CA2093505A1 - Invert emulsions for well drilling comprising polydiorganosiloxanes - Google Patents
Invert emulsions for well drilling comprising polydiorganosiloxanesInfo
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Abstract
INVERT EMULSIONS FOR WELL DRILLING
COMPRISING POLYDIORGANOSILOXANES
ABSTRACT
This disclosure deals with a novel combination which is a composition of matter which is useful for well drilling operations and maintenance. The combination comprises an emulsifier composition comprising a solid, benzene-soluble organopolysiloxane resin copolymer; a hydrolytically stable compound having at least two organo-polysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical; a polydiorgano-siloxane-polyoxyalkylene copolymer having at least one long chain alkyl group and at least one polyoxyalkylene group on the same molecule; and, a polysiloxane-polyoxyalkylene copolymer surfactant. Also disclosed are invert emulsions made with brine, hydrocarbon and the emulsifier combination and methods of making them.
COMPRISING POLYDIORGANOSILOXANES
ABSTRACT
This disclosure deals with a novel combination which is a composition of matter which is useful for well drilling operations and maintenance. The combination comprises an emulsifier composition comprising a solid, benzene-soluble organopolysiloxane resin copolymer; a hydrolytically stable compound having at least two organo-polysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical; a polydiorgano-siloxane-polyoxyalkylene copolymer having at least one long chain alkyl group and at least one polyoxyalkylene group on the same molecule; and, a polysiloxane-polyoxyalkylene copolymer surfactant. Also disclosed are invert emulsions made with brine, hydrocarbon and the emulsifier combination and methods of making them.
Description
~ l ~ 3 ~ j INYERT EMULSIONS FOR WELL DRILLING
COMPRISING POLYDIORGANOSILOXANES
The present invention relates to emulsifier compositions for the well drilling industry. The present invention also relates to compositions comprising emulsions of brines in liquid hydrocarbons which are useful in well drilling operations, such as in gas and/or oil well drilling, as a drilling fluid, a completion fluid, a workover fluid, a casing pack fluid, a fracturing fluid, a packer fluid or a spacer fluid.
Invert emulsions, in the form of drilling muds, completion fluids and packer fluids are well known in the well drilling art. Invert emulsions typically consist of a fluid phase comprising from 15 to 45 percent by volume of a CaC12 brine and 55 to 85 percent by volume of diesel oil and a solid phase comprising agents for pressure control, filtration control, viscosity control, gelling, etc. An invert emulsion drilling mud generally contains from 5 to 30 percent by volume of the brine.
While conventional invert emulsions are used in drilling deep wells, where high temperature and pressure are commonly encountered, they are not completely satisfactory for such a use. For example, invert emulsions are sometimes not sufficiently stable at the high temperatures encountered in deep wells. Furthermore, the use of excessive amounts of a weighting agent in an invert emulsion to achieve pressure control in deep wells is often undesirable because performance and properties of the emulsion can be adversely affected. Heavier brines, such as CaBr2 brines and/or ZnBr2 brines, have been used to increase the density of the invert emulsions, thereby achieving greater pressure control;
,3 ~ ~
however, sometimes the thermal stahility of these heavier emulsions is marginal or non-existent. FurthPr improvements in temperature stability of the invert emulsion are needed.
It is an ob~ect of this invention to provide an emulsifier composition comprising: (I) a viscosifier composition selected from the groups consisting e~sentially of (A) ~ (B), (A) + (C) and (A) + (B) + (C) and (II) a surfactant (D), wherein (A) is a solid, benzene-soluble organopolysiloxane resin copolymer; (B) is a hydrolytically stable compound having at least two organopolysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical; (C) is a polydiorgansiloxane-polyoxyalkylene selected from the group consisting of copolymers having the following formula:
a- Z3SiO{(CH3)2SiO}x~(CH3)(R)SiO}y~(CH3)(Q)SiO}zSiZ3 and b- Z3sio{(cH3)(R)sio}y~(cH3)(Q)sio}zsiz3~
wherein Q denotes a polyoxyalkylene radical having the formula -R' (OCH2CH2)p(0CH2CHCH3)qOR" ~nd (D) is a polysiloxane-polyoxyalkylene copolymer surfactant selected from the group consisting of copolymers having the general formula:
a R (CH3)2SiO{(CH3)2SiO}x,{(CH3)(Q )SiO}z~Si(CH3)2R
and b R (CH3)2SiO~(CH3)(Q )SiO}z,Si(CH3)2~
wherein Q' denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p,(0CH2CHCH3)q,0R .
It is another object of this invention to provide a solids-free invert emulsion which is suitable for use in the well drilling industry utilizing the emulsifier compositions described above.
It is yet another ob~ect of this invention to provide invert emulsions of a high density brine which have stability at higher temperatures. It is still a further ~ ~ ~3 3 . ~ ~3 ob~ect of this invention to provide improved invert emulsion muds. Further, it i9 another ob~ect of this invention to provide solids-free invert emul~ions having high den.sity and being suitable for use in the deep well drilling industry.
It is also an ob~ect of this invention to provide a method for preparing the invert emulsions of this invention. It is yet another ob~ect of this invention to provide an emulsion concentrate which is useful for preparing improved invert emulsions.
These ob~ects and others will become obvious when considering the following disclosure and appended claims.
According to this invention, it is possible not only to prepare a highly thermally stable emulsion of a high density brine but also to prepare a stable emulsion comprising a fluid phase having a ma~or amount of a high density brine and a minor amount of a liquid hydrocarbon.
The resulting invert emulsions are sufficiently dense to permit their use as solids-free oil well fluids in deep well drilling. They can also be formulated to contain solid and/or liquid components which are commonly used in the well drilling art for various purposes, such as for preparing invert emulsion drilling muds.
The present invention relates to emulsifier combinations comprising a blend of (I) viscosifiers, which themselves are a blend of certain solid resinous siloxanes and an alkyl/polyoxyalkylene containing material, or, a solid resinous siloxane and a crosslinked alkyl/polyoxyalkylene containing material, or, a blend of a solid resinous siloxane and a combination of an alkyl/polyoxyalkylene containing material and its crosslinked counterpart and (II), a surface active agent.
