CA2245032A1 - Methods and compositions for sealing pipe strings in well bores - Google Patents
Methods and compositions for sealing pipe strings in well bores Download PDFInfo
- Publication number
- CA2245032A1 CA2245032A1 CA002245032A CA2245032A CA2245032A1 CA 2245032 A1 CA2245032 A1 CA 2245032A1 CA 002245032 A CA002245032 A CA 002245032A CA 2245032 A CA2245032 A CA 2245032A CA 2245032 A1 CA2245032 A1 CA 2245032A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- group
- amount
- range
- weight
- 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
Links
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
-
- 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
-
- 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
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The present invention provides improved methods and compositions for sealing a pipe string in a well bore. The methods basically comprise the steps of preparing a hardenable epoxy sealing composition which hardens into a resilient solid mass having high bond strength comprising an epoxide containing liquid, an organosilane compound and a hardening agent, placing the epoxy composition in the annulus between the pipe and the walls of the well bore and allowing the epoxy composition to harden.
Description
CA 0224~032 1998-08-14 M~l~.O~S AND COMPOSITIONS FOR SEALING PIPE
STRINGS IN WELL BORES
RELATED U.S. APPLICATION DATA
This application is a continuation-in-part of application Serial No. 08/914,594 filed on August 18, 1997.
BACK~OUND OF THE INVENTION
1. Field of the Invention.
The present invention relates generally to improved methods and COmpO~;itiOnS for sealing pipe strings in well bores, and more particularly, to such methods and compositions wherein the sealanz is corrosion resistant, highly resilient and has high bond strength.
STRINGS IN WELL BORES
RELATED U.S. APPLICATION DATA
This application is a continuation-in-part of application Serial No. 08/914,594 filed on August 18, 1997.
BACK~OUND OF THE INVENTION
1. Field of the Invention.
The present invention relates generally to improved methods and COmpO~;itiOnS for sealing pipe strings in well bores, and more particularly, to such methods and compositions wherein the sealanz is corrosion resistant, highly resilient and has high bond strength.
2. Description of the Prior Art.
Hydraulic cement compositions are commonly utilized as sealants in subterranean well construction and repair procedures. F'or example, hydraulic cement compositions are used in primary sealing operations whereby strings of pipe such as casing and liners are sealed in well bores. In performing primary cementing, a hydraulic cement composition is pumped into the annular space between the walls of the well bore and the exter.or surfaces of pipe disposed therein. The cement composition is permitted to set in the annular space thereby forming an annular sheath of hardened substantially impermeable cement therein. The cement sheath supports and positions the pipe in the well bore and bonds the exterior surfaces of the pipe to the walls of the well bore whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented.
CA 0224~032 1998-08-14 When conventional cement compositions are utilized for sealing pipe strings in well bores, they set into brittle solid masses. Consequently, the solid cement often does not have sufficient resiliency to resist loss of pipe and/or formation bond, cracking or shattering as the result of pipe movements caused by expansion, contraction, impacts or shocks.
The bond loss, cracking or shattering of the set cement allows leakage of formation fluids through at least portions of the well bore ky way of the annulus therein which can be highly detrimental.
Hardenable epoxy resin compositions have heretofore been used for sealing pipe strings in well bores which penetrate subterranean zones containing corrosive fluids. For example, waste fluids such as salt water, acidic materials, caustic materials, organic materials, chemical by-product materials and the like are often disposed of by injecting them into disposal wells. ',uch disposal wells penetrate subterranean formations which accept large volumes of waste and are naturally separated from other subterranean formations. When a disposal well or other well where hydrocarbons are produced along with corrosive fluids is completed in the conventional manner whereby a st:ring of steel pipe is cemented in the well bore utilizing a hydraulic cement slurry, both the cement and steel pipe are often subjected to severe corrosion. A result of such corrosion in disposal wells can be that the liquid waste materials leak into and contaminate formations containing useful fluids such as hydrocarbons or potable water. In other wells where hydrocarbons are produced with CA 0224~032 1998-08-14 corrosive fluids, the corrosion can result in leakage of fluids between f'ormations and/or to the surface.
In order to prevent the corrosion of metal pipe strings in disposal and other similar wells, it has heretofore been the practice to seal the pipe strings in well bores with a hardenable epoxy resin composition. Epoxy resin compositions are highly resistant to degradation by acids and other corrosive fluids and their use at least reduces the corrosion of metal pipe strings and the chances that corrosive fluids will find their way to the surface or into other subterranean locations. However, like set cement compositions, hardened epoxy resin comFositions have often lacked sufficient resiliency as well as the necessary bond strength to resist failure as a result of pipe movements.
Thus, there are needs for improved methods and compositions fo:r seali.ng pipe strings in well bores whereby the hardened compositions can withstand the effects of contact with corrosive fluids and also have the resiliency and high bond strength required to withstand pipe movements without failure.
';U~lARY OF THE lNV151.~ lON
The present, invention provides improved methods and epoxy sealing compositiorLs f'or sealing a string of pipe in a well bore whereby upon h,ardening the compositions can withstand the effects of contact with corrosive fluids and pipe movements.
The methods basic3Llly comprise the steps of preparing a hardenable epoxy sealing composition which hardens into a solid mass having resiliency and high pipe and formation CA 0224~032 1998-08-14 surface bond strengths~ placing the epoxy composition into the annulus between the string of pipe and the walls of the well bore and allowing the epoxy composition to harden.
The epoxy -ompositions of this invention which have high resiliencies and high bond strengths are comprised of an epoxy resin or an epoxide containing liquid, or both, an organosilane compound and at least one hardening agent. The epoxy compositions preferably also include a filler such as crystalline silica or the like.
It is, therefore, a general object: of the present invention to provide improved methods and compositions for sealing pipe strings in well bores.
Other and further objects, features and advantages of the present invention will be apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.
DESCRIPTION OF PREFERRED ENBODIMENTS
The present invention provides improved methods and compositions for sealing pipe strings in well bores whereby the hardened sealing compositions can withstand the effects of contact with corrosive fluids as well as pipe movements due to expansion, contrac ion, impacts, shocks or the like. In accordance with the methods, an epoxy composition which hardens into a resilient solid mass having high pipe and formation bond strengths is prepared, placed in the annulus between a pipe or pipe string and the walls of a well bore and allowed to harden therein. The sealant compositions which are useful in accordance with the present invention are epoxy CA 0224~032 1998-08-14 compositions basically comprised of an epoxy resin or an epoxide containing liquid, or both, an organosilane compound and at least one hardening agent.
While various epoxy resins can be utilized, preferred such resins are those selected from the condensation products of epichlorohydrin and bisphenol A. A particularly suitable such resin is commercially available from the Shell Chemical Company under the trade designation "EPON~RESIN 828". This epoxy resin has a molecular weight of about 340 and a one gram equivalent of epoxide per about 180 to about 195 grams of resin. When used, the epoxy resin is generally included in an epoxy composition of this invention in an amount in the range of from about 101; to about 90~ by weight of the epoxy composition, preferably in an amount of about 50~.
A solvent or a low viscosity epoxide containing liquid or a mixture of such epoxide containing liquids can be utilized to modify the visc09ity of the epoxy resin used and to add flexibility and resiliency to the epoxy composition after hardening. An epichlorohydrin/bisphenol A condensation epoxy resin which has been modified with an aromatic solvent is commercially available from the Shell Chemical Company under the trade designati~n "EPSEAL RE2".
When an epoxide containing liquid Cl- mixture of such liquids is includecL in an epoxy composition of this invention to modify the viscosity of an epoxy resin therein, the epoxide containing liquid or mixture is generally present in an amount in the range of from about 20~ to about 50~ by weight of the epoxy composition, preferably in an amount of about 27~. An CA 0224~032 1998-08-14 epoxide containing liquid or a mixture of such liquids can also be utilized as the only epoxide source in an epoxy composition of this invention.
