. More preferably, in one embodiment the system may comprise 0.3% by weight to 5% by weight synthetic polymer and 0.2% by weight to 20% TEA. Still more preferably, in one embodiment the system may comprise 0.6% by weight to 2.6% by weight synthetic polymer and 0.6% by weight to 11.1% by weight TEA.
- TEA is miscible in water, which prevents any undesirable phase separation.
- MDEA methyldiethanol amine
- DMEA dimethylethanol amine
- DEA diethanol amine
- MEA monoethanol amine
- TEA/glycol system a TEA/alcohol system
- Suitable alcohols would include methanol, ethanol, n-propanol and its isomers, n-butanol and its isomers, n-pentanol and its isomers, n-hexanol and its isomers, etc.
- TEA may act as a pH buffer.
- Many of the above mentioned synthetic polymers contain ether linkages in the main chain of the polymer.
- some of these cleavage mechanisms are acid-catalyzed.
- TEA may help to prevent an acid-catalyzed degradation of a synthetic polymer.
- the present invention advantageously increases the effective temperature range for synthetic polymer systems in an inexpensive, easy-to-implement method.
- the addition of miscible amines into the synthetic polymer system dramatically increases the temperature resistivity of the solution and enhances the overall stability of the system.
- the present invention specifically contemplates that the above described compositions may be used to treat a well.
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Abstract
The present invention relates to methods and compositions for increasing the effective temperature range for viscosified fluids, including particularly fluids that have been viscosified by the addition of a synthetic polymer. In one embodiment, the present invention relates to a method for increasing the effective temperature range for a synthetic polymer-viscosified fluid used as a well fluid, which includes adding a miscible tertiary, secondary, and/or primary amine compound into a polymer solution. In another embodiment, the present invention relates to a thermally stable well fluid, which includes a synthetic polymer, a solvent, and a tertiary, secondary, and/or primary amine miscible in the solvent.
Description
- This Application claims the benefit of U.S. Provisional Patent Application No. 60/297,491, filed on Jun. 11, 2001.
- 1. Field of the Invention
- The invention relates generally to the exploitation of hydrocarbon-containing formations. More specifically, the invention relates to the fields of fluid rheology, thickeners, viscosifiers, viscoelastic fluids, drilling fluids, well fracturing fluids, well treatment fluids and fluid control pills.
- 2. Background Art
- When drilling or completing wells in earth formations, various fluids typically are used in the well for a variety of reasons. The fluid often is aqueous. For the purposes herein, such fluid will be referred to as “well fluid.” Common uses for well fluids include: lubrication and cooling of drill bit cutting surfaces while drilling generally or drilling-in (i.e., drilling in a targeted petroliferous formation), transportation of “cuttings” (pieces of formation dislodged by the cutting action of the teeth on a drill bit) to the surface, controlling formation pressure to prevent blowouts, maintaining well stability, suspending solids in the well, minimizing fluid loss into and stabilizing the formation through which the well is being drilled, fracturing the formation in the vicinity of the well, displacing the fluid within the well with another fluid, cleaning the well, testing the well, implacing a packer fluid, abandoning the well or preparing the well for abandonment, and otherwise treating the well or the formation. Brines (such as CaBr2) commonly are used as well fluids because of their wide density range and the fact that brines are typically substantially free of suspended solids. Additionally, brines typically do not damage certain types of downhole formations.
- A variety of compounds typically are added to the brine-based well fluids. For example, a brine-based well fluid also may include corrosion inhibitors, lubricants, pH control additives, surfactants, solvents, and/or weighting agents, among other additives. Some typical brine-based well fluid viscosifying additives include synthetic polymers and oligomers such as poly(ethylene glycol) (PEG), poly(diallyl amine), poly(acrylamide), poly(aminomethylpropylsulfonate [AMPS]), poly(acrylonitrile), poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl amine), poly(vinyl sulfonate), poly(styryl sulfonate), poly(acrylate), poly(methyl acrylate), poly(methacrylate), poly(methyl methacrylate), poly(vinylpyrrolidone), poly(vinyl lactam) and co-, ter-, and quater-polymers of the following co-monomers: ethylene, butadiene, isoprene, styrene, divinylbenzene, divinyl amine, 1,4-pentadiene-3-one (divinyl ketone), 1,6-heptadiene-4-one (diallyl ketone), diallyl amine, ethylene glycol, acrylamide, AMPS, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl amine, vinyl sulfonate, styryl sulfonate, acrylate, methyl acrylate, methacrylate, methyl methacrylate, vinylpyrrolidone, and vinyl lactam.