The present invention also relates to an emulsion composition to be used in well drilling and comprising (i) ~3~
from 1 to 75 parts by volume of a brine as a discontinuou~
phase, (ii) from 25 to 95 parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100F. as a continuous phase and (iii) from 0.05 to 15 parts by weight, for every 100 parts by weight of brine plus liquid hydrocarbon, of the the emulsifier combination.
The present invention further relates to a method for preparing the emulsion compositions of this invention.
With specificity, this invention deals with emulsifier compositions comprising (~) a vi~cosifier composition selected from the groups consisting essentially of (A) + (~), (A) ~ (C) and (A) + (B) I (C) and (II) a surfactant (D), wherein (A) is a solid, benzene-soluble organopoly-siloxane resin copolymer consisting essentially of (CH3)3SiOl/2 siloxane units and SiO4/2 siloxane unit, there being from 0.6 to 0.9, inclusive, of said (CH3)3SiOl/2 siloxane units for every SiO4/2;
(B) is a hydrolytically stable compound having at least two organopolysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical;
(C) is a polydiorganosiloxane-polyoxyalkylene selected from the group consisting of copolymers having the following formula:
a- Z3sio{(cH3)2sio}x{(cH3)(R)sio}yl(cH3)(Q)sio}zsiz3 and b- Z3sio{(~H3)(R)sio}y{(cH3)(Q)sio}zsiz3~
wherein Q denotes a polyoxyalkylene radical having the formula ~R~(OCHzCH2)p(0CH2CHCH3)qOR~ wherein R denotes a monovalent hydrocarbon radical having from 6 to 18 carbon atoms, inclusive, R' denotes a divalent radical bonded to a 3~
silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals; Z denotes a monovalent hydrocarbon radical having from 1 to 5 carbon atoms, inclusive or an R radical or a Q
radical; x has an average value of from 1 to 400, y has an average value of from 1 to 400, z has an average value of from 1 to 5, x+y+z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p+q has an average value sufficient to provide a formula weight of from 600 to 3500 for the ~(OCH2CH2)p(0CH2CHCH3)q~ portion of the Q radical, there being an average of at leas~ one Q radical and an average of at least one R radical per molecule and, (D) is a polysiloxane-polyoxyalkylene copolymer surfactant selected from the group consisting of copolymers having the general formula:
a R (CH3)2SiO{(CH3)2SiO}x,~(CH3)(Q )SiO}z,Si(CH3)2R
and b' R''''(CH3)2SiO~(CH3)(Q')SiO}z,Si(CH3)2R
wherein Q' denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p,(0CH2CHCH3)q,OR", wherein R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, R"" den.otes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, inclusive or a Q' radical, x' has an average value of from 1 to 100, z' has an average value of from 1 to 10, x'+ z' has an average value of from 8 to 100, p' has an average value equal to or greater than the average value of q' and p'+ q' hac an average value sufficient to provide a formula weight of from 300 to 3500 for the ~(OCH2CH2)p,(0CH2CHCH3)q,~
-6- ~ ) tj portion of the Q' radical, there being an average of at least one Q' radical per molecule of the polydiorganosiloxane, wherein the ratio of (A) to (B) in (A) + (B), the ratio of (A) to (C) in (A) ~ (C) and the ratio of (A) to (B) + (C) in (A) + (B) + (C) is in the range of 15:85 to 35065 and the amount of (D) present in the composition is from 5 to 70 weight percent based on the weight of (I) and (II). For purposes of this invention, component (D) must be water soluble and the statement "...p' has an average value equal to or greater than the average value of q'..." satisfies that requirement.
The present invention further relates to a method for preparing the emulsion compositions of this invention comprising (I) mixing to form a solution, (i) 0.5 to 15 parts by weight of an emulsifier composition of this invention (ii) aV parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100F., (II) mixing the solution of step (I) with bV parts by volume of the liquid hydrocarbon, (III) mixing V' parts by volume of a brine with the solution of step (II) with sufficient shear energy to provide an emulsion having a brine particle size of less than 10 micrometers in diameter and (IV) mixing the emulsion of step (III) with cV parts by volume of liquid hydrocarbon, wherein V has an average of from 25 to 99 pa.rts by volume, a has a value of from greater than zero to 1, b has a value of from zero to less than 1, c has a value of from zero to less than 1, a+b+c has a value of 1, V' has a value of from 1 to 75 parts by volume and the weight of V + V' has a value of 100 parts by weight.
The present invention further relates to a concentrate comprising from 0.5 to 15 parts by weight of an -7~ 3 i ~3 ~
emulsifier composition of this invention and a portion of the liquid hydrocarbon equal to from 0.0001 to 0.1 of the total amount of liquid hydrocarbon component that is used to prepare the emulsion compositions of this invention.
The discontinuous phase of the emulsion compositions of this invention is a brine. Herein, the term brine is used in its broadest sense, i.e. an aqueous solution of a salt containing at least 3 percent by weight of the salt. Preferably the brine is a saturated aqueous solution of the salt at 20C. The term brine further includes brine occurring naturally or brine prepared synthetically. It is within the scope and spirit of this invention to dissolve one or more salts in natural brine to prepare a brine suitable for use in the compositions of this invention.
The salt portion of the brine preferably has a high solubility in water at room temperature so that the emulsion compositions of this invention can be formulated to have a wide range of densities. The salt advantageously has, in addition to a high solubility in water, a large formula weight so that the brine can be formulated to have a high density, for example, up to 22 pounds per gallon (2642 kilograms per cubic meter).
Salts typically used in the well drilling art and being suitable for use in the compositions of this invention include sodium chloride, sodium carbonate, potassium chloride, potassium carbonate, calcium chloride, calcium bromide, zinc chloride, zinc bromide and mixtures thereof.