While various epoxide containing liquids can be used, preferred such. liquids are the diglycidyl ether of 1,4-butanediol, the diglycidyl ether of neopentyl glycol and the diglycidol ether of cyclohexanedimethanol. A suitable epoxide containing liquid ~omprised of the diglycidyl ether of 1,4-butanediol is commercially available from the Shell Chemical Company under the trade name "HELoXY(967 " . This epoxide containing liquid has a viscosity at 25~C in the range of from about 13 to about 18 centipoises, a molecular weight of 202 and a one gram equ.ivalent of epoxide per about 120 to about 130 grams of the liquid. A suitable di.glycidyl ether of neopentylglycol is commercially available from Shell Chemical Company under the trade name "HELOXY~68 " . This epoxide containing liqui.d has a viscosity at 25~C in the range of from about 13 to about 18 centipoises, a molecular weight of 216 and a one gram equ.iva:lent of epoxide per about 130 to about 140 grams of the liquid. A suitable diglycidyl ether of cyclohexanedimethan~l is commercially available from Shell Chemical Company under the trade name "HELOXY3107". This epoxide containi.ng liquid has a viscosity at 25~C in the range of from about 55 to about 75 centipoises, a molecular weight of 256 and a one gram equivalent of epoxide per about 155 to about 165 grams of the liquid.
When an epoxide containing liquid or mixture is utilized CA 0224~032 1998-08-14 as the only epoxicLe source in an epoxy composition of this invention, the epoxide containing liquid or mixture is generally present in an amount in the range 3f from about 20% to about 801i by weight of the epoxy composition, preferably in an am~unt: of about 50%.
The organosi:Lane compound functions in the epoxy compositions of this invention to impart high metal pipe surface and formation surface bond strengths to the compositions. 'rhe organosilane compound undergoes hydrolysis in the presence of trace quantities of water whereby trialkoxysilanols are formed which dehydrate and form strong bonds to pipe and formation surfaces. That is, the dehydration results in the formation of bonds with silica in the formation and iron oxide on the pipe.
Suitable organosilane compounds include 3-aminopropyltrimethy~xysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-ammopropyltriethoxysilane and 3-glycidoxy-propyltrimethoxysil~ne. Of these, 3-glycidoxypropyltri-methoxysilane is preferred. The organosilane compound is included in an epoxy composition of this invention in an amount in the range of from about 0.1~ to about 5% by weight of the epoxy composition, preferably in an amount of about 0.5%.
A variety of hardening agents including, but not limited to, aliphatic arnines, amide amines, amido amines, imidazoles, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, polyamides, polyethylamines and carboxylic acid anhydrides can be utilized in the compositions CA 0224~032 1998-08-14 of this invention containing the above described epoxy resins and/or epoxide containing liquids. Of these, aliphatic amines, aromatic amines and carboxylic acid anhydrides are the most suitable.
Examples of aliphatic and aromatic amine hardening agents are triethylenetetraamine, ethylenediamine, N-cocoalkyltri-methylenediamine, isophoronediamine, diethyltoluenediamine, and tris(dimethylaminomethylphenol). Examples of suitable carboxylic acid anhydrides are methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride and phthalic anhydride. Of these, triethylenetetraamine, ethylenediamine, N-cocoalkyltri-methylenediamine, isophoronediamine, diethyltoluenediamine and tris(dimethylaminom~thylphenol) are preferred, with isophoronediamine, diethyletoluenediamine and tris(dimethylaminomethylphenol) being the most preferred. The hardening agent or agents utilized are included in the epoxy compositions of the present invention in an amount in the range of from about 20~ to about 50~ by weight of the composlt lons .
As mentioned above, the epoxy compositions preferably also include a particulate filler such as crystalline silicas, amorphous silicas, clays, calcium carbonate or barite. When such a filler is utilized, it is added to an epoxy composition of this invention in an amount in the range of from about 100 to about 300~ by weight of the composition.
A preferred method of this invention for sealing a string of pipe in a well bore comprises the following steps. A
CA 0224~032 1998-08-14 hardenable epoxy sealing composition of this invention is prepared which hardens into a resilient solid mass having high bond strength. The epoxy composition is basically comprised of an epoxy res~n cr an epoxide containing liquid, or both, of the types described above, an organosilane compound of the type described above and at least one hardening agent of the type described above. After the epoxy composition has been prepared, it is placed in the annulus between a string of pipe and the walls of a well bore and the epoxy composition is allowed to harden therein. The epoxy composition also preferably includes a particulate filler of the type described above.
In order ~o further illustrate the methods and epoxy compositions of thiq invention, the following examples are given.
An epoxide containing liquid comprised of diglycidyl ether of cyclohexane dimethanol and an epoxide resin comprised of the condensation product of epichlorohydrin and bisphenol A
mixed with an aromatic solvent were tested individually and in 50~ mixtures with each other. The epoxides were mixed with an organosilane, i e., N-2-(aminoethyl)-3-aminopropyltrimeth-oxysilane and a hardening agent comprised of- 2-ethyl-4-methyl-imidazole or a mixture of diethyltoluenediamine and tris (dimethylaminoethylphenol). Microsand (powdered crystalline silica) was added to the mixtures, and the mixtures were tested for shear bond strength. Additional identical mixtures were prepared without the organosilane compound, and they were CA 0224~032 1998-08-14 also tested for she~r bond strength.
The apparatus used to determine the shear bond strength included a standard ASTM 2" x 2" x 2" cube mold with a plastic liner and a metal plate to which the epoxide mixtures tested bonded to. A plastic liner was used to prevent the epoxide mixtures from bonding to the sides and bottom of the mold. The metal plate was 2" wide x 3" high x 0.5" thick with smooth surfaced ends at the top and bottom of the 3" height.
The surfaced bottom served as a means to obtain a vertical positioning of the metal plate in the mold during pouring and curing of the epoxy mixture and the surfaced top was used for applying even loading to the plate. The other surfaces of the plate were sand blasted. The plate was placed in the center of the plastic mold and the epoxide mixtures tested were poured on both sides of the plate.
Each epoxide mixture tested was cured in the mold for 72 hours at 140~F. Thereafter, the bonding plate with the cured epoxy mixture bonded thereto was placed in a support apparatus whereby the bottom and sides of the cured epoxy mixture were supported but the area immediately below the bonding plate was not. The support system was then placed between the loading platens of a load press, and a load was applied to the bottom of the support syst:em and the top of the bonding plate. The load (in psi.) at which the bond between the plate surfaces and the epoxide mixture failed, i.e., the shear bond strength was noted.
The quantit:ies of the various components of each epoxide mixture tested and the shear bond strengths determined are set forth in Table I below.
TABLE I
SHEAR BOND STRENGTH TESTS
Sam Ouantities of C , % by weight of Epoxide Liquid, Epoxy Resin or mixtures tbereof. Shear Bond ple Strerlgtb, psi No.
Epoxide'Epoxy~ ResinFirst~Second4Third5 Micro6 Organo'-LiquidDilutef~ withHardeningHardening Hardenmg Sauld Silane Aromatic Soh,ent Agent Agent Agent Compour~
None 100 3 None None 150 0.05 185 2 50 50 3 None None 150 0.05 460 3 100 None None 28 0.3 150 ons 3020 4None 100 3 None None 150 None 81 5 50 50 3 None None 150 None 171 6 100 None None 28 0.3 150 None 258 ' Diglycidyl ether of cyclohexane dlmethar,ol - ~HELOXY~107" from Shell Chemical Co 2 Er ~,, and bisphenol A resin (" EPON~RESIN 828~) diluted with aromatic solvent - ~EPSEALIRE~ from Shell Chemical Co.