- The synthetic polymers and oligomers listed above have other uses in drilling applications as well. When drilling progresses to the level of penetrating a hydrocarbon bearing formation, special care may be required to maintain the stability of the wellbore. Examples of formations in which problems often arise are highly permeable and/or poorly consolidated formations. In these types of formations, a technique known as “under-reaming” may be employed.
- In this process, the wellbore is drilled to penetrate the hydrocarbon bearing zone using conventional techniques. A casing generally is set in the wellbore to a point just above the hydrocarbon bearing zone. The hydrocarbon bearing zone then may be re-drilled, for example, using an expandable under-reamer that increases the diameter of the wellbore. Under-reaming usually is performed using special “clean” drilling fluids. Typical drilling fluids used in under-reaming are expensive, aqueous, dense brines that are viscosified with a gelling and/or cross-linked polymer to aid in the removal of formation cuttings. The high permeability of the target formation, however, may allow large quantities of the drilling fluid to be lost into the formation.
- Once the drilling fluid is lost into the formation, it becomes difficult to remove. Calcium and zinc-bromide brines can form highly stable, acid insoluble compounds when reacted with the formation or substances contained therein. This reaction may reduce the permeability of the formation to any subsequent out-flow of the targeted hydrocarbons. The most effective way to prevent such damage to the formation is to limit fluid loss into the formation.
- Thus, providing effective fluid loss control is highly desirable to prevent damaging the formation in, for example, completion, drilling, drill-in, displacement, hydraulic fracturing, work-over, packer fluid implacement or maintenance, well treating, or testing operations. Techniques that have been developed to control fluid loss include the use of fluid loss “pills.” Significant research has been directed to determining suitable materials for the fluid loss pills, as well as controlling and improving the properties of the fluid loss pills. Typically, fluid loss pills work by enhancing filter-cake buildup on the face of the formation to inhibit fluid flow into the formation from the wellbore.
- Because of the high temperatures, high shear (caused by the pumping and placement), high pressures, and low pH to which well fluids are exposed (i.e., “stress conditions”), the synthetic polymeric materials used to form fluid loss pills and to viscosify the well fluids tend to degrade rather quickly. What is needed are synthetic polymer compositions that can withstand the stress conditions for extended periods of time without significant degradation. In particular, what is needed is a simple, inexpensive way to increase the thermal range for viscosifying agents used in downhole applications. Preferably, this thermal extender would be applicable to various viscosifying agents.
- In one aspect, the present invention relates to a method for increasing the thermal and pressure stability of viscosifying agents, particularly synthetic polymers, used in a well fluid which comprises mixing a miscible tertiary amine compound into the fluid.
- In another aspect, the present invention relates to a method for increasing the thermal and pressure stability of viscosifying agents, and particularly synthetic polymers, in a well fluid which comprises mixing a miscible secondary amine compound into the fluid.
- In another aspect, the present invention relates to a method for increasing the thermal and pressure stability of viscosifying agents, and particularly synthetic polymers, in a well fluid which comprises mixing a miscible primary amine compound into the fluid.
- In another aspect, the present invention relates to a thermally stable viscosifying system for well fluids which comprises a synthetic polymer, a solvent, and a tertiary amine miscible in the solvent.
- In another aspect, the present invention relates to a thermally stable viscosifying system for well fluids, which comprises a synthetic polymer, a solvent, and a secondary amine miscible in the solvent.
- In another aspect, the present invention relates to a thermally stable viscosifying system for well fluids, which comprises a synthetic polymer, a solvent, and a primary amine miscible in the solvent.
- Other aspects and advantages of the invention will be apparent from the following description and the appended claims.
- The present invention relates to a novel composition for increasing the thermal durability of synthetic polymers used in downhole applications. Further, the present invention relates to increasing the thermal and pressure stability of viscosified well fluids by including an effective amount of an amine into a synthetic polymer system. “Effective” simply means an amount sufficient to raise the temperature stability of the synthetic polymer system by a measurable amount.