Conveniently, a suitable brine for the composition of this invention can be the natural brine that is frequently present at the drilling site where these compositions are u~ed. In this case the present invention contemplates the storing of the other components of these compositions hereinafter delineated, at the drilling site as separate -8- ~ v ,' and/or mixed components and formulating the emulsions of this invention in the field, as desired. Said natural brine can be further mixed with a salt, if desired.
A preferred brine in the emulsion compositions of this invention comprise water saturated with a mixture of calcium bromide and zinc bromide and having a density of about 20 pounds per gallon at 20C. Such a brine can be emulsified in a liquid hydrocarbon according to this invention to provide an emulsion that needs no additional weighting agent, such as barium sulfate, to permit its use as a fluid in petroleum and/or gas well drillings. Said emulsions can also be readily formulated with well-known additives to provide improved drilling muds which are useful in well drilling operations, such as in gas and/or oil well drilling, as a drilling fluid, a completion fluid, a workover fluid, a casing pack fluid, a fracturing fluid, a packer fluid or a spacer fluid for deep petroleum and/or gas well drillings.
The continuous phase of the emulsion compositions of this invention is a liquid hydrocarbon selected from the group consisting of paraffins having a flash point of at least 100F., kerosene, turbine fuel, crude oil, diesel oil, gas oil, mineral oil and mixtures thereof.
Conveniently and economically, the liquid hydrocarbon can be the crude oil that is being recovered from and/or the hydrocarbon fuel such as diesel fuel, that is being used at, the drilling site where the compositions of this invention are used. When additional factors beyond convenience and economics, such as safety, handling and environmental factors, are considered, mineral oil can be advantageously used as the liquid hydrocarbon in the compositions of this invention because of its relatively low volatility and relatively low odor. In any case the -9- ~ v ~ J
polydiorganosiloxanes, delineated below, can be conveniently stored at the drilling field as a neat component or as a concentrate in a liquid hydrocarbon if desired and the compositions of this invention can be prepared therefrom in the the field as desired.
The (A) component of the compositions of this invention are described in detail in U.S. Patent 4,421,656.
These materials are described therein as part (b) of an emulsifier composition and comprise a solid, benzene soluble organopolysiloxane resin copolymer consisting essentially of (CH3)3SiOl/2 siloxane units and SiO4/2 siloxane units, there being from 0.6 to 0.9, inclusive, of said (CH3)3SiOl/2 siloxane units for every SiO4/2 siloxane unit.
Component (B) of this combination comprises hydrolytically stable organopolysiloxane-polyoxyalkylene copolymers having at least two organopolysiloxane-polyoxyalkylene molecules cross linked by a hydrolytically stable cross linking radical. Such materials are set forth and described in U.S. Patent No. 4,853,474 to teach the (B) compositions of this invention and their preparation.
Component (C) of this combination comprises emulsifiers which are polysiloxane-polyoxyalkylene copolymers which have both long chain alkyl groups in the molecules and, certain polyoxyalkylene groups, in combination to give unique emulsifier properties. Such materials are set forth and disclosed in U.S. Patent 4,381,241 to teach the (C) compositions of this invention and their preparation.
Component (D) of this invention is a polysiloxane-polyoxyalkylene surfactant that lends surfactancy to the inventive combination herein. Such materials are set forth and disclosed in U.S. Patent 3,629,308 to teach the (D) compositions and their preparation.
- 10- ~ ?,~ ~r3 ~ ~
The emulsion compositions of this invention can be prepared by conventional emulsifying methods as disclosed in the '241 and '656 patents. Preferably, the components are dissolved in all or a portion, of the liquid hydrocarbon component to form a solution and the brine component is thereafter emulsified therein with sufficient shear energy to provide an emulsion having a brine particle size of less than 10, preferably less than 1, micrometer in diameter, any remaining liquid hydrocarbon being mixed thereafter with said emulsion.
The following examples are disclosed to further teach how to make and use the present invention.
ExamPle A number of compositions were screened using maximum interfacial tension reduction as a screening technique.
The method of evaluating the materials was to measure the interfacial tension (IFT) between brine and diesel oil using the polysiloxane materials of the instant invention. When interfacial tension is minimized, better stability of the emulsion results.
Various surfactants were added at la/~ concentration to Diesel oil ~2. The solution was placed on various brines and allowed to equilibrate for 1 hour. The interfacial tension was measured between the brine and Diesel oil solution using the Denoy ring method. The table below sets forth the results.
3 ~ ~ 3 TABLE I
INTERFACIAL T~NSION AS MEASURED BETWEEN
BRINE AND DIESEL OIL #2 IN DYNES/CENTIMETER
BRINE LAYER
density in g/cc Sample ZnBr2 NaCl CaC12 2.51 1.19 1.3g A 0.~3 0.06 0.28 ~ 0.86 0.20 0.18 A = (CH3)3SiOI~CH3)2SiO~8{(CH3)(Q )SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)12OH
B = (CH3)3SiO{(CH3)zSiOl8{(CH3)(Q )SiO}4Si(CH3)3 where Q' is -R'(OcH2cH2)70H
ExamPle 2 Emulsion PreParation The most difficult test is when the heaviest brine ZnBr2 is used. The objective is to have no free brine after heat aging. Thus an emulsion was made by mixing 60% by volume (192 ml) brine and 40% by volume Diesel #2 (128 ml) to which the stabilizing surfactant mixture was added before hand. The emulsion is prepared by slowly adding the brine solution to the Diesel/surfactant mixture while mixing using a Hamilton-Beach mixer for shear. All emulsions were creamy, uniform and stable at room temperature. They were tested for high temperature stability by placing a portion thereof in a stainless ~teel pressure vessel, pressurizing the vessel with nitrogen and heating the pressurized vessel at 350F or 400~F
for the specified time. Table II shows the results.