3 2~ hyl q ~1 imidazole 4 Di b~ ' ' 5 Tris(!" b~
Hydraulic cement compositions are commonly utilized as sealants in subterranean well construction and repair procedures. F'or example, hydraulic cement compositions are used in primary sealing operations whereby strings of pipe such as casing and liners are sealed in well bores. In performing primary cementing, a hydraulic cement composition is pumped into the annular space between the walls of the well bore and the exter.or surfaces of pipe disposed therein. The cement composition is permitted to set in the annular space thereby forming an annular sheath of hardened substantially impermeable cement therein. The cement sheath supports and positions the pipe in the well bore and bonds the exterior surfaces of the pipe to the walls of the well bore whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented.
CA 0224~032 1998-08-14 When conventional cement compositions are utilized for sealing pipe strings in well bores, they set into brittle solid masses. Consequently, the solid cement often does not have sufficient resiliency to resist loss of pipe and/or formation bond, cracking or shattering as the result of pipe movements caused by expansion, contraction, impacts or shocks.
The bond loss, cracking or shattering of the set cement allows leakage of formation fluids through at least portions of the well bore ky way of the annulus therein which can be highly detrimental.
Hardenable epoxy resin compositions have heretofore been used for sealing pipe strings in well bores which penetrate subterranean zones containing corrosive fluids. For example, waste fluids such as salt water, acidic materials, caustic materials, organic materials, chemical by-product materials and the like are often disposed of by injecting them into disposal wells. ',uch disposal wells penetrate subterranean formations which accept large volumes of waste and are naturally separated from other subterranean formations. When a disposal well or other well where hydrocarbons are produced along with corrosive fluids is completed in the conventional manner whereby a st:ring of steel pipe is cemented in the well bore utilizing a hydraulic cement slurry, both the cement and steel pipe are often subjected to severe corrosion. A result of such corrosion in disposal wells can be that the liquid waste materials leak into and contaminate formations containing useful fluids such as hydrocarbons or potable water. In other wells where hydrocarbons are produced with CA 0224~032 1998-08-14 corrosive fluids, the corrosion can result in leakage of fluids between f'ormations and/or to the surface.
In order to prevent the corrosion of metal pipe strings in disposal and other similar wells, it has heretofore been the practice to seal the pipe strings in well bores with a hardenable epoxy resin composition. Epoxy resin compositions are highly resistant to degradation by acids and other corrosive fluids and their use at least reduces the corrosion of metal pipe strings and the chances that corrosive fluids will find their way to the surface or into other subterranean locations. However, like set cement compositions, hardened epoxy resin comFositions have often lacked sufficient resiliency as well as the necessary bond strength to resist failure as a result of pipe movements.
Thus, there are needs for improved methods and compositions fo:r seali.ng pipe strings in well bores whereby the hardened compositions can withstand the effects of contact with corrosive fluids and also have the resiliency and high bond strength required to withstand pipe movements without failure.
';U~lARY OF THE lNV151.~ lON
The present, invention provides improved methods and epoxy sealing compositiorLs f'or sealing a string of pipe in a well bore whereby upon h,ardening the compositions can withstand the effects of contact with corrosive fluids and pipe movements.
The methods basic3Llly comprise the steps of preparing a hardenable epoxy sealing composition which hardens into a solid mass having resiliency and high pipe and formation CA 0224~032 1998-08-14 surface bond strengths~ placing the epoxy composition into the annulus between the string of pipe and the walls of the well bore and allowing the epoxy composition to harden.
The epoxy -ompositions of this invention which have high resiliencies and high bond strengths are comprised of an epoxy resin or an epoxide containing liquid, or both, an organosilane compound and at least one hardening agent. The epoxy compositions preferably also include a filler such as crystalline silica or the like.
It is, therefore, a general object: of the present invention to provide improved methods and compositions for sealing pipe strings in well bores.
Other and further objects, features and advantages of the present invention will be apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.
DESCRIPTION OF PREFERRED ENBODIMENTS
The present invention provides improved methods and compositions for sealing pipe strings in well bores whereby the hardened sealing compositions can withstand the effects of contact with corrosive fluids as well as pipe movements due to expansion, contrac ion, impacts, shocks or the like. In accordance with the methods, an epoxy composition which hardens into a resilient solid mass having high pipe and formation bond strengths is prepared, placed in the annulus between a pipe or pipe string and the walls of a well bore and allowed to harden therein. The sealant compositions which are useful in accordance with the present invention are epoxy CA 0224~032 1998-08-14 compositions basically comprised of an epoxy resin or an epoxide containing liquid, or both, an organosilane compound and at least one hardening agent.
While various epoxy resins can be utilized, preferred such resins are those selected from the condensation products of epichlorohydrin and bisphenol A. A particularly suitable such resin is commercially available from the Shell Chemical Company under the trade designation "EPON~RESIN 828". This epoxy resin has a molecular weight of about 340 and a one gram equivalent of epoxide per about 180 to about 195 grams of resin. When used, the epoxy resin is generally included in an epoxy composition of this invention in an amount in the range of from about 101; to about 90~ by weight of the epoxy composition, preferably in an amount of about 50~.
A solvent or a low viscosity epoxide containing liquid or a mixture of such epoxide containing liquids can be utilized to modify the visc09ity of the epoxy resin used and to add flexibility and resiliency to the epoxy composition after hardening. An epichlorohydrin/bisphenol A condensation epoxy resin which has been modified with an aromatic solvent is commercially available from the Shell Chemical Company under the trade designati~n "EPSEAL RE2".
When an epoxide containing liquid Cl- mixture of such liquids is includecL in an epoxy composition of this invention to modify the viscosity of an epoxy resin therein, the epoxide containing liquid or mixture is generally present in an amount in the range of from about 20~ to about 50~ by weight of the epoxy composition, preferably in an amount of about 27~. An CA 0224~032 1998-08-14 epoxide containing liquid or a mixture of such liquids can also be utilized as the only epoxide source in an epoxy composition of this invention.
While various epoxide containing liquids can be used, preferred such. liquids are the diglycidyl ether of 1,4-butanediol, the diglycidyl ether of neopentyl glycol and the diglycidol ether of cyclohexanedimethanol. A suitable epoxide containing liquid ~omprised of the diglycidyl ether of 1,4-butanediol is commercially available from the Shell Chemical Company under the trade name "HELoXY(967 " . This epoxide containing liquid has a viscosity at 25~C in the range of from about 13 to about 18 centipoises, a molecular weight of 202 and a one gram equ.ivalent of epoxide per about 120 to about 130 grams of the liquid. A suitable di.glycidyl ether of neopentylglycol is commercially available from Shell Chemical Company under the trade name "HELOXY~68 " . This epoxide containing liqui.d has a viscosity at 25~C in the range of from about 13 to about 18 centipoises, a molecular weight of 216 and a one gram equ.iva:lent of epoxide per about 130 to about 140 grams of the liquid. A suitable diglycidyl ether of cyclohexanedimethan~l is commercially available from Shell Chemical Company under the trade name "HELOXY3107". This epoxide containi.ng liquid has a viscosity at 25~C in the range of from about 55 to about 75 centipoises, a molecular weight of 256 and a one gram equivalent of epoxide per about 155 to about 165 grams of the liquid.
When an epoxide containing liquid or mixture is utilized CA 0224~032 1998-08-14 as the only epoxicLe source in an epoxy composition of this invention, the epoxide containing liquid or mixture is generally present in an amount in the range 3f from about 20% to about 801i by weight of the epoxy composition, preferably in an am~unt: of about 50%.
The organosi:Lane compound functions in the epoxy compositions of this invention to impart high metal pipe surface and formation surface bond strengths to the compositions. 'rhe organosilane compound undergoes hydrolysis in the presence of trace quantities of water whereby trialkoxysilanols are formed which dehydrate and form strong bonds to pipe and formation surfaces. That is, the dehydration results in the formation of bonds with silica in the formation and iron oxide on the pipe.
Suitable organosilane compounds include 3-aminopropyltrimethy~xysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-ammopropyltriethoxysilane and 3-glycidoxy-propyltrimethoxysil~ne. Of these, 3-glycidoxypropyltri-methoxysilane is preferred. The organosilane compound is included in an epoxy composition of this invention in an amount in the range of from about 0.1~ to about 5% by weight of the epoxy composition, preferably in an amount of about 0.5%.