- In general, the present invention relates to compositions for the creation of, and methods of using fluid loss control pills and similar fluids that can sustain stress conditions for extended periods of time without significant fluid loss or loss of desirable Theological properties. The stress conditions may include, for example, exposure to high shear in pumping and placement, exposure to oxidizing breakers (including oxygen dissolved in the fluid), exposure to brines having high divalent cation content, high temperature, high differential pressure, low pH, extended time, and a combination of two or more of such stress conditions. These pills and fluids are advantageously applied in or in connection with drilling, drill-in, displacement, completion, hydraulic fracturing, work-over, packer fluid implacement or maintenance, well treating, testing, or abandonment.
- In general, one embodiment of the invention is related to the effect of triethanol amine (TEA) on a conventional synthetic polymer well fluid system, such as a system containing polyethylene glycol (PEG). PEG is a water soluble polymer that may be generated from a condensation reaction between ethylene glycol monomers. The general structure of a single repeat unit of PEG is shown below:
-
- In one embodiment, the effects of high temperatures for long periods of time on the fluid control abilities of synthetic polymers were measured on a TEA-containing composition. Specifically, 10.0 grams per lab barrel (g/Lbbl) of high molecular weight PEG (MW ˜400,000 g/mol) and 7.0 g/Lbbl of low molecular weight PEG (MW ˜800 g/mol) were added slowly to an agitated brine solution. Note that throughout the specification, the term “lab barrel” is used as a unit of volume—a lab barrel is equivalent to about 350 milliliters. (A lab barrel of water weighs about 350 grams, just as a regular barrel of water weighs the same number of pounds, about 350. This is the formal origin of the term “lab barrel.”Additionally, while the particular embodiments describe a particular order of addition for the chemical components, such a description is not intended to limit the scope of the invention in any fashion.
- In this embodiment, the brine solution comprises 0.888 Lbbl of a 19.2 pounds per gallon (ppg) density ZnBr2/CaBr2 in water. The 19.2 pounds per gallon ZnBr2/CaBr2 brine solution is roughly 52.8% by weight ZnBr2, 22.8% CaBr2, with the balance being water. Next, 15.0 g/Lbbl amount of an oxygen scavenger (sodium thiosulfate pentahydrate in this embodiment) was mixed as a dry reagent into the brine. Next, 5.0 g/Lbbl of TEA (85% TEA in water) was added to the brine. After the addition of the TEA, 5.0 g/Lbbl of gilsonite was added as a dry reagent into the brine. Gilsonite is a natural, resinous hydrocarbon which is often used as an additive in well fluids because of its corrosion inhibiting properties. In addition, 5.0 g/Lbbl of lignite was added to the brine as a dry reagent. To this mixture, 30.0 g/Lbbl of calcium carbonate (CaCO3) was added. It should be noted that all of the additional chemicals added to the TEA/PEG/brine system discussed above were added only to approximate a “typical” well fluid. It is explicitly within the scope of the invention that a variety of other well fluid additives may be present in addition to the amine/synthetic polymer/brine system described above.
- The fluid loss properties of the compositions described in the following embodiments were determined as follows. Fluid loss tests of durations ranging from 30 seconds to 48 hours were performed in an API standard high pressure high temperature (HPHT) apparatus (Ref.: API 13-BI with one modification: substituting an Aloxite or ceramic disk for paper). The testing temperature used in obtaining the below readings was predetermined, such as, for example, in accordance with a bottom-hole temperature at which the fluid will be used in the field. The HPHT apparatus was operated at 250 to 600 psig differential pressure, using, for example, a 50-2000 milliDarcy Aloxite disc (HPHT cell). In general, the HPHT cell is loaded into the HPHT apparatus, which is then pressurized and heated to a predetermined temperature. A discharge valve located on the HPHT apparatus is then opened, and a filtrate volume is measured as a function of time.
- In the first embodiment, after mixing the above components, the composition was placed in a HPHT cell and heated for 45 minutes at 250° F. In this embodiment, a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for 6 hours. The tables reproduced in the specification, therefore, merely extract the relevant data, rather than reproducing the data in toto.