-12~ Jr' TABLE II
HEAT AGING BRINE SOLUTIONS IN THE EMULSION
FORM USING STABILIZERS OF THIS INVENTION
FORMULATIONS
A B ¦ C D E F
I
PROPERTY
MEAS~RED 1-Top Oil % 17 ¦ 21 25 25 25 Emulsion % 83 1 79 60 75 75 Free Brine % 13 0 ¦ 0 15 0 A = 128 ml Diesel, 25 Grams of a mixture of a 1:3 ratio of a benzene soluble resin of this invention and a material ha~ing the formulation (CH3)3SiO{(CH3)SiO}38{CH3SiOCH2CH2Si(CH3)2} ____ _ o CH3 ( CH2 ) ~
(CH3)3SiO{(CH3)SiO}1~63 H(OCHCH2)19(0CH2CH2)190(CH2)3 _ CH3, _ 2 -13- ~3 ~'3 which is a commercial material for this application and 192 ml of brine heated 7 da~s at 400F.
= A and 3 grams of (cH3)3sioE(cH3)2siolg~(cH3)(Qi)sio}4si(cH3)3 where Q' i9 -R'(OCH2CH2)120H heated for 7 da~s at 400F.
C = A and 3 grams of (CH3)3SiOI(CH3)2SiO}8~(CH3)(Q')SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)70H heated for 7 da~s at 400F.
D = A and 3 grams of (CH3)3SiO{(CH3)2SiO}g{(CH3)(Q')SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)70H heated for 30 days at 400F.
E = A and 3 grams of (CH3)3SiO((CH3)2SiO3g{(CH3)(Q')SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)120H heated for 120 days at 400F.
F = A and 3 grams of (cH3)3sio{(cH3)2sio}g{(cH3)(Q~)sio}4si(cH3)3 where Q' is -R'(OCH2CH2)120H heated for 180 da~s at 350F.
COMPRISING POLYDIORGANOSILOXANES
The present invention relates to emulsifier compositions for the well drilling industry. The present invention also relates to compositions comprising emulsions of brines in liquid hydrocarbons which are useful in well drilling operations, such as in gas and/or oil well drilling, as a drilling fluid, a completion fluid, a workover fluid, a casing pack fluid, a fracturing fluid, a packer fluid or a spacer fluid.
Invert emulsions, in the form of drilling muds, completion fluids and packer fluids are well known in the well drilling art. Invert emulsions typically consist of a fluid phase comprising from 15 to 45 percent by volume of a CaC12 brine and 55 to 85 percent by volume of diesel oil and a solid phase comprising agents for pressure control, filtration control, viscosity control, gelling, etc. An invert emulsion drilling mud generally contains from 5 to 30 percent by volume of the brine.
While conventional invert emulsions are used in drilling deep wells, where high temperature and pressure are commonly encountered, they are not completely satisfactory for such a use. For example, invert emulsions are sometimes not sufficiently stable at the high temperatures encountered in deep wells. Furthermore, the use of excessive amounts of a weighting agent in an invert emulsion to achieve pressure control in deep wells is often undesirable because performance and properties of the emulsion can be adversely affected. Heavier brines, such as CaBr2 brines and/or ZnBr2 brines, have been used to increase the density of the invert emulsions, thereby achieving greater pressure control;
,3 ~ ~
however, sometimes the thermal stahility of these heavier emulsions is marginal or non-existent. FurthPr improvements in temperature stability of the invert emulsion are needed.
It is an ob~ect of this invention to provide an emulsifier composition comprising: (I) a viscosifier composition selected from the groups consisting e~sentially of (A) ~ (B), (A) + (C) and (A) + (B) + (C) and (II) a surfactant (D), wherein (A) is a solid, benzene-soluble organopolysiloxane resin copolymer; (B) is a hydrolytically stable compound having at least two organopolysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical; (C) is a polydiorgansiloxane-polyoxyalkylene selected from the group consisting of copolymers having the following formula:
a- Z3SiO{(CH3)2SiO}x~(CH3)(R)SiO}y~(CH3)(Q)SiO}zSiZ3 and b- Z3sio{(cH3)(R)sio}y~(cH3)(Q)sio}zsiz3~
wherein Q denotes a polyoxyalkylene radical having the formula -R' (OCH2CH2)p(0CH2CHCH3)qOR" ~nd (D) is a polysiloxane-polyoxyalkylene copolymer surfactant selected from the group consisting of copolymers having the general formula:
a R (CH3)2SiO{(CH3)2SiO}x,{(CH3)(Q )SiO}z~Si(CH3)2R
and b R (CH3)2SiO~(CH3)(Q )SiO}z,Si(CH3)2~
wherein Q' denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p,(0CH2CHCH3)q,0R .
It is another object of this invention to provide a solids-free invert emulsion which is suitable for use in the well drilling industry utilizing the emulsifier compositions described above.
It is yet another ob~ect of this invention to provide invert emulsions of a high density brine which have stability at higher temperatures. It is still a further ~ ~ ~3 3 . ~ ~3 ob~ect of this invention to provide improved invert emulsion muds. Further, it i9 another ob~ect of this invention to provide solids-free invert emul~ions having high den.sity and being suitable for use in the deep well drilling industry.
It is also an ob~ect of this invention to provide a method for preparing the invert emulsions of this invention. It is yet another ob~ect of this invention to provide an emulsion concentrate which is useful for preparing improved invert emulsions.
These ob~ects and others will become obvious when considering the following disclosure and appended claims.
According to this invention, it is possible not only to prepare a highly thermally stable emulsion of a high density brine but also to prepare a stable emulsion comprising a fluid phase having a ma~or amount of a high density brine and a minor amount of a liquid hydrocarbon.
The resulting invert emulsions are sufficiently dense to permit their use as solids-free oil well fluids in deep well drilling. They can also be formulated to contain solid and/or liquid components which are commonly used in the well drilling art for various purposes, such as for preparing invert emulsion drilling muds.
The present invention relates to emulsifier combinations comprising a blend of (I) viscosifiers, which themselves are a blend of certain solid resinous siloxanes and an alkyl/polyoxyalkylene containing material, or, a solid resinous siloxane and a crosslinked alkyl/polyoxyalkylene containing material, or, a blend of a solid resinous siloxane and a combination of an alkyl/polyoxyalkylene containing material and its crosslinked counterpart and (II), a surface active agent.