A variety of hardening agents including, but not limited to, aliphatic arnines, amide amines, amido amines, imidazoles, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, polyamides, polyethylamines and carboxylic acid anhydrides can be utilized in the compositions CA 0224~032 1998-08-14 of this invention containing the above described epoxy resins and/or epoxide containing liquids. Of these, aliphatic amines, aromatic amines and carboxylic acid anhydrides are the most suitable.
Examples of aliphatic and aromatic amine hardening agents are triethylenetetraamine, ethylenediamine, N-cocoalkyltri-methylenediamine, isophoronediamine, diethyltoluenediamine, and tris(dimethylaminomethylphenol). Examples of suitable carboxylic acid anhydrides are methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride and phthalic anhydride. Of these, triethylenetetraamine, ethylenediamine, N-cocoalkyltri-methylenediamine, isophoronediamine, diethyltoluenediamine and tris(dimethylaminom~thylphenol) are preferred, with isophoronediamine, diethyletoluenediamine and tris(dimethylaminomethylphenol) being the most preferred. The hardening agent or agents utilized are included in the epoxy compositions of the present invention in an amount in the range of from about 20~ to about 50~ by weight of the composlt lons .
As mentioned above, the epoxy compositions preferably also include a particulate filler such as crystalline silicas, amorphous silicas, clays, calcium carbonate or barite. When such a filler is utilized, it is added to an epoxy composition of this invention in an amount in the range of from about 100 to about 300~ by weight of the composition.
A preferred method of this invention for sealing a string of pipe in a well bore comprises the following steps. A
CA 0224~032 1998-08-14 hardenable epoxy sealing composition of this invention is prepared which hardens into a resilient solid mass having high bond strength. The epoxy composition is basically comprised of an epoxy res~n cr an epoxide containing liquid, or both, of the types described above, an organosilane compound of the type described above and at least one hardening agent of the type described above. After the epoxy composition has been prepared, it is placed in the annulus between a string of pipe and the walls of a well bore and the epoxy composition is allowed to harden therein. The epoxy composition also preferably includes a particulate filler of the type described above.
In order ~o further illustrate the methods and epoxy compositions of thiq invention, the following examples are given.
An epoxide containing liquid comprised of diglycidyl ether of cyclohexane dimethanol and an epoxide resin comprised of the condensation product of epichlorohydrin and bisphenol A
mixed with an aromatic solvent were tested individually and in 50~ mixtures with each other. The epoxides were mixed with an organosilane, i e., N-2-(aminoethyl)-3-aminopropyltrimeth-oxysilane and a hardening agent comprised of- 2-ethyl-4-methyl-imidazole or a mixture of diethyltoluenediamine and tris (dimethylaminoethylphenol). Microsand (powdered crystalline silica) was added to the mixtures, and the mixtures were tested for shear bond strength. Additional identical mixtures were prepared without the organosilane compound, and they were CA 0224~032 1998-08-14 also tested for she~r bond strength.
The apparatus used to determine the shear bond strength included a standard ASTM 2" x 2" x 2" cube mold with a plastic liner and a metal plate to which the epoxide mixtures tested bonded to. A plastic liner was used to prevent the epoxide mixtures from bonding to the sides and bottom of the mold. The metal plate was 2" wide x 3" high x 0.5" thick with smooth surfaced ends at the top and bottom of the 3" height.
The surfaced bottom served as a means to obtain a vertical positioning of the metal plate in the mold during pouring and curing of the epoxy mixture and the surfaced top was used for applying even loading to the plate. The other surfaces of the plate were sand blasted. The plate was placed in the center of the plastic mold and the epoxide mixtures tested were poured on both sides of the plate.
Each epoxide mixture tested was cured in the mold for 72 hours at 140~F. Thereafter, the bonding plate with the cured epoxy mixture bonded thereto was placed in a support apparatus whereby the bottom and sides of the cured epoxy mixture were supported but the area immediately below the bonding plate was not. The support system was then placed between the loading platens of a load press, and a load was applied to the bottom of the support syst:em and the top of the bonding plate. The load (in psi.) at which the bond between the plate surfaces and the epoxide mixture failed, i.e., the shear bond strength was noted.
The quantit:ies of the various components of each epoxide mixture tested and the shear bond strengths determined are set forth in Table I below.
TABLE I
SHEAR BOND STRENGTH TESTS
Sam Ouantities of C , % by weight of Epoxide Liquid, Epoxy Resin or mixtures tbereof. Shear Bond ple Strerlgtb, psi No.
Epoxide'Epoxy~ ResinFirst~Second4Third5 Micro6 Organo'-LiquidDilutef~ withHardeningHardening Hardenmg Sauld Silane Aromatic Soh,ent Agent Agent Agent Compour~
None 100 3 None None 150 0.05 185 2 50 50 3 None None 150 0.05 460 3 100 None None 28 0.3 150 ons 3020 4None 100 3 None None 150 None 81 5 50 50 3 None None 150 None 171 6 100 None None 28 0.3 150 None 258 ' Diglycidyl ether of cyclohexane dlmethar,ol - ~HELOXY~107" from Shell Chemical Co 2 Er ~,, and bisphenol A resin (" EPON~RESIN 828~) diluted with aromatic solvent - ~EPSEALIRE~ from Shell Chemical Co.
3 2~ hyl q ~1 imidazole 4 Di b~ ' ' 5 Tris(!" b~
6 Powdered crystalline silica 7 N-2-(: ,1)-3 , U,U~
From Table I it can be seen that the presence of the organosilane compound in the epoxide mixtures substantially increased the shear bond strengths of the mixtures.
Additional epoxide mixtures of the type described above were prepared except that the hardening agent utilized was a mixture of diethyltoluenediamine and tris(dimethylaminoethyl-phenol). Also, two different organosilane compounds were utilized which were compared to each other a:nd to identical epoxy mixtures with~ut a silane compound. T:he results of these tests are set forth in Table II below.
COMPRES'ilVE STRENGTH AND SHEAR BOND STRENGTH TESTS
Ouantities of C~ , % by Weight of Epoxide Liquid, Epoxy Resin or Mixture r. c~ ShearBond Thereof. Strength, Sample Strength, psi No. psi Epoxide' Epoxy7 I irst Second4 Micro5 FirsP Second7 Liquid Resin }larden Harden- San~lOrgano- Organo Diluted -ing ing Silane Silane With Agent Agent Compound Compouml Aro-matic Solvent 100None 28 2.5 150 0.5 None20,900 1294 2 80 20 28 2.5 150 0.5 None18,780 628 3 60 40 28 2.5 150 0.5 Nooe14,410 288 4 100None 28 2.5 150 I None22,900 1315 80 20 28 2.5 150 I None21,900 583 6 60 40 28 2.5 150 I None17,280 476 7 100None 28 2.5 150None 0.522,400 963 8 80 20 28 2.5 150None 0.520,100 538 9 60 40 28 2.. 5 150 None 0.5 15,770 362 100None 28 2 5 150None None17,620 759 11 80 20 28 2.5 150None None16,940 566 12 60 40 28 2.. 5 150 None Nore 14,450 408 ' Diglycidyl ether of c~, ' ' dlmethawl - ~HELOXY~107" from Shell Chemical Co.
2 ~JiL,IllUlUllJ.' ~ and bispnewl A resin ("EPON~RESIN 828~) diluted with aromatic solvent - "Y,PSEAL~RE~ from Shell Chemical Co.
3D; ~'' " .
4 Tris(!' 'l;' ' ~1~.1~1).
5 Powdered crystalline silica.
3 ~ .,ulw~ u~ ilnlu 7 3 ~,~ .. .. ~ ., CA 0224~032 1998-08-14 From Table lI it can be seen that t:he presence of an organosilane compound in the epoxide mixtures substantially increased both the compressive strengths and shear bond strengths of the ha:rdened mixtures.