- For comparison, an experiment was run under conditions similar to those described above without the addition of TEA. In the comparison, 15.0 g/Lbbl of high molecular weight PEG (MW ˜400,000 g/mol) and 7.0 g/Lbbl of low molecular weight PEG (MW ˜800 g/mol) were added slowly to 0.879 Lbbl of agitated brine solution. As in the previous embodiment, the brine solution comprised a 19.2 pounds per gallon (ppg) ZnBr2/CaBr2 in water. The lignite, gilsonite, calcium carbonate, and oxygen scavenger were added as in the above embodiment. The amounts of lignite, gilsonite, and calcium carbonate were substantially identical to those described above, while less (5.0 g/Lbbl compared to 15.0 g/Lbbl) oxygen scavenger was used.
- As in the first embodiment, after mixing the above components, the composition was placed in a HPHT cell and heated for 45 minutes at 250° F. In this embodiment, a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for approximately 6 hours.
- The results are summarized below:
TABLE 1 COMPARISON OF FLUID LOSS (MEASURED IN ML) FOR TEA VS. NON-TEA SYSTEMS Com- 30 15 30 60 90 180 285 350 position sec min min min min min min min Embodi- 2.0 no 5.0 no 6.8 8.4 10.1 11.5 ment 1 reading (27 reading min) Com- 10 25 63 147 blow- — — — parative out Example (70 min) - The data in Table 1 shows that the TEA containing system prevents significant fluid loss from occurring, while the system without the TEA suffers a “blowout” (i.e., the loss of all fluid) after 70 minutes. The TEA-containing system, however, maintains its integrity even after approximately 6 hours. Further experiments revealed that the fluid control properties of the TEA-containing system remain substantially intact under the HPHT conditions described above for at least 48 hours. The loss of fluid control exhibited by the non-TEA-containing system is attributed, at least in part, to polymer degradation. A mechanism for how TEA provides the additional thermal stability (as shown in Table 1) is proposed below.
- In a second embodiment, the effectiveness of the TEA on a system having higher PEG concentration than the first embodiment was determined. In this embodiment, 15.0 g/Lbbl of high molecular weight PEG (MW ˜400,000) and 7.0 g/Lbbl of low molecular weight PEG were added to 0.888 Lbbl of a 19.2 ZnBr2/CaCl2 in water. As in the first embodiment, the 19.2 pounds per gallon ZnBr2/CaBr2 water mixture is roughly 52.8% by weight ZnBr2, 22.8% CaBr2, with the balance being water. To the PEG/brine mixture, the oxygen scavenger, lignite, gilsonite, TEA, and calcium carbonate were added in the same amounts and in the same manner as in the first embodiment described above.
- As in the first embodiment, after mixing the above components, the composition was placed in a HPHT cell and heated for 45 minutes at 250° F. In the second embodiment, a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for approximately 6 hours.
- The results are summarized below:
TABLE 2 COMPARISON OF FLUID LOSS (MEASURED IN ML) FOR HIGHER CONCENTRATION PEG 30 6 27 70 90 180 285 350 Composition sec min min min min min min min Embodiment 1 2.0 3.8 5.0 5.8 6.8 8.4 10.1 11.5 Embodiment 2 3.2 4.0 5.1 5.6 6.0 7.6 9.5 10.0 - The data in Table 2 shows that the system suffers substantially no adverse effect on the fluid control properties (i.e., the thermal stability) when the concentration of PEG is raised by about 50%.
- In a third embodiment, the effect of increased TEA concentration was determined. In this embodiment, 15.0 g/Lbbl of high molecular weight PEG and 7 g/Lbbl of low molecular weight PEG were added to 0.676 Lbbl of 19.2 ppg ZnBr2 /CaBr2 in water. To this mixture, 80.0 g/Lbbl of TEA was added. In addition, the oxygen scavenger, the lignite, the gilsonite, and the calcium carbonate were added in the same amounts and in the same manner as in the first and second embodiments.
- As in the first and second embodiments, after mixing the above components, the composition was placed in a HPHT cell and heated for 45 minutes at 250° F. In the third embodiment, a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed into the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid lost was then recorded over approximately 10 to 15 minute intervals for approximately 3 hours.