The present invention also relates to an emulsion composition to be used in well drilling and comprising (i) ~3~
from 1 to 75 parts by volume of a brine as a discontinuou~
phase, (ii) from 25 to 95 parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100F. as a continuous phase and (iii) from 0.05 to 15 parts by weight, for every 100 parts by weight of brine plus liquid hydrocarbon, of the the emulsifier combination.
The present invention further relates to a method for preparing the emulsion compositions of this invention.
With specificity, this invention deals with emulsifier compositions comprising (~) a vi~cosifier composition selected from the groups consisting essentially of (A) + (~), (A) ~ (C) and (A) + (B) I (C) and (II) a surfactant (D), wherein (A) is a solid, benzene-soluble organopoly-siloxane resin copolymer consisting essentially of (CH3)3SiOl/2 siloxane units and SiO4/2 siloxane unit, there being from 0.6 to 0.9, inclusive, of said (CH3)3SiOl/2 siloxane units for every SiO4/2;
(B) is a hydrolytically stable compound having at least two organopolysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical;
(C) is a polydiorganosiloxane-polyoxyalkylene selected from the group consisting of copolymers having the following formula:
a- Z3sio{(cH3)2sio}x{(cH3)(R)sio}yl(cH3)(Q)sio}zsiz3 and b- Z3sio{(~H3)(R)sio}y{(cH3)(Q)sio}zsiz3~
wherein Q denotes a polyoxyalkylene radical having the formula ~R~(OCHzCH2)p(0CH2CHCH3)qOR~ wherein R denotes a monovalent hydrocarbon radical having from 6 to 18 carbon atoms, inclusive, R' denotes a divalent radical bonded to a 3~
silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals; Z denotes a monovalent hydrocarbon radical having from 1 to 5 carbon atoms, inclusive or an R radical or a Q
radical; x has an average value of from 1 to 400, y has an average value of from 1 to 400, z has an average value of from 1 to 5, x+y+z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p+q has an average value sufficient to provide a formula weight of from 600 to 3500 for the ~(OCH2CH2)p(0CH2CHCH3)q~ portion of the Q radical, there being an average of at leas~ one Q radical and an average of at least one R radical per molecule and, (D) is a polysiloxane-polyoxyalkylene copolymer surfactant selected from the group consisting of copolymers having the general formula:
a R (CH3)2SiO{(CH3)2SiO}x,~(CH3)(Q )SiO}z,Si(CH3)2R
and b' R''''(CH3)2SiO~(CH3)(Q')SiO}z,Si(CH3)2R
wherein Q' denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p,(0CH2CHCH3)q,OR", wherein R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, R"" den.otes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, inclusive or a Q' radical, x' has an average value of from 1 to 100, z' has an average value of from 1 to 10, x'+ z' has an average value of from 8 to 100, p' has an average value equal to or greater than the average value of q' and p'+ q' hac an average value sufficient to provide a formula weight of from 300 to 3500 for the ~(OCH2CH2)p,(0CH2CHCH3)q,~
-6- ~ ) tj portion of the Q' radical, there being an average of at least one Q' radical per molecule of the polydiorganosiloxane, wherein the ratio of (A) to (B) in (A) + (B), the ratio of (A) to (C) in (A) ~ (C) and the ratio of (A) to (B) + (C) in (A) + (B) + (C) is in the range of 15:85 to 35065 and the amount of (D) present in the composition is from 5 to 70 weight percent based on the weight of (I) and (II). For purposes of this invention, component (D) must be water soluble and the statement "...p' has an average value equal to or greater than the average value of q'..." satisfies that requirement.
The present invention further relates to a method for preparing the emulsion compositions of this invention comprising (I) mixing to form a solution, (i) 0.5 to 15 parts by weight of an emulsifier composition of this invention (ii) aV parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100F., (II) mixing the solution of step (I) with bV parts by volume of the liquid hydrocarbon, (III) mixing V' parts by volume of a brine with the solution of step (II) with sufficient shear energy to provide an emulsion having a brine particle size of less than 10 micrometers in diameter and (IV) mixing the emulsion of step (III) with cV parts by volume of liquid hydrocarbon, wherein V has an average of from 25 to 99 pa.rts by volume, a has a value of from greater than zero to 1, b has a value of from zero to less than 1, c has a value of from zero to less than 1, a+b+c has a value of 1, V' has a value of from 1 to 75 parts by volume and the weight of V + V' has a value of 100 parts by weight.
The present invention further relates to a concentrate comprising from 0.5 to 15 parts by weight of an -7~ 3 i ~3 ~
emulsifier composition of this invention and a portion of the liquid hydrocarbon equal to from 0.0001 to 0.1 of the total amount of liquid hydrocarbon component that is used to prepare the emulsion compositions of this invention.
The discontinuous phase of the emulsion compositions of this invention is a brine. Herein, the term brine is used in its broadest sense, i.e. an aqueous solution of a salt containing at least 3 percent by weight of the salt. Preferably the brine is a saturated aqueous solution of the salt at 20C. The term brine further includes brine occurring naturally or brine prepared synthetically. It is within the scope and spirit of this invention to dissolve one or more salts in natural brine to prepare a brine suitable for use in the compositions of this invention.
The salt portion of the brine preferably has a high solubility in water at room temperature so that the emulsion compositions of this invention can be formulated to have a wide range of densities. The salt advantageously has, in addition to a high solubility in water, a large formula weight so that the brine can be formulated to have a high density, for example, up to 22 pounds per gallon (2642 kilograms per cubic meter).
Salts typically used in the well drilling art and being suitable for use in the compositions of this invention include sodium chloride, sodium carbonate, potassium chloride, potassium carbonate, calcium chloride, calcium bromide, zinc chloride, zinc bromide and mixtures thereof.
Conveniently, a suitable brine for the composition of this invention can be the natural brine that is frequently present at the drilling site where these compositions are u~ed. In this case the present invention contemplates the storing of the other components of these compositions hereinafter delineated, at the drilling site as separate -8- ~ v ,' and/or mixed components and formulating the emulsions of this invention in the field, as desired. Said natural brine can be further mixed with a salt, if desired.