Thus, the precent invention is well adapted to carry out the objects and attain the features and ad.vantages mentioned as well as those which are inherent therein. While numerous changes may be made. by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended cla:ims.
From Table I it can be seen that the presence of the organosilane compound in the epoxide mixtures substantially increased the shear bond strengths of the mixtures.
Additional epoxide mixtures of the type described above were prepared except that the hardening agent utilized was a mixture of diethyltoluenediamine and tris(dimethylaminoethyl-phenol). Also, two different organosilane compounds were utilized which were compared to each other a:nd to identical epoxy mixtures with~ut a silane compound. T:he results of these tests are set forth in Table II below.
COMPRES'ilVE STRENGTH AND SHEAR BOND STRENGTH TESTS
Ouantities of C~ , % by Weight of Epoxide Liquid, Epoxy Resin or Mixture r. c~ ShearBond Thereof. Strength, Sample Strength, psi No. psi Epoxide' Epoxy7 I irst Second4 Micro5 FirsP Second7 Liquid Resin }larden Harden- San~lOrgano- Organo Diluted -ing ing Silane Silane With Agent Agent Compound Compouml Aro-matic Solvent 100None 28 2.5 150 0.5 None20,900 1294 2 80 20 28 2.5 150 0.5 None18,780 628 3 60 40 28 2.5 150 0.5 Nooe14,410 288 4 100None 28 2.5 150 I None22,900 1315 80 20 28 2.5 150 I None21,900 583 6 60 40 28 2.5 150 I None17,280 476 7 100None 28 2.5 150None 0.522,400 963 8 80 20 28 2.5 150None 0.520,100 538 9 60 40 28 2.. 5 150 None 0.5 15,770 362 100None 28 2 5 150None None17,620 759 11 80 20 28 2.5 150None None16,940 566 12 60 40 28 2.. 5 150 None Nore 14,450 408 ' Diglycidyl ether of c~, ' ' dlmethawl - ~HELOXY~107" from Shell Chemical Co.
2 ~JiL,IllUlUllJ.' ~ and bispnewl A resin ("EPON~RESIN 828~) diluted with aromatic solvent - "Y,PSEAL~RE~ from Shell Chemical Co.
3D; ~'' " .
4 Tris(!' 'l;' ' ~1~.1~1).
5 Powdered crystalline silica.
3 ~ .,ulw~ u~ ilnlu 7 3 ~,~ .. .. ~ ., CA 0224~032 1998-08-14 From Table lI it can be seen that t:he presence of an organosilane compound in the epoxide mixtures substantially increased both the compressive strengths and shear bond strengths of the ha:rdened mixtures.
Thus, the precent invention is well adapted to carry out the objects and attain the features and ad.vantages mentioned as well as those which are inherent therein. While numerous changes may be made. by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended cla:ims.
Claims (23)
1. An improved method of sealing pipe in a well bore comprising the steps of:
(a) preparing a hardenable epoxy sealing composition which hardens into a resilient solid mass having high bond strength comprising an epoxide containing liquid, an organosilane compound and a hardening agent;
(b) placing said epoxy composition into the annulus between said pipe and the walls of said well bore; and (c) allowing said epoxy composition to harden.
(a) preparing a hardenable epoxy sealing composition which hardens into a resilient solid mass having high bond strength comprising an epoxide containing liquid, an organosilane compound and a hardening agent;
(b) placing said epoxy composition into the annulus between said pipe and the walls of said well bore; and (c) allowing said epoxy composition to harden.
2. The method of claim 1 wherein said epoxide containing liquid is selected from the group of the diglycidyl ether of neopentyl glycol, the diglycidyl ether of cyclohexane-dimethanol and mixtures of such liquids and is present in said composition in an amount in the range of from about 20% to about 80% by weight thereof.
3. The method of claim 1 wherein said organosilane compound is selected from the group of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane and 3-glycidoxy-propyltrimethoxysilane and is present in said composition in an amount in the range of from about 0.1% to about 5% by weight thereof.
4. The method of claim 1 wherein said hardening agent is at least one member selected from the group of aliphatic amines, aromatic amines, amide amines, amido amines, imidazoles and carboxylic acid anhydrides and is present in said composition in an amount in the range of from about 20 to about 50% by weight thereof.
5. The method of claim 1 wherein sa.id hardening agent is at least one member selected from the group of triethylenetetraamine, ethylenediamine, N-cocoalykyltrimethylenediamine, isophoronediamine; diethyltoluenediamine and tris(dimethylaminomethylphenol) and is present in said composition in an amount in the range of from about 20% to about 50% by weight thereof.
6. The method of claim 1 wherein said epoxy composition further comprises a particulate filler.
7. The method of claim 6 wherein said particulate filler is selected from the group consisting of crystalline silicas, amorphous silicas, clays, calcium carbonate and barite and is added to said composition in an amount in the range of from about 100% to about 300% by weight thereof.
8. An improved method of sealing pipe in a well bore whereby the sealant can withstand the effects of contact with corrosive fluids and pipe movements comprising the steps of:
(a) preparing a hardenable epoxy sealing composition which hardens into a resilient solid mass having high bond strength comprising an epoxy resin, an organosilane compound and a hardening agent;
(b) placing said epoxy composition into the annulus between said pipe and the walls of said well bore; and (c) allowing said epoxy composition to harden.
(a) preparing a hardenable epoxy sealing composition which hardens into a resilient solid mass having high bond strength comprising an epoxy resin, an organosilane compound and a hardening agent;
(b) placing said epoxy composition into the annulus between said pipe and the walls of said well bore; and (c) allowing said epoxy composition to harden.
9. The method of claim 8 wherein said epoxy resin is selected from the group of the condensation products of epichlorohydrin and bisphenol A and is present in said composition in an amount in the range of from about 20% to about 50% by we1ght thereof.
10. The method of claim 8 wherein said organosilane compound is selected from the group of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane and is present in said composition in an amount in the range of from about 0.1% to about 5% by weight thereof.
11. The method of claim 8 wherein said hardening agent is at least one member selected from the group of aliphatic amines, aromatic amines, amide amines, amido amines, imidazoles and carboxylic acid anhydrides and is present in said composition in an amount in the range of from about 20% to about 50% by weight thereof.
12. The method of claim 8 wherein said hardening agent is at least one member selected from the group of triethylenetetraamine, ethylenediamine, N-cocoalykyltrimethylenediamine, isophoronediamine, diethyltoluenediamine and tris(dimethylaminomethylphenol) and is present in said composition in an amount in the range of from about 20% to about 50% by weight thereof.
13. The method of claim 8 wherein said epoxy composition further comprises an epoxide containing liquid selected from the group of the diglycidyl ether of 1,4-butanediol, the diglycidyl ether of neopentyl glycol and t:he diglycidyl ether of cyclohexanedimethanol and mixtures of such liquids and is present in said composition in an amount in the range of from about 20% to about 80% by weight thereof.
14. The method of claim 8 wherein said composition further comprises a particulate filler.
15. The method of claim 14 wherein said filler is selected from the group consisting of crystalline silicas, amorphous silicas, clays, calcium carbonate and barite and is added to said composition in an amount in the range of from about 100% to ahout 300% by weight thereof.
16. An improved composition for sealing pipe in a well bore which hardens into a resilient solid mass having high bond strength comprising:
an epoxide containing liquid or mixture of such liquids present in said composition in an amount in the range of from about 20% to about 80% by weight thereof;
an organosilane compound present in said composition in an amount in the range of from about 0.1% to about 5% by weight thereof; and a hardening agent present in said composition in an amount in the range of from about 20% to about 50% by weight thereof.
an epoxide containing liquid or mixture of such liquids present in said composition in an amount in the range of from about 20% to about 80% by weight thereof;
an organosilane compound present in said composition in an amount in the range of from about 0.1% to about 5% by weight thereof; and a hardening agent present in said composition in an amount in the range of from about 20% to about 50% by weight thereof.