- The results are tabulated below:
TABLE 3 FLUID LOSS (MEASURED IN ML) FOR HIGHER CONCENTRATION TEA Composition 30 sec 27 min 70 min 90 min 180 min Embodiment 3 7.0 16.0 40.0 45.0 101 (25 min) (75 min) (190 min) - The data in Table 3 shows that higher amounts of TEA still prevent a blowout from occurring.
- In a fourth embodiment, the effect of TEA on mixed polymer systems was determined. In this embodiment, 15.0 g/Lbbl of high molecular weight PEG and 7.0 g/Lbbl of low molecular weight PEG were added to 0.648 Lbbl of 19.2 ZnBr2/CaBr2 in water. Then, 3.0 g/Lbbl of a polymer sold under the trade name HE-300 and 3.0 g/Lbbl of a polymer sold under the trade name of HE-400 were added. Both HE-300 and HE-400 are sold by Drilling Specialties, Inc. of Bartlesville, Okla. 74004. HE-300 and HE-400 polymers are a family of synthetic, divalent-cation-tolerant, high temperature polymers that work in brine and freshwater environments for many applications. In addition, they may be crosslinked, so that they form rigid gels in a petroleum bearing reservoir for conformance control of unwanted water or gas production. When drilling or completing with clear brine fluids, HE-300 and HE-400 polymers have been used to viscosify brines at temperatures as high as 240° C. and will remain stable in solution without precipitation. 87.0 g/Lbbl of TEA was then added to this mixture. 5.0 g/Lbbl of both lignite and gilsonite were then added to the mixture. In addition, 10.0 g/Lbbl of magnesium oxide and 30.0 g/Lbbl of calcium carbonate were added as dry reagents.
- As in the above embodiments, after mixing the above components, the composition was placed in a HPHT cell and heated for 45 minutes at 250° F. In the fourth embodiment, a HPHT cell fitted with an Aloxite disk having a nominal permeability of 60 milliDarcys was used. After allowing the HPHT cell to cool, the HPHT cell was placed in the HPHT apparatus and was pressurized to 500 psig at a temperature of 395° F. The amount of fluid loss was then recorded over approximately 10 to 15 minute intervals for approximately 16 hours.
- The results are summarized below:
TABLE 4 FLUID LOSS (MEASURED IN ML) FOR TEA/MIXED POLYMER SYSTEMS 30 20 60 120 215 375 965 Composition sec min min min min min min Embodiment 6.0 7.0 8.0 15.0 22.0 49.0 94.0 4 - The data in Table 4 shows that even when subjected to temperatures well in excess of 250° F., the TEA/mixed polymer system maintains its thermal/pressure stability.
- In addition, while specific amounts of the chemicals used are described in the above embodiments, it is specifically within the contemplation of the invention that amounts different than those described above may be used to provide the desired thermal stability, depending on the particular application. For example, in one embodiment, a suitable system for increasing polymer stability may comprise 0.1% by weight to 99% by weight synthetic polymer and 0.1% by weight to 99% by weight TEA. More preferably, in one embodiment the system may comprise 0.3% by weight to 5% by weight synthetic polymer and 0.2% by weight to 20% TEA. Still more preferably, in one embodiment the system may comprise 0.6% by weight to 2.6% by weight synthetic polymer and 0.6% by weight to 11.1% by weight TEA.
- Significantly, like PEG, TEA is miscible in water, which prevents any undesirable phase separation. While the foregoing embodiments reference a limited number of compounds, it should be recognized that chemical compounds having the same general characteristics also will function in an analogous fashion. For example, it is expressly within the scope of the present invention that methyldiethanol amine (MDEA), dimethylethanol amine (DMEA), diethanol amine (DEA), monoethanol amine (MEA), or other suitable tertiary, secondary, and primary amines and ammonia could be substituted, in whole or in part, for the triethanol amine described herein. In addition, it also is expressly within the scope of the invention that other mixed TEA systems may be used as additives, such as a TEA/glycol system or a TEA/alcohol system. Suitable alcohols would include methanol, ethanol, n-propanol and its isomers, n-butanol and its isomers, n-pentanol and its isomers, n-hexanol and its isomers, etc.