A preferred brine in the emulsion compositions of this invention comprise water saturated with a mixture of calcium bromide and zinc bromide and having a density of about 20 pounds per gallon at 20C. Such a brine can be emulsified in a liquid hydrocarbon according to this invention to provide an emulsion that needs no additional weighting agent, such as barium sulfate, to permit its use as a fluid in petroleum and/or gas well drillings. Said emulsions can also be readily formulated with well-known additives to provide improved drilling muds which are useful in well drilling operations, such as in gas and/or oil well drilling, as a drilling fluid, a completion fluid, a workover fluid, a casing pack fluid, a fracturing fluid, a packer fluid or a spacer fluid for deep petroleum and/or gas well drillings.
The continuous phase of the emulsion compositions of this invention is a liquid hydrocarbon selected from the group consisting of paraffins having a flash point of at least 100F., kerosene, turbine fuel, crude oil, diesel oil, gas oil, mineral oil and mixtures thereof.
Conveniently and economically, the liquid hydrocarbon can be the crude oil that is being recovered from and/or the hydrocarbon fuel such as diesel fuel, that is being used at, the drilling site where the compositions of this invention are used. When additional factors beyond convenience and economics, such as safety, handling and environmental factors, are considered, mineral oil can be advantageously used as the liquid hydrocarbon in the compositions of this invention because of its relatively low volatility and relatively low odor. In any case the -9- ~ v ~ J
polydiorganosiloxanes, delineated below, can be conveniently stored at the drilling field as a neat component or as a concentrate in a liquid hydrocarbon if desired and the compositions of this invention can be prepared therefrom in the the field as desired.
The (A) component of the compositions of this invention are described in detail in U.S. Patent 4,421,656.
These materials are described therein as part (b) of an emulsifier composition and comprise a solid, benzene soluble organopolysiloxane resin copolymer consisting essentially of (CH3)3SiOl/2 siloxane units and SiO4/2 siloxane units, there being from 0.6 to 0.9, inclusive, of said (CH3)3SiOl/2 siloxane units for every SiO4/2 siloxane unit.
Component (B) of this combination comprises hydrolytically stable organopolysiloxane-polyoxyalkylene copolymers having at least two organopolysiloxane-polyoxyalkylene molecules cross linked by a hydrolytically stable cross linking radical. Such materials are set forth and described in U.S. Patent No. 4,853,474 to teach the (B) compositions of this invention and their preparation.
Component (C) of this combination comprises emulsifiers which are polysiloxane-polyoxyalkylene copolymers which have both long chain alkyl groups in the molecules and, certain polyoxyalkylene groups, in combination to give unique emulsifier properties. Such materials are set forth and disclosed in U.S. Patent 4,381,241 to teach the (C) compositions of this invention and their preparation.
Component (D) of this invention is a polysiloxane-polyoxyalkylene surfactant that lends surfactancy to the inventive combination herein. Such materials are set forth and disclosed in U.S. Patent 3,629,308 to teach the (D) compositions and their preparation.
- 10- ~ ?,~ ~r3 ~ ~
The emulsion compositions of this invention can be prepared by conventional emulsifying methods as disclosed in the '241 and '656 patents. Preferably, the components are dissolved in all or a portion, of the liquid hydrocarbon component to form a solution and the brine component is thereafter emulsified therein with sufficient shear energy to provide an emulsion having a brine particle size of less than 10, preferably less than 1, micrometer in diameter, any remaining liquid hydrocarbon being mixed thereafter with said emulsion.
The following examples are disclosed to further teach how to make and use the present invention.
ExamPle A number of compositions were screened using maximum interfacial tension reduction as a screening technique.
The method of evaluating the materials was to measure the interfacial tension (IFT) between brine and diesel oil using the polysiloxane materials of the instant invention. When interfacial tension is minimized, better stability of the emulsion results.
Various surfactants were added at la/~ concentration to Diesel oil ~2. The solution was placed on various brines and allowed to equilibrate for 1 hour. The interfacial tension was measured between the brine and Diesel oil solution using the Denoy ring method. The table below sets forth the results.
3 ~ ~ 3 TABLE I
INTERFACIAL T~NSION AS MEASURED BETWEEN
BRINE AND DIESEL OIL #2 IN DYNES/CENTIMETER
BRINE LAYER
density in g/cc Sample ZnBr2 NaCl CaC12 2.51 1.19 1.3g A 0.~3 0.06 0.28 ~ 0.86 0.20 0.18 A = (CH3)3SiOI~CH3)2SiO~8{(CH3)(Q )SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)12OH
B = (CH3)3SiO{(CH3)zSiOl8{(CH3)(Q )SiO}4Si(CH3)3 where Q' is -R'(OcH2cH2)70H
ExamPle 2 Emulsion PreParation The most difficult test is when the heaviest brine ZnBr2 is used. The objective is to have no free brine after heat aging. Thus an emulsion was made by mixing 60% by volume (192 ml) brine and 40% by volume Diesel #2 (128 ml) to which the stabilizing surfactant mixture was added before hand. The emulsion is prepared by slowly adding the brine solution to the Diesel/surfactant mixture while mixing using a Hamilton-Beach mixer for shear. All emulsions were creamy, uniform and stable at room temperature. They were tested for high temperature stability by placing a portion thereof in a stainless ~teel pressure vessel, pressurizing the vessel with nitrogen and heating the pressurized vessel at 350F or 400~F
for the specified time. Table II shows the results.
-12~ Jr' TABLE II
HEAT AGING BRINE SOLUTIONS IN THE EMULSION
FORM USING STABILIZERS OF THIS INVENTION
FORMULATIONS
A B ¦ C D E F
I
PROPERTY
MEAS~RED 1-Top Oil % 17 ¦ 21 25 25 25 Emulsion % 83 1 79 60 75 75 Free Brine % 13 0 ¦ 0 15 0 A = 128 ml Diesel, 25 Grams of a mixture of a 1:3 ratio of a benzene soluble resin of this invention and a material ha~ing the formulation (CH3)3SiO{(CH3)SiO}38{CH3SiOCH2CH2Si(CH3)2} ____ _ o CH3 ( CH2 ) ~
(CH3)3SiO{(CH3)SiO}1~63 H(OCHCH2)19(0CH2CH2)190(CH2)3 _ CH3, _ 2 -13- ~3 ~'3 which is a commercial material for this application and 192 ml of brine heated 7 da~s at 400F.