17. The method of claim 16 wherein said epoxide containing liquid is selected from the group of the diglycidyl ether of 1,4-butanediol, the diglycidyl ether of neopentyl glycol, the diglycidyl ether of cyclohexanedimethanol and mixtures of such liquids.
18. The method of claim 16 wherein said organosilane compound is selected from the group of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.
19. The method of claim 16 wherein said hardening agent is at least one member selected from the group of aliphatic amines, aromatic amines, amide amines, amido amines, imidazoles and carboxylic acid anhydrides.
20. The method of claim 16 wherein said hardening agent is at least one member selected from the group of triethylenetetraamine, ethylenediamine, N-cocoalykyltrimethylenediamine, isophoronediamine, diethyltoluenediamine and tris(dimethylaminomethylphenol).
21. The method of claim 16 wherein said epoxy composition further comprises a particulate filler.
22. The method of claim 21 wherein said particulate filler is selected from the group consisting of crystalline silicas, amorphous silicas, clays, calcium carbonate and barite and is added to said composition in an amount in the range of from about 100% to about 300% by weight thereof.
23. The method of claim 16 wherein said epoxy composition further comprises an epoxy resin selected from the group of the condensation products of epichlorohydrin and bisphenol A and is present in said composition in an amount in the ranqe of from about 20% to about 50% by weiqht thereof.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/914,594 | 1997-08-18 | ||
| US08/914,594 US5873413A (en) | 1997-08-18 | 1997-08-18 | Methods of modifying subterranean strata properties |
| US09/059,273 US5875845A (en) | 1997-08-18 | 1998-04-13 | Methods and compositions for sealing pipe strings in well bores |
| US09/059,273 | 1998-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2245032A1 true CA2245032A1 (en) | 1999-02-18 |
Family
ID=26738565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002245032A Abandoned CA2245032A1 (en) | 1997-08-18 | 1998-08-14 | Methods and compositions for sealing pipe strings in well bores |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6006836A (en) |
| EP (1) | EP0898050A1 (en) |
| CA (1) | CA2245032A1 (en) |
| NO (1) | NO983752L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10428260B2 (en) | 2014-12-10 | 2019-10-01 | Halliburton Energy Services, Inc. | Curable composition and resin for treatment of a subterranean formation |
Families Citing this family (60)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124246A (en) * | 1997-11-17 | 2000-09-26 | Halliburton Energy Services, Inc. | High temperature epoxy resin compositions, additives and methods |
| US6006835A (en) * | 1998-02-17 | 1999-12-28 | Halliburton Energy Services, Inc. | Methods for sealing subterranean zones using foamed resin |
| US6068055A (en) | 1998-06-30 | 2000-05-30 | Halliburton Energy Services, Inc. | Well sealing compositions and methods |
| US6059035A (en) * | 1998-07-20 | 2000-05-09 | Halliburton Energy Services, Inc. | Subterranean zone sealing methods and compositions |
| US6098711A (en) * | 1998-08-18 | 2000-08-08 | Halliburton Energy Services, Inc. | Compositions and methods for sealing pipe in well bores |
| US6279652B1 (en) | 1998-09-23 | 2001-08-28 | Halliburton Energy Services, Inc. | Heat insulation compositions and methods |
| US6271181B1 (en) | 1999-02-04 | 2001-08-07 | Halliburton Energy Services, Inc. | Sealing subterranean zones |
| US6328106B1 (en) | 1999-02-04 | 2001-12-11 | Halliburton Energy Services, Inc. | Sealing subterranean zones |
| US6244344B1 (en) | 1999-02-09 | 2001-06-12 | Halliburton Energy Services, Inc. | Methods and compositions for cementing pipe strings in well bores |
| US6234251B1 (en) | 1999-02-22 | 2001-05-22 | Halliburton Energy Services, Inc. | Resilient well cement compositions and methods |
| US20030075342A1 (en) * | 2000-04-26 | 2003-04-24 | Bengt Gunnarsson | Packer, setting tool for a packer and method for setting a packer |
| US6454001B1 (en) | 2000-05-12 | 2002-09-24 | Halliburton Energy Services, Inc. | Method and apparatus for plugging wells |
| US6321841B1 (en) | 2001-02-21 | 2001-11-27 | Halliburton Energy Services, Inc. | Methods of sealing pipe strings in disposal wells |
| US6367549B1 (en) | 2001-09-21 | 2002-04-09 | Halliburton Energy Services, Inc. | Methods and ultra-low density sealing compositions for sealing pipe in well bores |
| US6691780B2 (en) | 2002-04-18 | 2004-02-17 | Halliburton Energy Services, Inc. | Tracking of particulate flowback in subterranean wells |
| US6951250B2 (en) * | 2003-05-13 | 2005-10-04 | Halliburton Energy Services, Inc. | Sealant compositions and methods of using the same to isolate a subterranean zone from a disposal well |
| US7032667B2 (en) * | 2003-09-10 | 2006-04-25 | Halliburtonn Energy Services, Inc. | Methods for enhancing the consolidation strength of resin coated particulates |
| US20050173116A1 (en) | 2004-02-10 | 2005-08-11 | Nguyen Philip D. | Resin compositions and methods of using resin compositions to control proppant flow-back |
| US7156172B2 (en) | 2004-03-02 | 2007-01-02 | Halliburton Energy Services, Inc. | Method for accelerating oil well construction and production processes and heating device therefor |
| US7211547B2 (en) | 2004-03-03 | 2007-05-01 | Halliburton Energy Services, Inc. | Resin compositions and methods of using such resin compositions in subterranean applications |
| US6978834B1 (en) * | 2004-05-26 | 2005-12-27 | Halliburton Energy Services, Inc. | Foamed and non-foamed cement compositions including silane treated amorphous silica and methods |
| US7299875B2 (en) | 2004-06-08 | 2007-11-27 | Halliburton Energy Services, Inc. | Methods for controlling particulate migration |
| US7757768B2 (en) | 2004-10-08 | 2010-07-20 | Halliburton Energy Services, Inc. | Method and composition for enhancing coverage and displacement of treatment fluids into subterranean formations |
| US7883740B2 (en) | 2004-12-12 | 2011-02-08 | Halliburton Energy Services, Inc. | Low-quality particulates and methods of making and using improved low-quality particulates |
| US8703659B2 (en) * | 2005-01-24 | 2014-04-22 | Halliburton Energy Services, Inc. | Sealant composition comprising a gel system and a reduced amount of cement for a permeable zone downhole |
| US7673686B2 (en) | 2005-03-29 | 2010-03-09 | Halliburton Energy Services, Inc. | Method of stabilizing unconsolidated formation for sand control |
| US7318474B2 (en) | 2005-07-11 | 2008-01-15 | Halliburton Energy Services, Inc. | Methods and compositions for controlling formation fines and reducing proppant flow-back |
| US7776797B2 (en) * | 2006-01-23 | 2010-08-17 | Halliburton Energy Services, Inc. | Lost circulation compositions |
| US8132623B2 (en) | 2006-01-23 | 2012-03-13 | Halliburton Energy Services Inc. | Methods of using lost circulation compositions |
| US7819192B2 (en) | 2006-02-10 | 2010-10-26 | Halliburton Energy Services, Inc. | Consolidating agent emulsions and associated methods |
| US8613320B2 (en) * | 2006-02-10 | 2013-12-24 | Halliburton Energy Services, Inc. | Compositions and applications of resins in treating subterranean formations |