- Similarly, other synthetic polymers may be substituted for PEG, such as, for example, poly(acrylonitrile), poly(acetates), and other synthetic polymers known in the art. We have additional data showing the utility of amines in non-CaBr2-containing brine solutions, specifically including those based on NaHCO2, KHCO2, CsHCO2, and combinations thereof. Furthermore, it should be noted that while most of the above examples discuss the utility of amines in CaBr2-containing brine solutions, it will be clear to one of ordinary skill in the art that other brine solutions, such as ZnCl2, CaBr2, and ZnBr2, NaCl, KC1, NH4Cl, MgCl2, seawater, NaBr, Na2S2O3, and combinations thereof may be used.
- In addition, while specific amounts of the chemicals used are described in the above embodiments, it is specifically within the contemplation of the invention that amounts different than those described above may be used to provide the desired thermal stability, depending on the particular application.
- A proposed mechanism for how the addition of TEA assists in maintaining the stability of synthetic polymer systems is based on the belief that TEA may act as a pH buffer. Many of the above mentioned synthetic polymers contain ether linkages in the main chain of the polymer. There are mechanisms for the cleavage of ether linkages (which are slowly catalyzed by acidic conditions), which under severe conditions of stress, can be effected upon the backbone of bonds which tie the units of the polymer together. Cleaving one or more of the bonds which constitute the backbone of the polymer leads directly to de-polymerization and hence to degradation of the polymer. As stated above, some of these cleavage mechanisms are acid-catalyzed. Thus, by maintaining the pH level above that of the base brine pH, or as near to 7 as possible, TEA may help to prevent an acid-catalyzed degradation of a synthetic polymer.
- In the above discussion involving an acid-catalyzed mechanisms for polymer degradation, it should be noted explicitly that both Bronsted-Lowry and Lewis definitions of acids are equally applicable. Thus in aqueous systems where acids may be present and acting as such through the Bronsted-Lowry definition of an acid, the role of the acid would be that of a “proton-donor” while the complementary role of the TEA would be that of a “proton-acceptor.”Furthermore, in systems such as, for example, those containing the Lewis acid zinc bromide, where the acid may be acting as such through the Lewis definition of an acid, the role of the acid would be that of an “electron-acceptor” while the complementary role of the TEA would be that of a “electron-donor.”
- The present invention advantageously increases the effective temperature range for synthetic polymer systems in an inexpensive, easy-to-implement method. The addition of miscible amines into the synthetic polymer system dramatically increases the temperature resistivity of the solution and enhances the overall stability of the system. In addition, the present invention specifically contemplates that the above described compositions may be used to treat a well.
- While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (29)
1] A method for increasing the thermal stability of a well fluid comprising:
mixing an effective amount of a miscible amine in the well fluid, wherein the well fluid comprises a synthetic polymer.
2] The method of claim 1, wherein the miscible amine comprises an amine selected from the group consisting of primary, secondary and tertiary amines, and mixtures thereof.
3] The method of claim 1, wherein the miscible amine comprises about 0.2% to about 20% by weight of the well fluid.
4] The method of claim 3, wherein the miscible amine comprises about 0.6% to about 12% by weight of the well fluid.
5] The method of claim 3, wherein the synthetic polymer comprises about 0.3% to about 5% by weight of the well fluid.
6] The method of claim 4, wherein the synthetic polymer comprises about 0.6% to about 2.6% by weight of the well fluid.
7] The method of claim 1, wherein the synthetic polymer comprises polyethylene glycol.
8] The method of claim 1, wherein the miscible amine comprises triethanol amine.
9] A method for increasing the thermal stability of a well fluid comprising:
mixing about 0.2% to about 20% by weight of a miscible amine into the well fluid, wherein the well fluid comprises a synthetic polymer.
10] The method of claim 9, wherein the miscible amine comprises an amine selected from the group consisting of primary, secondary and tertiary amines, and mixtures thereof.
11] The method of claim 9, wherein the synthetic polymer comprises polyethylene glycol.
12] The method of claim 10, wherein the synthetic polymer comprises about 0.3% to about 5% by weight of the well fluid.
13] The method of claim 9, wherein the miscible amine comprises triethanol amine.
14] A thermally stable well fluid comprising:
a synthetic polymer; and
an effective amount of miscible amine.