= A and 3 grams of (cH3)3sioE(cH3)2siolg~(cH3)(Qi)sio}4si(cH3)3 where Q' i9 -R'(OCH2CH2)120H heated for 7 da~s at 400F.
C = A and 3 grams of (CH3)3SiOI(CH3)2SiO}8~(CH3)(Q')SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)70H heated for 7 da~s at 400F.
D = A and 3 grams of (CH3)3SiO{(CH3)2SiO}g{(CH3)(Q')SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)70H heated for 30 days at 400F.
E = A and 3 grams of (CH3)3SiO((CH3)2SiO3g{(CH3)(Q')SiO}4Si(CH3)3 where Q' is -R'(OCH2CH2)120H heated for 120 days at 400F.
F = A and 3 grams of (cH3)3sio{(cH3)2sio}g{(cH3)(Q~)sio}4si(cH3)3 where Q' is -R'(OCH2CH2)120H heated for 180 da~s at 350F.
Claims (4)
1. An emulsifier composition comprising:
(I) a viscosifier composition selected from the groups consisting essentially of (A) + (B), (A) + (C) and (A) + (B) + (C), and (II) a surfactant (D), wherein (A) is a solid, benzene-soluble organopolysiloxane resin copolymer consisting essentially of (CH3)3SiO1/2 siloxane units and SiO4/2 siloxane units, there being from 0.6 to 0.9, inclusive, of said (CH3)3SiO1/2 siloxane units for every SiO4/2;
(B) is a hydrolytically stable compound having at least two organopolysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical;
(C) is a polydiorganosiloxane-polyoxyalkylene selected from the group consisting of copolymers having the following formula:
a. Z3SiO{(CH3)2SiO}x{(CH3)(R)SiO}y{(CH3)(Q)SiO}zSiZ3 and b. Z3SiO{(CH3)(R)SiO}y{(CH3)(Q)SiO}zSiZ3, wherein Q denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p(OCH2CHCH3)qOR", wherein R denotes a monovalent hydrocarbon radical having from 6 to 18 carbon atoms, inclusive, R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals; Z denotes a monovalent hydrocarbon radical having from 1 to 5 carbon atoms, inclusive or an R radical or a Q
radical; x has an average value of from 1 to 400, y has an average value of from 1 to 400, z has an average value of from 1 to 5, x+y+z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p+q has an average value sufficient to provide a formula weight of from 600 to 3500 for the -(OCH2CH2)p(OCH2CHCH3)q- portion of the Q radical, there being an average of at least one Q radical and an average of at least one R radical per molecule and, (D) is a polysiloxane-polyoxyalkylene copolymer surfactant selected from the group consisting of copolymers having the general formula:
a' R""(CH3)2SiO{(CH3)2SiO}x,{(CH3)(Q')SiO}z,Si(CH3)2R""
and b' R""(CH3)2SiO{(CH3)(Q')SiO}z,Si(CH3)2R""
wherein Q' denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p,(OCH2CHCH3)q,OR", wherein R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, aryl-alkyl and acyl radicals, R"" denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, inclusive or a Q' radical, x' has an average value of from 1 to 100, z' has an average value of from 1 to 10, x'+ z' has an average value of from 8 to 100, p' has an average value equal to or greater than the average value of q' and p'+ q' has an average value sufficient to provide a formula weight of from 300 to 3500 for the -(OCH2CH2)p,(OCH2CHCH3)q,- portion of the Q' radical, there being an average of at least one Q' radical per molecule of the polydiorganosiloxane, wherein the ratio of (A) to (B) in (A) + (B), the ratio of (A) to (C) in (A) + (C) and the ratio of (A) to (B) + (C) in (A) + (B) + (C) is in the range of 15:85 to 35:65 and the amount of (D) present in the composition is from 5 to 70 weight percent based on the weight of (I) and (II).
(I) a viscosifier composition selected from the groups consisting essentially of (A) + (B), (A) + (C) and (A) + (B) + (C), and (II) a surfactant (D), wherein (A) is a solid, benzene-soluble organopolysiloxane resin copolymer consisting essentially of (CH3)3SiO1/2 siloxane units and SiO4/2 siloxane units, there being from 0.6 to 0.9, inclusive, of said (CH3)3SiO1/2 siloxane units for every SiO4/2;
(B) is a hydrolytically stable compound having at least two organopolysiloxane-polyoxyalkylene molecules crosslinked by a hydrolytically stable cross-linking radical;
(C) is a polydiorganosiloxane-polyoxyalkylene selected from the group consisting of copolymers having the following formula:
a. Z3SiO{(CH3)2SiO}x{(CH3)(R)SiO}y{(CH3)(Q)SiO}zSiZ3 and b. Z3SiO{(CH3)(R)SiO}y{(CH3)(Q)SiO}zSiZ3, wherein Q denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p(OCH2CHCH3)qOR", wherein R denotes a monovalent hydrocarbon radical having from 6 to 18 carbon atoms, inclusive, R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals; Z denotes a monovalent hydrocarbon radical having from 1 to 5 carbon atoms, inclusive or an R radical or a Q
radical; x has an average value of from 1 to 400, y has an average value of from 1 to 400, z has an average value of from 1 to 5, x+y+z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p+q has an average value sufficient to provide a formula weight of from 600 to 3500 for the -(OCH2CH2)p(OCH2CHCH3)q- portion of the Q radical, there being an average of at least one Q radical and an average of at least one R radical per molecule and, (D) is a polysiloxane-polyoxyalkylene copolymer surfactant selected from the group consisting of copolymers having the general formula:
a' R""(CH3)2SiO{(CH3)2SiO}x,{(CH3)(Q')SiO}z,Si(CH3)2R""
and b' R""(CH3)2SiO{(CH3)(Q')SiO}z,Si(CH3)2R""
wherein Q' denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p,(OCH2CHCH3)q,OR", wherein R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, aryl-alkyl and acyl radicals, R"" denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, inclusive or a Q' radical, x' has an average value of from 1 to 100, z' has an average value of from 1 to 10, x'+ z' has an average value of from 8 to 100, p' has an average value equal to or greater than the average value of q' and p'+ q' has an average value sufficient to provide a formula weight of from 300 to 3500 for the -(OCH2CH2)p,(OCH2CHCH3)q,- portion of the Q' radical, there being an average of at least one Q' radical per molecule of the polydiorganosiloxane, wherein the ratio of (A) to (B) in (A) + (B), the ratio of (A) to (C) in (A) + (C) and the ratio of (A) to (B) + (C) in (A) + (B) + (C) is in the range of 15:85 to 35:65 and the amount of (D) present in the composition is from 5 to 70 weight percent based on the weight of (I) and (II).
2. An emulsion composition to be used in well drilling and comprising (A) from 1 to 75 parts by volume of a brine as a discontinuous phase, (B) from 25 to 95 parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100°F. as a continuous phase; (C) from 0.05 to 15 parts by weight, for every 100 parts by weight of brine plus liquid hydrocarbon, of the composition of claim 1.
3. A method for preparing the emulsion compositions of this invention comprising (I) mixing the following to form a solution:
(i) 0.5 to 15 parts by weight of the composition of claim 1;
(ii) aV parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100°F., (II) mixing the solution of step (I) with bV parts by volume of the liquid hydrocarbon, (III) mixing V' parts by volume of a brine with the solution of step (II) with sufficient shear energy to provide an emulsion having a brine particle size of less than 10 micrometers in diameter, and (IV) mixing the emulsion of step (III) with cV parts by volume of liquid hydrocarbon, wherein V has an average of from 25 to 99 parts by volume, a has a value of from greater than zero to 1, b has a value of from zero to less than 1, c has a value of from zero to less than 1, a+b+c has a value of 1, V' has a value of from 1 to 75 parts by volume and the weight of V + V' has a value of 100 parts by weight.
(i) 0.5 to 15 parts by weight of the composition of claim 1;
(ii) aV parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100°F., (II) mixing the solution of step (I) with bV parts by volume of the liquid hydrocarbon, (III) mixing V' parts by volume of a brine with the solution of step (II) with sufficient shear energy to provide an emulsion having a brine particle size of less than 10 micrometers in diameter, and (IV) mixing the emulsion of step (III) with cV parts by volume of liquid hydrocarbon, wherein V has an average of from 25 to 99 parts by volume, a has a value of from greater than zero to 1, b has a value of from zero to less than 1, c has a value of from zero to less than 1, a+b+c has a value of 1, V' has a value of from 1 to 75 parts by volume and the weight of V + V' has a value of 100 parts by weight.
4. A concentrate comprising from 0.5 to 15 parts by weight of an emulsifier composition of claim 1 and a portion of liquid hydrocarbon equal to from 0.0001 to 0.1 of the total amount of liquid hydrocarbon component that is used to prepare well drilling emulsion compositions.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86839292A | 1992-04-14 | 1992-04-14 | |
| US07/868,392 | 1992-04-14 | ||
| US98391392A | 1992-12-01 | 1992-12-01 | |
| US07/983,913 | 1992-12-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2093505A1 true CA2093505A1 (en) | 1993-10-15 |
Family
ID=27128049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093505A Abandoned CA2093505A1 (en) | 1992-04-14 | 1993-04-06 | Invert emulsions for well drilling comprising polydiorganosiloxanes |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0625531A (en) |
| CA (1) | CA2093505A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996007710A1 (en) * | 1994-09-07 | 1996-03-14 | Sofitech N.V. | Stabilising emulsions |
| EP0707134A1 (en) * | 1994-09-29 | 1996-04-17 | Wacker-Chemie GmbH | Method of oil recovery |
| GB2307653A (en) * | 1994-09-07 | 1997-06-04 | Sofitech Nv | Stabilising emulsions |
| US20120067586A1 (en) * | 2010-09-16 | 2012-03-22 | Momentive Performance Materials Inc. | Aqueous foaming compositions with high tolerance to hydrocarbons |
-
1993
- 1993-04-06 CA CA002093505A patent/CA2093505A1/en not_active Abandoned
- 1993-04-13 JP JP5086064A patent/JPH0625531A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996007710A1 (en) * | 1994-09-07 | 1996-03-14 | Sofitech N.V. | Stabilising emulsions |
| GB2307653A (en) * | 1994-09-07 | 1997-06-04 | Sofitech Nv | Stabilising emulsions |
| GB2307653B (en) * | 1994-09-07 | 1999-01-27 | Sofitech Nv | Stabilising emulsions |
| EP0707134A1 (en) * | 1994-09-29 | 1996-04-17 | Wacker-Chemie GmbH | Method of oil recovery |
| US5630474A (en) * | 1994-09-29 | 1997-05-20 | Wacker-Chemie Gmbh | Process for the extraction of crude oil |
| US20120067586A1 (en) * | 2010-09-16 | 2012-03-22 | Momentive Performance Materials Inc. | Aqueous foaming compositions with high tolerance to hydrocarbons |
| EP2616635A2 (en) * | 2010-09-16 | 2013-07-24 | Momentive Performance Materials Inc. | Aqueous foaming compositions with high tolerance to hydrocarbons |
| US8524641B2 (en) * | 2010-09-16 | 2013-09-03 | Momentive Performance Materials Inc. | Aqueous foaming compositions with high tolerance to hydrocarbons |
| EP2616635A4 (en) * | 2010-09-16 | 2014-04-16 | Momentive Performance Mat Inc | AQUEOUS COMPOSITIONS FORMING FOAM WITH HIGH HYDROCARBON TOLERANCE |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0625531A (en) | 1994-02-01 |
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