| US7926591B2 (en) | 2006-02-10 | 2011-04-19 | Halliburton Energy Services, Inc. | Aqueous-based emulsified consolidating agents suitable for use in drill-in applications |
| US7665517B2 (en) | 2006-02-15 | 2010-02-23 | Halliburton Energy Services, Inc. | Methods of cleaning sand control screens and gravel packs |
| US20080060811A1 (en) * | 2006-09-13 | 2008-03-13 | Halliburton Energy Services, Inc. | Method to control the physical interface between two or more fluids |
| US7934557B2 (en) | 2007-02-15 | 2011-05-03 | Halliburton Energy Services, Inc. | Methods of completing wells for controlling water and particulate production |
| DK178243B1 (en) | 2008-03-06 | 2015-09-28 | Mærsk Olie Og Gas As | Fremgangsmåde til forsegling af en ringformet åbning i et borehul |
| DK178742B1 (en) | 2008-03-06 | 2016-12-19 | Maersk Olie & Gas | Method and apparatus for injecting one or more treatment fluids down into a borehole |
| DK178489B1 (en) | 2008-03-13 | 2016-04-18 | Maersk Olie & Gas | Tools and methods for sealing openings or leaks in a wellbore |
| FR2940401B1 (en) * | 2008-12-24 | 2011-03-18 | Irsn | ENCLOSURE CLOSED UNDER VACUUM OR UNDER PRESSURE |
| US7762329B1 (en) | 2009-01-27 | 2010-07-27 | Halliburton Energy Services, Inc. | Methods for servicing well bores with hardenable resin compositions |
| WO2013107789A1 (en) | 2012-01-18 | 2013-07-25 | Mærsk Olie Og Gas A/S | Sealing fluid for setting a packer |
| US20130220612A1 (en) * | 2012-02-24 | 2013-08-29 | Halliburton Energy Services, Inc. | Shear Bond Strength of Set Cement |
| CA2954265C (en) | 2014-08-15 | 2019-08-13 | Halliburton Energy Services, Inc. | Naphthol-based epoxy resin additives for use in well cementing |
| WO2016053346A1 (en) * | 2014-10-03 | 2016-04-07 | Halliburton Energy Services, Inc. | Delayed curing silane-based curable resin system |
| US10214988B2 (en) | 2015-08-12 | 2019-02-26 | Csi Technologies Llc | Riserless abandonment operation using sealant and cement |
| EP3350282B1 (en) * | 2015-09-14 | 2020-11-04 | Saudi Arabian Oil Company | Pendant epoxide polymers and methods of treating subterranean formations |
| CA2997423A1 (en) | 2015-09-14 | 2017-03-23 | Saudi Arabian Oil Company | Maleic anhydride polymers and methods of treating subterranean formations |
| WO2018085405A1 (en) | 2016-11-04 | 2018-05-11 | Saudi Arabian Oil Company | Compositions and methods for sealing off flow channels in contact with set cement |
| US10428261B2 (en) | 2017-06-08 | 2019-10-01 | Csi Technologies Llc | Resin composite with overloaded solids for well sealing applications |
| US10378299B2 (en) | 2017-06-08 | 2019-08-13 | Csi Technologies Llc | Method of producing resin composite with required thermal and mechanical properties to form a durable well seal in applications |
| GB2561638B8 (en) * | 2017-11-10 | 2020-03-11 | Total E&P Danmark As | Epoxy compositions for treating a region of a subterranean formation |
| US11168243B2 (en) | 2018-08-30 | 2021-11-09 | Saudi Arabian Oil Company | Cement compositions including epoxy resin systems for preventing fluid migration |
| US11352541B2 (en) | 2018-08-30 | 2022-06-07 | Saudi Arabian Oil Company | Sealing compositions and methods of sealing an annulus of a wellbore |
| US10696888B2 (en) | 2018-08-30 | 2020-06-30 | Saudi Arabian Oil Company | Lost circulation material compositions and methods of isolating a lost circulation zone of a wellbore |
| US11370956B2 (en) | 2019-12-18 | 2022-06-28 | Saudi Arabian Oil Company | Epoxy-based LCM compositions with controlled viscosity and methods of treating a lost circulation zone of a wellbore |
| US11332656B2 (en) | 2019-12-18 | 2022-05-17 | Saudi Arabian Oil Company | LCM composition with controlled viscosity and cure time and methods of treating a lost circulation zone of a wellbore |
| US11193052B2 (en) | 2020-02-25 | 2021-12-07 | Saudi Arabian Oil Company | Sealing compositions and methods of plugging and abandoning of a wellbore |
| US11236263B2 (en) | 2020-02-26 | 2022-02-01 | Saudi Arabian Oil Company | Method of sand consolidation in petroleum reservoirs |
| US11827841B2 (en) | 2021-12-23 | 2023-11-28 | Saudi Arabian Oil Company | Methods of treating lost circulation zones |
| US11661815B1 (en) | 2022-06-06 | 2023-05-30 | Halliburton Energy Services, Inc. | Resins for repair of well integrity issues |
Family Cites Families (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2815079A (en) * | 1954-06-29 | 1957-12-03 | Gulf Oil Corp | Method of and composition for recovering circulation of drilling fluids in wells |
| US3082823A (en) * | 1960-03-31 | 1963-03-26 | Halliburton Co | Composition and method for sealing porous formations |
| FR1315462A (en) * | 1962-02-19 | 1963-01-18 | Shell Int Research | Method of consolidating an unconsolidated or substantially unconsolidated mass |
| US3208525A (en) * | 1962-06-25 | 1965-09-28 | Exxon Production Research Co | Recompletion of wells |
| US3310111A (en) * | 1964-02-17 | 1967-03-21 | Dow Chemical Co | Method of controlling solids in fluids from wells |
| GB1019122A (en) * | 1964-03-26 | 1966-02-02 | Shell Int Research | Method for treating a permeable mass |
| US3416604A (en) * | 1967-03-20 | 1968-12-17 | Hailiburton Company | Epoxy resin grouting fluid and method for stabilizing earth formations |
| US3467208A (en) * | 1968-03-29 | 1969-09-16 | Mobil Oil Corp | Lost circulation control |
| US3750768A (en) * | 1972-01-27 | 1973-08-07 | Shell Oil Co | Oil base drilling fluid filtrate-effected sand consolidation |
| US3782466A (en) * | 1972-07-19 | 1974-01-01 | Shell Oil Co | Bonding casing with syntactic epoxy resin |
| US3976135A (en) * | 1972-10-02 | 1976-08-24 | Halliburton Company | Method of forming a highly permeable solid mass in a subterranean formation |
| US4042032A (en) * | 1973-06-07 | 1977-08-16 | Halliburton Company | Methods of consolidating incompetent subterranean formations using aqueous treating solutions |
| US3960801A (en) * | 1973-06-18 | 1976-06-01 | Halliburton Company | Pumpable epoxy resin composition |
| US4072194A (en) * | 1973-06-18 | 1978-02-07 | Halliburton Company | Pumpable epoxy resin composition |
| US3933204A (en) * | 1974-10-15 | 1976-01-20 | Shell Oil Company | Plugging subterranean regions with acrylic-epoxy resin-forming emulsions |
| US4042031A (en) * | 1975-11-13 | 1977-08-16 | Shell Oil Company | Plugging subterranean earth formations with aqueous epoxy emulsions containing fine solid particles |
| US4074760A (en) * | 1976-11-01 | 1978-02-21 | The Dow Chemical Company | Method for forming a consolidated gravel pack |
| GB1550713A (en) * | 1977-05-30 | 1979-08-15 | Shell Int Research | Method of treating an underground formation around a borehole |
| US4220566A (en) * | 1978-03-21 | 1980-09-02 | The Dow Chemical Company | Aqueous based slurry containing enediol breaker and method for forming a consolidated gravel pack |
| US4272384A (en) * | 1978-07-07 | 1981-06-09 | The Dow Chemical Company | Composition for preventing a resin system from setting up in a well bore |
| US4215001A (en) * | 1978-10-20 | 1980-07-29 | Halliburton Company | Methods of treating subterranean well formations |
| US4339000A (en) * | 1980-08-28 | 1982-07-13 | Cronmiller Clifford P | Method and apparatus for a bridge plug anchor assembly for a subsurface well |