15] The well fluid of claim 14, wherein the miscible amine comprises an amine selected from the group consisting of primary, secondary and tertiary amines, and mixtures thereof.
16] The well fluid of claim 14, wherein the synthetic polymer comprises polyethylene glycol.
17] The well fluid of claim 14, wherein the miscible amine comprises triethanol amine.
18] The well fluid of claim 14, wherein the miscible amine comprises about 0.2% to about 20% by weight of the well fluid.
19] The well fluid of claim 18, wherein the miscible amine comprises about 0.6% to about 12% by weight of the well fluid.
20] The well fluid of claim 18, wherein the synthetic polymer comprises about 0.3% to about 5% by weight of the well fluid.
21] The well fluid of claim 19, wherein the synthetic polymer comprises about 0.6% to about 2.6% by weight of the well fluid.
22] A method of treating a well comprising:
injecting a well treating fluid into the well, wherein the well treating fluid comprises a synthetic polymer and an effective amount of a miscible amine.
23] The method of claim 22, wherein the miscible amine comprises an amine selected from the group consisting of primary, secondary and tertiary amines and mixtures thereof.
24] The method of claim 22, wherein the synthetic polymer comprises polyethylene glycol.
25] The method of claim 22, wherein the miscible amine comprises triethanol amine.
26] The method of claim 22, wherein the miscible amine comprises about 0.2% to about 20% by weight of the well treating fluid.
27] The method of claim 26, wherein the miscible amine comprises about 0.6% to about 12% by weight of the well treating fluid.
28] The method of claim 26, wherein the synthetic polymer comprises about 0.3% to about 5% by weight of the well treating fluid.
29] The method of claim 27, wherein the synthetic polymer comprises about 0.6% to about 2.6% by weight of the well treating fluid.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/901,444 US20030017953A1 (en) | 2001-06-11 | 2001-07-09 | Thermal extenders for well fluid applications involving synthetic polymers |
EP02737431A EP1397463A1 (en) | 2001-06-11 | 2002-06-07 | Thermal extenders for well fluid applications involving synthetic polymers |
PCT/US2002/018166 WO2002100973A1 (en) | 2001-06-11 | 2002-06-07 | Thermal extenders for well fluid applications involving synthetic polymers |
CA002450277A CA2450277A1 (en) | 2001-06-11 | 2002-06-07 | Thermal extenders for well fluid applications involving synthetic polymers |
NO20035533A NO20035533D0 (en) | 2001-06-11 | 2003-12-11 | Thermal fillers for use in high degree complementary fluid as synthetic polymer polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US29749101P | 2001-06-11 | 2001-06-11 | |
US09/901,444 US20030017953A1 (en) | 2001-06-11 | 2001-07-09 | Thermal extenders for well fluid applications involving synthetic polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030017953A1 true US20030017953A1 (en) | 2003-01-23 |
Family
ID=26970180
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/901,444 Abandoned US20030017953A1 (en) | 2001-06-11 | 2001-07-09 | Thermal extenders for well fluid applications involving synthetic polymers |
Country Status (5)
Country | Link |
---|---|
US (1) | US20030017953A1 (en) |
EP (1) | EP1397463A1 (en) |
CA (1) | CA2450277A1 (en) |
NO (1) | NO20035533D0 (en) |
WO (1) | WO2002100973A1 (en) |
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US20100252259A1 (en) * | 2009-04-01 | 2010-10-07 | Horton Robert L | Oil-based hydraulic fracturing fluids and breakers and methods of preparation and use |
US20100263867A1 (en) * | 2009-04-21 | 2010-10-21 | Horton Amy C | Utilizing electromagnetic radiation to activate filtercake breakers downhole |
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Also Published As
Publication number | Publication date |
---|---|
NO20035533D0 (en) | 2003-12-11 |
WO2002100973A1 (en) | 2002-12-19 |
EP1397463A1 (en) | 2004-03-17 |
CA2450277A1 (en) | 2002-12-19 |
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Owner name: M-I, L.L.C., TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HORTON, ROBERT L.;KIPPIE, DAVID P.;FOXENBERG, WILLIAM E.;REEL/FRAME:012458/0607;SIGNING DATES FROM 20011002 TO 20011008 |
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