| US4336842A (en) * | 1981-01-05 | 1982-06-29 | Graham John W | Method of treating wells using resin-coated particles |
| US4483888A (en) * | 1981-09-01 | 1984-11-20 | Phillips Petroleum Company | Carbon dioxide treatment of epoxy resin compositions |
| US4489785A (en) * | 1983-07-19 | 1984-12-25 | Halliburton Company | Method of completing a well bore penetrating a subterranean formation |
| US4665988A (en) * | 1986-04-04 | 1987-05-19 | Halliburton Company | Method of preparation of variable permeability fill material for use in subterranean formations |
| US4785884A (en) * | 1986-05-23 | 1988-11-22 | Acme Resin Corporation | Consolidation of partially cured resin coated particulate material |
| US4741401A (en) * | 1987-01-16 | 1988-05-03 | The Dow Chemical Company | Method for treating subterranean formations |
| US4921047A (en) * | 1989-08-10 | 1990-05-01 | Conoco Inc. | Composition and method for sealing permeable subterranean formations |
| NO171308C (en) * | 1989-08-21 | 1993-02-24 | Borregaard Ind | APPLICATION OF COPOLYMERS AS ADDITIVE FOR CEMENT MORTAL MIXTURES, CEMENT MORTAL MIXTURES, AND COPOLYMER DISPERSION |
| US4972906A (en) * | 1989-09-07 | 1990-11-27 | Conoco Inc. | Method for selective plugging of a zone in a well |
| US5090478A (en) * | 1990-11-30 | 1992-02-25 | Conoco Inc. | Method for reducing water production from a gravel packed well |
| US5133409A (en) * | 1990-12-12 | 1992-07-28 | Halliburton Company | Foamed well cementing compositions and methods |
| US5159980A (en) * | 1991-06-27 | 1992-11-03 | Halliburton Company | Well completion and remedial methods utilizing rubber latex compositions |
| US5168928A (en) * | 1991-08-15 | 1992-12-08 | Halliburton Company | Preparation and use of gelable silicate solutions in oil field applications |
| US5211234A (en) * | 1992-01-30 | 1993-05-18 | Halliburton Company | Horizontal well completion methods |
| US5213161A (en) * | 1992-02-19 | 1993-05-25 | Halliburton Company | Well cementing method using acid removable low density well cement compositions |
| US5428178A (en) * | 1992-10-13 | 1995-06-27 | Shell Oil Company | Polyethercyclipolyols from epihalohydrins, polyhydric alcohols, and metal hydroxides or epoxy alcohols and optionally polyhydric alcohols with thermal condensation |
| NO176878C (en) * | 1992-11-20 | 1995-06-14 | Sinvent As | Cementing material with regulated curing time, for use in deep, hot oil wells |
| US5325723A (en) * | 1992-12-04 | 1994-07-05 | Halliburton Company | Core sample test method and apparatus |
| US5377757A (en) * | 1992-12-22 | 1995-01-03 | Mobil Oil Corporation | Low temperature epoxy system for through tubing squeeze in profile modification, remedial cementing, and casing repair |
| US5404950A (en) * | 1992-12-22 | 1995-04-11 | Mobil Oil Corporation | Low temperature underwater epoxy system for zone isolation, remedial cementing, and casing repair |
| US5314023A (en) * | 1993-01-19 | 1994-05-24 | Dartez Terry R | Method for selectively treating wells with a low viscosity epoxy resin-forming composition |
| US5358044A (en) * | 1993-05-27 | 1994-10-25 | Shell Oil Company | Drilling and cementing with blast furnace slag/soluble/insoluble alcohol |
| US5361841A (en) * | 1993-05-27 | 1994-11-08 | Shell Oil Company | Drilling and cementing with blast furnace slag/polyalcohol fluid |
| US5361842A (en) * | 1993-05-27 | 1994-11-08 | Shell Oil Company | Drilling and cementing with blast furnace slag/silicate fluid |
| US5337824A (en) * | 1993-06-28 | 1994-08-16 | Shell Oil Company | Coal slag universal fluid |
| US5373901A (en) * | 1993-07-27 | 1994-12-20 | Halliburton Company | Encapsulated breakers and method for use in treating subterranean formations |
| US5368102A (en) * | 1993-09-09 | 1994-11-29 | Halliburton Company | Consolidatable particulate material and well treatment method |
| US5335726A (en) * | 1993-10-22 | 1994-08-09 | Halliburton Company | Water control |
| US5358051A (en) * | 1993-10-22 | 1994-10-25 | Halliburton Company | Method of water control with hydroxy unsaturated carbonyls |
| US5559086A (en) * | 1993-12-13 | 1996-09-24 | Halliburton Company | Epoxy resin composition and well treatment method |
| US5547027A (en) * | 1994-07-14 | 1996-08-20 | Dowell, A Division Of Schlumberger Technology Corporation | Low temperature, low rheology synthetic cement |
| US5458195A (en) * | 1994-09-28 | 1995-10-17 | Halliburton Company | Cementitious compositions and methods |
| US5711383A (en) * | 1996-04-19 | 1998-01-27 | Halliburton Company | Cementitious well drilling fluids and methods |
| US5873413A (en) * | 1997-08-18 | 1999-02-23 | Halliburton Energy Services, Inc. | Methods of modifying subterranean strata properties |
-
1998
- 1998-05-29 US US09/087,405 patent/US6006836A/en not_active Expired - Lifetime
- 1998-08-14 CA CA002245032A patent/CA2245032A1/en not_active Abandoned
- 1998-08-17 NO NO983752A patent/NO983752L/en not_active Application Discontinuation
- 1998-08-18 EP EP98306573A patent/EP0898050A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10428260B2 (en) | 2014-12-10 | 2019-10-01 | Halliburton Energy Services, Inc. | Curable composition and resin for treatment of a subterranean formation |
| US11268008B2 (en) | 2014-12-10 | 2022-03-08 | Halliburton Energy Services, Inc. | Curable composition and resin for treatment of a subterranean formation |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0898050A1 (en) | 1999-02-24 |
| US6006836A (en) | 1999-12-28 |
| NO983752D0 (en) | 1998-08-17 |
| NO983752L (en) | 1999-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5875845A (en) | Methods and compositions for sealing pipe strings in well bores | |
| CA2245032A1 (en) | Methods and compositions for sealing pipe strings in well bores | |
| US6321841B1 (en) | Methods of sealing pipe strings in disposal wells | |
| US6098711A (en) | Compositions and methods for sealing pipe in well bores | |
| US6006835A (en) | Methods for sealing subterranean zones using foamed resin | |
| US6330917B2 (en) | Resilient well cement compositions and methods | |
| US6367549B1 (en) | Methods and ultra-low density sealing compositions for sealing pipe in well bores | |
| US3854533A (en) | Method for forming a consolidated gravel pack in a subterranean formation | |
| KR20210050553A (en) | Cement composition comprising an epoxy resin system to prevent fluid movement | |
| EP0903461A1 (en) | Methods of sealing plugs in well bores | |
| KR20210052509A (en) | Sealing composition and method for sealing annular portion of well bore | |
| US6702021B1 (en) | Methods and drilling fluids for drilling well bores and sealing pipe strings therein | |
| EP0899415A1 (en) | Method of sealing pipe string in well bores | |
| CA2245033A1 (en) | Remedial well bore sealing methods | |
| EP0899416A1 (en) | Method of sealing conduits in lateral well bores | |
| WO2021173430A1 (en) | Sealing compositions and methods of plugging and abandoning of a wellbore | |
| US3878893A (en) | Method for forming a consolidated gravel pack in a well borehole | |
| EP0899317A1 (en) | Well drilling fluid | |
| US20040262003A1 (en) | Methods and compositions for sealing pipe and forming barriers in well bores | |
| EP0899418A1 (en) | Modifying subterranean strata |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |