CA1160032A - Oil base fluids containing organophilic clays - Google Patents
Oil base fluids containing organophilic claysInfo
- Publication number
- CA1160032A CA1160032A CA000390140A CA390140A CA1160032A CA 1160032 A CA1160032 A CA 1160032A CA 000390140 A CA000390140 A CA 000390140A CA 390140 A CA390140 A CA 390140A CA 1160032 A CA1160032 A CA 1160032A
- Authority
- CA
- Canada
- Prior art keywords
- group
- fluid
- carbon atoms
- clay
- gellant
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/502—Oil-based compositions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
Abstract
ABSTRACT
An oil base fluid containing an organophilic clay gellant is disclosed. The gellant is the reaction product of an organic cationic compound and a smectite-type clay.
An oil base fluid containing an organophilic clay gellant is disclosed. The gellant is the reaction product of an organic cationic compound and a smectite-type clay.
Description
~6~03;~
OIL BASE FLUIDS CONTAININIG ORGANOPHILIC CLAYS
This invention relates to organophilic organic-clay complexes which are dispersible in organic liquids to form a gel therein. More particularly such gels are useful in oil base muds and oil base packer fluids.
It is well known that organic compounds containing a cation will react with clays which contain a negative layer-lattice and exchangeable cations to form organo-philic organic-clay products. The reaction of an organic cation containing at Ieast one alkyl group of at least 10 carbon atoms with clay generally results in organoclays swellable in certain organic liquids.
Prior publications include U.S. Pat. No. 2,531,427, and U.S. Pat. No. 2,966,506 and the book "Clay Mineralogy", 2nd Edition, 1968 by Ralph E. Grim (McGraw Hill Book Co., ; 15 Inc.), particularly Chapter lQ, Clay-Mineral-Organic Reactions; pp. 356-368 - Ionic Reactions, Smectite; and pp. 392-401 - Organophilic Clay-Mineral Complexes.
Maximum gelling (thickening) efficiency fro~ these organoclays is achieved by adding a low molecular weight polar organic dispersing material to the composition.
Such materials are disclosed in U.S. Patents: O'H~lloran
OIL BASE FLUIDS CONTAININIG ORGANOPHILIC CLAYS
This invention relates to organophilic organic-clay complexes which are dispersible in organic liquids to form a gel therein. More particularly such gels are useful in oil base muds and oil base packer fluids.
It is well known that organic compounds containing a cation will react with clays which contain a negative layer-lattice and exchangeable cations to form organo-philic organic-clay products. The reaction of an organic cation containing at Ieast one alkyl group of at least 10 carbon atoms with clay generally results in organoclays swellable in certain organic liquids.
Prior publications include U.S. Pat. No. 2,531,427, and U.S. Pat. No. 2,966,506 and the book "Clay Mineralogy", 2nd Edition, 1968 by Ralph E. Grim (McGraw Hill Book Co., ; 15 Inc.), particularly Chapter lQ, Clay-Mineral-Organic Reactions; pp. 356-368 - Ionic Reactions, Smectite; and pp. 392-401 - Organophilic Clay-Mineral Complexes.
Maximum gelling (thickening) efficiency fro~ these organoclays is achieved by adding a low molecular weight polar organic dispersing material to the composition.
Such materials are disclosed in U.S. Patents: O'H~lloran
2,677,661; McCarthy et al. 2,704,276; Stratton 2,833,720;~
Stratton 2,879,229; and Stansfield et al. 3,294,683. The use of such dispersion aids was found unnecessary when us-ing particular organophilic clays derived from substituted . ~ '~
i -~6(~)3Z
quaternary ammonium compounds as disclosed in Finlayson et al. 4,105,S78 and Finlayson 4,208,218.
Prior organophilic clays have exhibited limited broad range gelling utility due to fluctuating dispersion and viscosity properties. While the materials disclosed in U.S. Patent 4,105,578 have not shown such deficiencies, such materials are difficult and costly to produce.
Summary of the Invention An oil-base fluid of this invention which comprises an organophilic gellant comprising the reaction product of an oil phase, and from about 1 to about 50 lbs. per barrel of an organic cationic compound and a smectite-type clay having a cation exchange capacity of at least 75 milli-equivalents per 100 grams of said clay, the organic cationic - compound containing:
(a) a first member selected rom the group consisting of a ~,~ -unsaturated alkyl group, having less than 7 aliphatic carbon atoms and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof, (b) a second group comprising a long chain alkyl group having 8 to 60 carbon atoms and (c) a third and fourth member selected from a group consistin~ of a~ unsaturated alkyl group having less than 7 aliphatic carbon atoms , a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, and an alkyl group having 1 to 22 carbon atoms and mixtures thereof; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100%
active clay basis.
Detailed Description of the Invention The oil base fluid of the present invention consists of an oil phase and from about 1 to about 50 lbs.
per barrel of an organophilic clay gellant. Preferably, the fluid is non-aqueous.
A suitable oil phase of this invention ma~ be crude petroleum and fractions thereof, including but not limited to diesel oil, kerosene, fuel oil, light lubricating oil fractions, and heavy naphtha having a boiling range ,, ~L~L6~t3;~
between about 300 to 600F. The preferred material is diesel oil.
The amount of the organophilic clay employed is that amount which is effective in obtaining the necessary degree of gellation (thickening) of the oil-base fluid for the intended application~ that is, drilling fluid or packer fluid. The minimwn concentration of organophilic clay needed to gel a particular fluid is dependent upon factors such as the type of organophilic clay used, the characteris-tics of the oil phase and emulsif~ied water phase if any, and the maximum temperature to which the fluid is to be raised.
The maximum concentration of organophilic clay is limited to that which will form a pumpable fluid.
The concentration of organophilic clay within the range of about 1 to about 50 lbs. per barrel (42 gallon barrel) will generally provide a sufficiently gelled fluid for broad applications. Preferably about 1 to about 10 lbs.
per barrel are employed in the preparation of oil-base drilling fluids whereas amounts from about 6 to 50 lbs. per barrel have been found adequate for the preparation of oil-base packer fluids. ~t has been found that when the organophilic clay is mixed into the oil-base fluid, essen-tially complete gelling is achieved at low shear mixing.The resulting oil-base fluid is a stable oil-base fluid at surface temperatures below -20F and down-hole temperatures up to 500F. The formation of the stable fluid occurs in a matter of minutes following addition and low shear mixing of the organophilic clay in the oil base fluid.
A packer fluid is prepared in accordance with this invention by adding to an oil medium the organophilic clay.
The composition of the packer fluid is regulated as discussed above to provide a pumpable composition. The optional emulsifiers, weighting agents, and fluid loss control materials may be added at any time. It is only necessary to obtain a stable the fluid prior to usage of the fluid. Once prepared, the packer fluid is transferred, such as by pumping, into a well bore or to tubing canulas, at least one portion of which is to be filled.
_4_ ~LG~3Z
The oil-base drilling fluid can be prepared and used either before drillinq commences or while drilling is in progress. The method of adding the ingredient to prepare the fluid is not critical. Mixing is accomplished with conventional devices capable of employing a low shear mixing force. Greater mixing force may be employed even though not necessary. Once prepared, the drilling fluid is trans-ferred, such as by pumping, into a well bore andcirculated to the bit and through the borehole in contact with the walls thereof.
The organophilic clays of this invention can be prepared by admixing the clay, quaternary ammonium compound and water together, preferably at a temperature within the range from 20C to 100C, and most preferably from 35C to 77C for a period of time sufficient for the organic compound to react with the clay particles, followed by filtering, washing, drying and grinding. The ~uaternary compound is added in the desired milliequivalent ratio, preferably dispersed in isopropanol or water. In using the organophilic clays in emulsions, the drying and grinding steps may be eliminated. When the clay, quaternary ammonium compound and water are admixed in such concentrations that a slurry is not formed, filtration and washing steps may be eliminated.
The organic cationic compounds useful in this invention may be selected from a wide range of materials that are capable of forming an organophilic clay by exchange of cations with the smectite-type clay. The or~anic cationic compound must have a positive charge localized on a single atom or on a small group of atoms within the compound.
Preferably the organic cation is selected from the group consisting of quarternary ammonium salts, phosphonium salts, and mixtures thereof, as well as equivalent salts. The organic cation preferably contains at least one member selected from each of two groups, the first group consisting of a ~, y-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon ~5~ ~6~32 atoms and mixtures thereof and the second group consisting of a long chain alkyl group.
A representative formula of the organic cation is ~
wherein Rl is selected from the group consisting of a ~,y -unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are selected from a group consisting of a ~, y-unsaturated alkyl group having less than 7 aliphatic carbon atoms , a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof ; and X is phosphorous or nitrogen.
Rl The ~,y -unsaturated alkyl group may be select~ed from a wide range of materials. These compounds may be cyclic or acyclic, unsubstituted or substituted. ~,r-unsaturated alkyl radicals should contain less than 7aliphatic carbon atoms. The aliphatic radical of the ~,y -unsaturated alkyl radicals preferably contains less than 4 aliphatic carbons. The ~,y -unsaturated alkyl radical may be substituted with an aromatic ring that is con}ugated with the unsaturation of the ~, y moiety. The ~,y - radical may also be substituted with both aliphatic radicals and aromatic rings.
Representative examples of cyclic ~,y -unsaturated alkyl groups include 2-cyclohexenyl and 2-cyclopentenyl.
Representative examples of acyclic ~,y - unsaturated alkyl groups containing 6 or less carbon atoms include propargyl;
2-propenyl; 2-butenyl; 2-pentenyl; 2-hexenyl; 3-methyl-2-bu-tenyl; 3-methyl-2-pentenyl; 2,3-dimethyl-2-butenyl; 1,1-di-methyl-2-propenyl; 1,2-dimethyl-2-propenyl; 2,4-pentadienyl;
and 2,4-hexadienyl. Representative examples of acyclic-aromatic substituted compounds include 3-phenyl-2-propenyl;
2-phenyl-2-propenyl; and 3-(4-methoxyphenyl)-2-propenyl.
Representative examples of arornatic and aliphatic substituted materials include 3-phenyl-2-cyclohexenyl; 3-phenyl-2-cyclopentenyl. The alkyl group may be substituted with an aromatic rin~.
The hydroxyalkyl group may be selected from a hydroxyl substituted aliphatic radical having from 2 to 6 aliphatic carbons wherein the hydroxyl is not substituted at the carbon adjacent to the positive charged atom. The alkyl group may be substituted with an aromatic ring. Representa-tive examples include 2-hydroxyethyl; 3-hydroxypropyl;
4-hydroxypentyl; 6-hydroxyhexyl; 2~hydroxypropyl;
2-hydroxybutyl; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxy-cyclohexyl; 3-hydroxycyclohexyl; 4-hydroxycyclohexyl;
2-hydroxycyclopentyl; 3-hydroxycyclopentyl; 2-methyl-2-hydroxypropyl; 3-methyl-2-hydroxybutyl; and 5-hydroxy-2-pentenyl.
The long chain alkyl radicals may be branched orunbranched, saturated or unsaturated, substituted or unsub-stituted and should have from 8 to 60 carbon atoms in thestraight chain portion of the radical.
The long chain alkyl radicals may be derived from naturally occurring oils including various vegetable oils~
such as corn oil, coconut oil, soybean oil, cottonseed oil, and castor oil and various animal oils and fats such as tallow oil. The alkyl radicals may be derived synthetically from alpha olefins.
Representative examples of useful branched, saturated alkyl radicals include 12-methylstearyl; and 12-ethylstearyl. Representative examples of useful branched, ~6~Q3~
unsaturated radicals include 12-methyloleyl and 12-ethyloleyl.
Representative examples of unbranched saturated radicals include lauryl; stearyl; tridecyl; myristal (tetradecyl);
pentadecyl; hexadecyl; hydrogenated tallow; docosonyl.
Representative exar,lples of unbranched, unsaturated and unsubstituted long cnain alkyl radicals include oleyl, linoleyl; linolenyl, soya and tallow.
R3 and R4 R3 and R~ are individually selected from a group consisting of (a) a ~, ~-unsaturated alkyl group having less than 7 aliphatic carbon atoms, described above, (b) a hydroxyalkyl group having 2 to 6 carbon atoms, described above; (c) a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, and (d) an aralkyl group which includes benzyl and substituted benzyl moieties including fused ring moieties having linear or branched chains of 1 to 22 carbon atoms in the alkyl portion of the aralkyl group.
The long chain alkyl group of R3 and R4 may be linear or branched, cyclic or acyclic, substituted or unsubstituted, containing 1 to 22 carbon atoms. Representa-tive examples of useful alkyl groups include methyl; ethyl;
- 25 propyl; 2-propyl; iso-butyl; cyclopentyl; and cyclohexyl.
The alkyl radicals may be derived from sources similar to the long chain alkyl radical of R2 above.
Representative examples of an aralkyl group would include benzyl and those materials derived from compounds such as benzyl halides, benzhydryl halides, trityl halides, 1-halo-1-phenylalkanes wherein the alkyl chain has from 1 to 22 carbon atoms such as 1-halo-1-phenylethane;
1-halo-1-phenyl propane; and 1-halo-1-phenyloctadecane;
substituted benzyl moieties such as would be derived from ortho-, meta- and para-chlorobenzyl halides, para-methoxybenzyl halides; ortho-, meta- and para-nitrilobenzyl halides, and ortho-, meta- and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 22 carbon atoms; and fused ring benzyl-type moieties such as would be derived from 2-halomethyl-naphthalene, 9-halomethylanthracene and .
Stratton 2,879,229; and Stansfield et al. 3,294,683. The use of such dispersion aids was found unnecessary when us-ing particular organophilic clays derived from substituted . ~ '~
i -~6(~)3Z
quaternary ammonium compounds as disclosed in Finlayson et al. 4,105,S78 and Finlayson 4,208,218.
Prior organophilic clays have exhibited limited broad range gelling utility due to fluctuating dispersion and viscosity properties. While the materials disclosed in U.S. Patent 4,105,578 have not shown such deficiencies, such materials are difficult and costly to produce.
Summary of the Invention An oil-base fluid of this invention which comprises an organophilic gellant comprising the reaction product of an oil phase, and from about 1 to about 50 lbs. per barrel of an organic cationic compound and a smectite-type clay having a cation exchange capacity of at least 75 milli-equivalents per 100 grams of said clay, the organic cationic - compound containing:
(a) a first member selected rom the group consisting of a ~,~ -unsaturated alkyl group, having less than 7 aliphatic carbon atoms and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof, (b) a second group comprising a long chain alkyl group having 8 to 60 carbon atoms and (c) a third and fourth member selected from a group consistin~ of a~ unsaturated alkyl group having less than 7 aliphatic carbon atoms , a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, and an alkyl group having 1 to 22 carbon atoms and mixtures thereof; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100%
active clay basis.
Detailed Description of the Invention The oil base fluid of the present invention consists of an oil phase and from about 1 to about 50 lbs.
per barrel of an organophilic clay gellant. Preferably, the fluid is non-aqueous.
A suitable oil phase of this invention ma~ be crude petroleum and fractions thereof, including but not limited to diesel oil, kerosene, fuel oil, light lubricating oil fractions, and heavy naphtha having a boiling range ,, ~L~L6~t3;~
between about 300 to 600F. The preferred material is diesel oil.
The amount of the organophilic clay employed is that amount which is effective in obtaining the necessary degree of gellation (thickening) of the oil-base fluid for the intended application~ that is, drilling fluid or packer fluid. The minimwn concentration of organophilic clay needed to gel a particular fluid is dependent upon factors such as the type of organophilic clay used, the characteris-tics of the oil phase and emulsif~ied water phase if any, and the maximum temperature to which the fluid is to be raised.
The maximum concentration of organophilic clay is limited to that which will form a pumpable fluid.
The concentration of organophilic clay within the range of about 1 to about 50 lbs. per barrel (42 gallon barrel) will generally provide a sufficiently gelled fluid for broad applications. Preferably about 1 to about 10 lbs.
per barrel are employed in the preparation of oil-base drilling fluids whereas amounts from about 6 to 50 lbs. per barrel have been found adequate for the preparation of oil-base packer fluids. ~t has been found that when the organophilic clay is mixed into the oil-base fluid, essen-tially complete gelling is achieved at low shear mixing.The resulting oil-base fluid is a stable oil-base fluid at surface temperatures below -20F and down-hole temperatures up to 500F. The formation of the stable fluid occurs in a matter of minutes following addition and low shear mixing of the organophilic clay in the oil base fluid.
A packer fluid is prepared in accordance with this invention by adding to an oil medium the organophilic clay.
The composition of the packer fluid is regulated as discussed above to provide a pumpable composition. The optional emulsifiers, weighting agents, and fluid loss control materials may be added at any time. It is only necessary to obtain a stable the fluid prior to usage of the fluid. Once prepared, the packer fluid is transferred, such as by pumping, into a well bore or to tubing canulas, at least one portion of which is to be filled.
_4_ ~LG~3Z
The oil-base drilling fluid can be prepared and used either before drillinq commences or while drilling is in progress. The method of adding the ingredient to prepare the fluid is not critical. Mixing is accomplished with conventional devices capable of employing a low shear mixing force. Greater mixing force may be employed even though not necessary. Once prepared, the drilling fluid is trans-ferred, such as by pumping, into a well bore andcirculated to the bit and through the borehole in contact with the walls thereof.
The organophilic clays of this invention can be prepared by admixing the clay, quaternary ammonium compound and water together, preferably at a temperature within the range from 20C to 100C, and most preferably from 35C to 77C for a period of time sufficient for the organic compound to react with the clay particles, followed by filtering, washing, drying and grinding. The ~uaternary compound is added in the desired milliequivalent ratio, preferably dispersed in isopropanol or water. In using the organophilic clays in emulsions, the drying and grinding steps may be eliminated. When the clay, quaternary ammonium compound and water are admixed in such concentrations that a slurry is not formed, filtration and washing steps may be eliminated.
The organic cationic compounds useful in this invention may be selected from a wide range of materials that are capable of forming an organophilic clay by exchange of cations with the smectite-type clay. The or~anic cationic compound must have a positive charge localized on a single atom or on a small group of atoms within the compound.
Preferably the organic cation is selected from the group consisting of quarternary ammonium salts, phosphonium salts, and mixtures thereof, as well as equivalent salts. The organic cation preferably contains at least one member selected from each of two groups, the first group consisting of a ~, y-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon ~5~ ~6~32 atoms and mixtures thereof and the second group consisting of a long chain alkyl group.
A representative formula of the organic cation is ~
wherein Rl is selected from the group consisting of a ~,y -unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are selected from a group consisting of a ~, y-unsaturated alkyl group having less than 7 aliphatic carbon atoms , a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof ; and X is phosphorous or nitrogen.
Rl The ~,y -unsaturated alkyl group may be select~ed from a wide range of materials. These compounds may be cyclic or acyclic, unsubstituted or substituted. ~,r-unsaturated alkyl radicals should contain less than 7aliphatic carbon atoms. The aliphatic radical of the ~,y -unsaturated alkyl radicals preferably contains less than 4 aliphatic carbons. The ~,y -unsaturated alkyl radical may be substituted with an aromatic ring that is con}ugated with the unsaturation of the ~, y moiety. The ~,y - radical may also be substituted with both aliphatic radicals and aromatic rings.
Representative examples of cyclic ~,y -unsaturated alkyl groups include 2-cyclohexenyl and 2-cyclopentenyl.
Representative examples of acyclic ~,y - unsaturated alkyl groups containing 6 or less carbon atoms include propargyl;
2-propenyl; 2-butenyl; 2-pentenyl; 2-hexenyl; 3-methyl-2-bu-tenyl; 3-methyl-2-pentenyl; 2,3-dimethyl-2-butenyl; 1,1-di-methyl-2-propenyl; 1,2-dimethyl-2-propenyl; 2,4-pentadienyl;
and 2,4-hexadienyl. Representative examples of acyclic-aromatic substituted compounds include 3-phenyl-2-propenyl;
2-phenyl-2-propenyl; and 3-(4-methoxyphenyl)-2-propenyl.
Representative examples of arornatic and aliphatic substituted materials include 3-phenyl-2-cyclohexenyl; 3-phenyl-2-cyclopentenyl. The alkyl group may be substituted with an aromatic rin~.
The hydroxyalkyl group may be selected from a hydroxyl substituted aliphatic radical having from 2 to 6 aliphatic carbons wherein the hydroxyl is not substituted at the carbon adjacent to the positive charged atom. The alkyl group may be substituted with an aromatic ring. Representa-tive examples include 2-hydroxyethyl; 3-hydroxypropyl;
4-hydroxypentyl; 6-hydroxyhexyl; 2~hydroxypropyl;
2-hydroxybutyl; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxy-cyclohexyl; 3-hydroxycyclohexyl; 4-hydroxycyclohexyl;
2-hydroxycyclopentyl; 3-hydroxycyclopentyl; 2-methyl-2-hydroxypropyl; 3-methyl-2-hydroxybutyl; and 5-hydroxy-2-pentenyl.
The long chain alkyl radicals may be branched orunbranched, saturated or unsaturated, substituted or unsub-stituted and should have from 8 to 60 carbon atoms in thestraight chain portion of the radical.
The long chain alkyl radicals may be derived from naturally occurring oils including various vegetable oils~
such as corn oil, coconut oil, soybean oil, cottonseed oil, and castor oil and various animal oils and fats such as tallow oil. The alkyl radicals may be derived synthetically from alpha olefins.
Representative examples of useful branched, saturated alkyl radicals include 12-methylstearyl; and 12-ethylstearyl. Representative examples of useful branched, ~6~Q3~
unsaturated radicals include 12-methyloleyl and 12-ethyloleyl.
Representative examples of unbranched saturated radicals include lauryl; stearyl; tridecyl; myristal (tetradecyl);
pentadecyl; hexadecyl; hydrogenated tallow; docosonyl.
Representative exar,lples of unbranched, unsaturated and unsubstituted long cnain alkyl radicals include oleyl, linoleyl; linolenyl, soya and tallow.
R3 and R4 R3 and R~ are individually selected from a group consisting of (a) a ~, ~-unsaturated alkyl group having less than 7 aliphatic carbon atoms, described above, (b) a hydroxyalkyl group having 2 to 6 carbon atoms, described above; (c) a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, and (d) an aralkyl group which includes benzyl and substituted benzyl moieties including fused ring moieties having linear or branched chains of 1 to 22 carbon atoms in the alkyl portion of the aralkyl group.
The long chain alkyl group of R3 and R4 may be linear or branched, cyclic or acyclic, substituted or unsubstituted, containing 1 to 22 carbon atoms. Representa-tive examples of useful alkyl groups include methyl; ethyl;
- 25 propyl; 2-propyl; iso-butyl; cyclopentyl; and cyclohexyl.
The alkyl radicals may be derived from sources similar to the long chain alkyl radical of R2 above.
Representative examples of an aralkyl group would include benzyl and those materials derived from compounds such as benzyl halides, benzhydryl halides, trityl halides, 1-halo-1-phenylalkanes wherein the alkyl chain has from 1 to 22 carbon atoms such as 1-halo-1-phenylethane;
1-halo-1-phenyl propane; and 1-halo-1-phenyloctadecane;
substituted benzyl moieties such as would be derived from ortho-, meta- and para-chlorobenzyl halides, para-methoxybenzyl halides; ortho-, meta- and para-nitrilobenzyl halides, and ortho-, meta- and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 22 carbon atoms; and fused ring benzyl-type moieties such as would be derived from 2-halomethyl-naphthalene, 9-halomethylanthracene and .
3~
9-halomethyl-phenanthrene, wherein the halo group would be defined as chloro, bromo, iodo, or any other such group which serves as a leaving group in the nucleophilic attack of the benzyl type moiety such that the nucleophile replaces the leaving group on the benzyl type moiety.
A quaternary compound is formed of the above described organic cationic compound and an anionic radical which selected from the group consisting of chloride, bromide, nitrite, hydroxide, acetate and mixtures thereof.
Preferably the anion is selected from the group consisting of chloride and bromide, and mixtures thereof, and is more preferably chloride, although other anions such as iodide, acetate, hydroxide, nitrite, etc., may be present in the organic cationic compound to neutralize the cation.
Organic cationic salts may be prepared by methods as disclosed in U.S. 2,355,356, 2,775,617 and 3,136,819.
For convenience of handling it is preferred that the total organic content of the organophilic clay reaction products of this invention should be less than about 50~ by weight of the organoclay. While higher amounts are usable, the reaction product is difficult to filter, dry and grind.
The amount of organic cation added to the clay for purposes of this invention must be sufficient to impart to the clay the enhanced dispersion characteristic desired.
This amount is defined as the millequivalent ratio which is the number of milliequivalents (M.E.) of the organic cation in the organoclay per 100 grams of clay, 100% active clay basis. The organophilic clays of this invention must have a milliequivalent ratio from 90 to 140 and preferably 100 to 130. At lower milliequivalent ratios the organophilic clays produced are not effective gellants. At higher milliequivalent ratios the organophilic clays are poor gellants. However, the pre~erred milliequivalent ratio within the range from 90 to 140 will vary depending on the characteristics of the organic system to be gelled by the organophilic clay.
The manner in which the organic cation function~
in the organophilic clay reaction products of this invention -9- ~ V3Z
( is not fully known. The unique properties associated with the compositions of this invention are believed however to relate to the electron withdrawing and donating portions of the cation and particulariy to the essential presence of at least one long chain alkyl group coupled with a ~, -unsaturated alkyl group or a nydroxyalkyl group.
When bonded to a positivly charged atom the long chain a]jkyl group appears to function as an electron donor which aids in delocalizing the positive charge. More importantly however it enables the clay platel~ets to be separated sufficiently to allow further separation under moderate shear conditions. In contrast, the ~, y-unsaturated alkyl group appears to create a delocalization of the positive charge which may result from a resonance or inductive effect occurring with the unsaturated alkyl group. This effect does not occur tQ any significant extent with other prior art saturated alkyl groups. The enhanced function of the short chain hydroxyalkyl group appears to be related to the internal covalent bonded polar activating moiety t namely the hydroxyl group when not adjacent the positive charged atom. This effect is negated when the hydroxyl moiety is located on a carbon atom adjacent to the positive ~5 charged atom or on an alkyl gro~n greater than 6 carbon atoms.
Suitable smectite-type clays occur naturally or may be prepared synthetically. Such clays include mont-morillonite, bentonite, beidellite, hectorite, saponite, and stevensite. In particular smectite-type clays should have a cation exchange capacity of at least 75 milli-equivalents per 100 grams of clay. Particularly desirable types of clay are the naturally-occurring Wyoming varieties of bentonite and hectorite, a magnesium-lithium silicate clay. Suitable clays may also be synthesized by conven-tional means including pneumatolitic and hydrothermal methods.
The clays, especially the bentonite type clays, are preferably converted to the sodium form if they are no~
~0 already in this form. This can conveniently be done by preparinq an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form.
Alternatively, the clay can be mixed with water and a soluble sodium compound such as sodium carbonate and sodium hydroxide followed by shearing the mixture with a pugmill or extruder.
The cation exchange capacity of the smectite-type clays can be determinèd by the ammonium acetate method.
The clay is preferably dispersed in water in a weight concentration ranging from about 1 to about 80% and preferably from about 2~ to about 20%, and more preferably from about 2% to about 7%. The slurry is agitated prior to reaction.
The organic cationic compounds of the invention were prepared by standard prior art methods starting with an amine having the desired number of long chain alkyl groups bonded to the nitrogen atom. This long chain alkyl amine was then reacted by reductive alkylation with an aldehyde or by nucleophilic displacement of an alkyl halide to form the desired quaternary ammonium compound.
The fluid of this invention may contain an aqueous phase which includes aqueous solutions of inorganic salts such as sodium chloride and calcium chloride. While addi-tion of these salts is optional, such salts increase the osmotic pressure of the water phase to stabilize formations containing hydratable clays.
The concentration of water in the fluid is deter-mined by factors such as fluid weight requirements, flowproperties desired, bottom-hole temperatures and the opera-tional requirements of drilling, coring, or completion. In general, it has been found preferably to employ a volume percent of water ranging from about 2 to about 50%. This range renders the oil-base fluid fire~resistant upon expo-sure to temperatures that would ignite it. In addition, the fluid has excellent tolerance to water contamination; and fluid flow properties can be controlled at values comparable to those of water-based fluids.
In using an aqueous phase in the fluid, conven-~6(~3Z
tional emulsifiers should be employed for the water-in-oil phase. In the non-agueous fluid, emulsifiers may also be used. The amount of emulsifier employed is primarily dependent upon the amount of water present and the extent of emulsification desired. Generally from 2 to 30 lbs. per barrel and preferably from 1 to 15 lbs. per barrel have been found satisfactory to achieve the emulsion stability.
The compositions may optionally contain convention-al weighting agents such as barite for controlling fluid density between 7.5 and 22 lb/gal~as well as fluid loss control agents.
The smectite-type clays used in the Examples were hectorite and Wyomin~ bentonite. The clay was slurried n water and centrifuged to remove essentially all of the non-clay impurities which may amount to 10% to a~out 50% of the starting clay composition. The Wyoming bentonite clay slurry was passed through a bed of cation exchange resin to convert it to the sodium form.
The organic cationic compounds exemplified are representative of the cations of the invention and are not intended to be inclusive of the only operative compounds.
The following examples are given to illustrate the invention, but are not deemed to be limiting thereof.
All percentages given are based upon weight unless otherwise indicated. Plastic viscosity, yield point, and ten second gels were measured by the procedure described in API RP13B, American Petroleum Institutes Standard Procedure 0 for Testing Fluids, 6th Ed., April 1976.
Example 1 Allyl methyl di(hydrogenated-tallow) ammonium chloride (abbreviated AM2HT).
824.7 g methyl di(hydrogenated-tallow) amine, 350 ml isopropyl alcohol, 250 g NaHCO3, 191.3 g are placed allyl chloricle, and 10 g allyl bromide (as a catalyst) in a 4-liter reaction vessel equipped with a condenser, the mixture is heated and allowed to reflux. A sample was removed, filtered, and titrated with HCl and NaOH. The reaction was considered complete at 0.0~ amine HCl and 1.8%
!
amine. The final analysis showed an effective gram molecular weiqht of 831.17.
Examples 2-4 A 3~ clay slurry, the sodium form of Wyoming bentonite for Examples 2 and 3 and hectorite for Example 4, was heated to 60C with stirring. An isopropyl alochol solution of organic cationic compound, ethanol methyl di(hydrogenated tallow) ammonium chloride [E~fil2HT] - (Armak Co. Division of Akzona Corp.) at 80% activity in Example 2 and AM2HT, prepared in Example 1, for Examples 3 and 4 was added to the clay slurry and stirred for 20 minutes. The orgânoclay was collected on a vacuum filter. The filter cake was washed with 60C water and dried at 60C. The dried oryanoclay was ground using a hammer mill to reduce the particle size and sieved through a U.S. Standard 200 mesh screen.
Examples 5-8 ~0.63 bbl of diesel oil, 8 pounds emulsifier (Invermul, NL Industries~, Inc.), 8 pounds filtration control, amine lignite (Duratone~HT, NL Industries, Inc.) 4 pounds lime, 0.11 bbl. of water was stirred for 20 minutes.
22 pounds of calcium chloride, 325 pounds of barite (Baroid, NL Industries, Inc.) and 5 pounds of the two bentonite clay thickeners prepared in Examples 2 and 3 in addition to two commercial products, dimethyl~di(hydrogenated-tallow) ammonium chloride [2M2HT]/ bentonite and benzyl methyl di(hydrogenated-tallow) ammonium chloride [BM2HT]/ bentonite.
The mixed fluid was tested at 95E. for standard rheology data and the results are shown in Table 1~ None of the Examples settled following stirring:
Table 1 Yield 10 sec. 10 min.
Point Gel Gel Example Gellant #/ 2 #/ #/
No. Compound 100ft 100ft2 100ft2 EM2H'r/bentonite 18 9 13 6 AM2~3T/bentonite 20 11 14 7 2M2HT/bentonite 30 16 19 40 8 BM2~3T/bentonite 24 14 18 ~L~L6~6~32 The unstirred batches of Examples 5-8 were rolled at 150F for 16 hours and no settlinq was noted in any Example.
The batches were tested at 80F for standard rheology data as in Example 5. The results are shown in Table 2 below.
None of the Examples settled.
Table 2 Yield 10 sec. 10 min.
Point Gel Gel Example #/ ~/ #/
No. 100ft2 lOOft2 100ft Examples 9-13 350 ml. batches of of fluids consistin~ of 0.60 bbl o~ diesel oil, 8 pounds emulsifier (Invermul , NL
Industries, Inc.), 8 pounds amine lignite filtration control aid (Duratone~, NL Industries, Inc.), 5 pounds lime, 0.20 bbl of ll.0 lb. per gallon, aqueous calcium chloride, aqueous 320 pounds of barite (Baroid~, NL Industries, Inc.) was admixed, stirred for 15 minutes in a Hamilton Beach mixer and cooled to 28F in an ice bath. A 6 lb/bbl concentration of the clays EM2HT/bentonite, AM2~T/bentonite and A~12HT/hectorite produced in Examples 2, 3, and 4 respectively in addition to two commercial clays 2M2~T/bentonite and BM2HT/bentonite described in Examples 7 and 8 were stirred into the cold fluid batches over a 5 minute period at low shear with a Lightnin mixer.
The cold examples in a viscometer cup, were placed on a Fann 35 viscometer and stirred at 600 rpm while the temperature rose to 7QF. The batches were then placed in a preheated cup jackets set at 125F and allowed to heat to 110DF. The plastic viscosity, yield point and 10-sec gel were measured at every 5F increment between 30 to 70F and at every 10F
increment between 70 to 110F. The results of the measure-ments are presented in Fiqure 1.
Examples ~-13 at 115F were stirred for 15 minutes in a Hamilton Beach mixer and cooled to 8nF and tested as with Example 5. The results are presented in Table 3 below.
-14- ~ ~6~03Z
( Table 3 Yield 10 sec. 10 min.
Point Gel Gel Example#/ 2 `' #/ 2 ~/ 2 No. lnOft 100ft _ Oft Example 14-17 Fluids consisting of 0.41 bbl of diesel oil and 12 pounds of gellant clays prepared in Example 2 and 3 in addition to commercial clays 2M2HT/ bentonite and BM2HT/
bentonite were admixed and stirred for five minutes in a ~amilton Beach mixer at low speed. Fluids consis~ing of 0.41 bbl of diesel oil, 18 pounds asphalt (Baroid Asphalt, NL Industries, Inc.) and 275 pounds of barite, (Baroid~ NL
Industries, Inc.) were prepared and admixed with the prepared fluids above to form 350 ml batches which stirred for 15 minutes in a Hamilton Beach mixer.
350 ml samples of Examples 14 through 17 were tested for rheological properties as in Example 5 at 93F.
The results are presented in Table 4 below.
- Table~4 Yield lO sec. lO min.
Point Gel Gel ExampleGellant #/ #/ #/
No. Compound lOOft2 lOOft2 lOOft2 l4 EM2HT/bentonite 26 7 54 AM2HT/bentonite 30 ll 48 16 2M2HT/bentonite 54 34 74 17 BM2HT/bentonite 25 ll 40 350 ml samples of Examples 14 through 17 were hot rolled at 150F for 16 hoursO After cooling the batches to 80F, settling of solids were checked prior to measurement of rheological properties as in Example 5 at 93F. The results are shown in Table 5 below~
Table 5 Yield 10 sec. 10 min.
Point Gel Gel Example #/ #/ #/
No. lOOft2 ; lOOft2 lOOfk2 _ _ . . . ..
Example 14 shows improved results when mixed in a non-aqueous fluid. These results~show improvements in forming a gel quickly and remaining low at 10 minute gel indicating a maintenance of pumpability.
Mud cake and filtrates were stirred back into the respective samples and the batches were aged for 16 hours at 350~F. Each batch was cooled to 80F and checked for solids settling. The batches were stirred for 5 minutes and tested as with Example 5. The results are shown in Table 6 below.
Table 6 Yield 10 sec. 10 minO
Point Gel Gel Example ~ #/
No. lOOft2 lOOft2 lOOft2 lOS 31 83 Example 18-21 350 ml batches of fluids consisting of 0.69 bbl of diesel oil, 6 pounds emulsifier tEZ mul~, NL Industries, Inc.), 0.12 bbl of water, 225 pounds of barite, (Bario ~, NL Industries, Inc.), 24 pounds of calcium chloride and 6 pounds of gellant clays EM2HT/bentonite and AM2~T/bentonite prepared in Example 2 and 3 respectively in addition to 2M2HT/bentonite and BM2HT/bentonite were admixed and stirred for 20 rninutes in a Hamilton Beach mixer.
350 ml batch of Examples 18 through 21 were tested for rheological properties as in Example 5 at 88F~ The results are presented in Table 7 below.
~L~6~32 Table7 10 sec. 10 min.
Point Gel Gel Example Gellant ` #/ 2 / 2 / 2 Wo. Gellant Compound lOOft 100ft lOOft 18 EM2HT/bentonite 9 4 5 19 Al~l2HT/bentonite 8 S 6 2M2HT/bentonite 9 5 6 1021 ~M2HT/bentonite 8 4 5 350 ml sample of Example 18 through 21 were hot rolled at 150F for 16 hours. After cooling the batches to 80F, settling of solids was checked prior to measurement of rheological properties as in Example 5 at 84F. The results are shown in Table 8 below.
Table ~
Yield 10 sec.lO min.
Point Gel Gel Example#/ 2 #/ 2 No.100ft lOOft 100ft 201~ 11 5 8 lg 11 5 5 21 g Mud cake and filtrate were stirred back into the respective samples and the batches were aged for 16 hours at 350F.
Each batch was cooled to 80F, checked for solids settling and electrical stability. The batches were stirred for 5 minutes and tested as with Example 5. HT-HP filtrates were conducted on each batch at 350 F. The results are shown in Table 9 below.
Table 9 Yield 10 sec.lO min.
Point Gel Gel Example~/ 2 #/ 2#/ 2 No.lOOft lOOft lOOft l9 10 4 5 Example 22-27 350 ml batches of packer fluids consisting of 0.63 bbl of diesel oil, 8 pounds emulsifier (Invermul~ NL
Industries, Inc.), 0.11 bbl of water, 325 pounds of barite, (Baroid~3~L Industries, Inc.), 8 pounds filtration aid (Duratone, NL Industries, Inc.), 22 pounds of calcium chloride, 4 pounds lime and 9 pounds of gellant clays EM2HT/bentonite, AM2HT/bentonite, and A~2HT/hectorite prepared in Example 2, 3 and 4 respectively in addition to three commercial clays, dimethyl di(hydro~enated-tallow) ammonium chloride, 2~2HT/bentonite; benzyl methyl di-(hydrogenated-tallow) ammonium chloride, BM2HT/bentonite;
ana dimethyl di(hydrogenated-tallow) ammonium chloride, 2~2HT/hectorite were admixed and stirred for 20 minutes in a Hamilton Beach mixer.
350 ml sample of Examples 22 through 27 were tested for rheological properties as in Example 5 at 92 F.
The results are presented in TablelO.
Table lO
Yield10 sec. 10 min.
Point Gel Gel Example ~/ ~/ 2 2 No. Gellant Compound lOOft2100ft _ 100ft 2522 EM2HT/bentonite 36 11 16 23 AM2HT/bentonite 42 18 23 24 A~2HT/hectorite 55 23 27 2M2HT/bentonite 60 22 33 26 BM2HT/bentonite 51 24 28 3G27 BM2HT/hectorite 65 32 39 Mud cake and and filtrate were stirred back into each batch and the batches were aged at 350F for 16 hours. Each batch was cooled to 80F, checked for solids settling and electrical stability. The batches were admixed, stirred for 10 minutes and tested as with Example 5 at 90F. The results are shown in Table 10 below.
... . ~
~L6L3~3Z
f Table ll .
Yield 10 sec. 10 min.
Point Gel Gel Example / 2 #~ #/
No. lOOft lOOft2 lOOft2 350 ml batches of Examples 23, 24, 25 and 37 were aged for 16 hours at 300F, 400F and 450F. The batches were tested as above at 99F and the results are shown in Tablel2 .
Table 12 Yield 10 sec. 10 min.
Point Gel Gel ExampleTemperature #/ #/ #/ 2 No. F lOOft2 lOO~t2lOOft It will be obvious to one skilled in the art that the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are ; intended to be included within the scope of the following claims.
9-halomethyl-phenanthrene, wherein the halo group would be defined as chloro, bromo, iodo, or any other such group which serves as a leaving group in the nucleophilic attack of the benzyl type moiety such that the nucleophile replaces the leaving group on the benzyl type moiety.
A quaternary compound is formed of the above described organic cationic compound and an anionic radical which selected from the group consisting of chloride, bromide, nitrite, hydroxide, acetate and mixtures thereof.
Preferably the anion is selected from the group consisting of chloride and bromide, and mixtures thereof, and is more preferably chloride, although other anions such as iodide, acetate, hydroxide, nitrite, etc., may be present in the organic cationic compound to neutralize the cation.
Organic cationic salts may be prepared by methods as disclosed in U.S. 2,355,356, 2,775,617 and 3,136,819.
For convenience of handling it is preferred that the total organic content of the organophilic clay reaction products of this invention should be less than about 50~ by weight of the organoclay. While higher amounts are usable, the reaction product is difficult to filter, dry and grind.
The amount of organic cation added to the clay for purposes of this invention must be sufficient to impart to the clay the enhanced dispersion characteristic desired.
This amount is defined as the millequivalent ratio which is the number of milliequivalents (M.E.) of the organic cation in the organoclay per 100 grams of clay, 100% active clay basis. The organophilic clays of this invention must have a milliequivalent ratio from 90 to 140 and preferably 100 to 130. At lower milliequivalent ratios the organophilic clays produced are not effective gellants. At higher milliequivalent ratios the organophilic clays are poor gellants. However, the pre~erred milliequivalent ratio within the range from 90 to 140 will vary depending on the characteristics of the organic system to be gelled by the organophilic clay.
The manner in which the organic cation function~
in the organophilic clay reaction products of this invention -9- ~ V3Z
( is not fully known. The unique properties associated with the compositions of this invention are believed however to relate to the electron withdrawing and donating portions of the cation and particulariy to the essential presence of at least one long chain alkyl group coupled with a ~, -unsaturated alkyl group or a nydroxyalkyl group.
When bonded to a positivly charged atom the long chain a]jkyl group appears to function as an electron donor which aids in delocalizing the positive charge. More importantly however it enables the clay platel~ets to be separated sufficiently to allow further separation under moderate shear conditions. In contrast, the ~, y-unsaturated alkyl group appears to create a delocalization of the positive charge which may result from a resonance or inductive effect occurring with the unsaturated alkyl group. This effect does not occur tQ any significant extent with other prior art saturated alkyl groups. The enhanced function of the short chain hydroxyalkyl group appears to be related to the internal covalent bonded polar activating moiety t namely the hydroxyl group when not adjacent the positive charged atom. This effect is negated when the hydroxyl moiety is located on a carbon atom adjacent to the positive ~5 charged atom or on an alkyl gro~n greater than 6 carbon atoms.
Suitable smectite-type clays occur naturally or may be prepared synthetically. Such clays include mont-morillonite, bentonite, beidellite, hectorite, saponite, and stevensite. In particular smectite-type clays should have a cation exchange capacity of at least 75 milli-equivalents per 100 grams of clay. Particularly desirable types of clay are the naturally-occurring Wyoming varieties of bentonite and hectorite, a magnesium-lithium silicate clay. Suitable clays may also be synthesized by conven-tional means including pneumatolitic and hydrothermal methods.
The clays, especially the bentonite type clays, are preferably converted to the sodium form if they are no~
~0 already in this form. This can conveniently be done by preparinq an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form.
Alternatively, the clay can be mixed with water and a soluble sodium compound such as sodium carbonate and sodium hydroxide followed by shearing the mixture with a pugmill or extruder.
The cation exchange capacity of the smectite-type clays can be determinèd by the ammonium acetate method.
The clay is preferably dispersed in water in a weight concentration ranging from about 1 to about 80% and preferably from about 2~ to about 20%, and more preferably from about 2% to about 7%. The slurry is agitated prior to reaction.
The organic cationic compounds of the invention were prepared by standard prior art methods starting with an amine having the desired number of long chain alkyl groups bonded to the nitrogen atom. This long chain alkyl amine was then reacted by reductive alkylation with an aldehyde or by nucleophilic displacement of an alkyl halide to form the desired quaternary ammonium compound.
The fluid of this invention may contain an aqueous phase which includes aqueous solutions of inorganic salts such as sodium chloride and calcium chloride. While addi-tion of these salts is optional, such salts increase the osmotic pressure of the water phase to stabilize formations containing hydratable clays.
The concentration of water in the fluid is deter-mined by factors such as fluid weight requirements, flowproperties desired, bottom-hole temperatures and the opera-tional requirements of drilling, coring, or completion. In general, it has been found preferably to employ a volume percent of water ranging from about 2 to about 50%. This range renders the oil-base fluid fire~resistant upon expo-sure to temperatures that would ignite it. In addition, the fluid has excellent tolerance to water contamination; and fluid flow properties can be controlled at values comparable to those of water-based fluids.
In using an aqueous phase in the fluid, conven-~6(~3Z
tional emulsifiers should be employed for the water-in-oil phase. In the non-agueous fluid, emulsifiers may also be used. The amount of emulsifier employed is primarily dependent upon the amount of water present and the extent of emulsification desired. Generally from 2 to 30 lbs. per barrel and preferably from 1 to 15 lbs. per barrel have been found satisfactory to achieve the emulsion stability.
The compositions may optionally contain convention-al weighting agents such as barite for controlling fluid density between 7.5 and 22 lb/gal~as well as fluid loss control agents.
The smectite-type clays used in the Examples were hectorite and Wyomin~ bentonite. The clay was slurried n water and centrifuged to remove essentially all of the non-clay impurities which may amount to 10% to a~out 50% of the starting clay composition. The Wyoming bentonite clay slurry was passed through a bed of cation exchange resin to convert it to the sodium form.
The organic cationic compounds exemplified are representative of the cations of the invention and are not intended to be inclusive of the only operative compounds.
The following examples are given to illustrate the invention, but are not deemed to be limiting thereof.
All percentages given are based upon weight unless otherwise indicated. Plastic viscosity, yield point, and ten second gels were measured by the procedure described in API RP13B, American Petroleum Institutes Standard Procedure 0 for Testing Fluids, 6th Ed., April 1976.
Example 1 Allyl methyl di(hydrogenated-tallow) ammonium chloride (abbreviated AM2HT).
824.7 g methyl di(hydrogenated-tallow) amine, 350 ml isopropyl alcohol, 250 g NaHCO3, 191.3 g are placed allyl chloricle, and 10 g allyl bromide (as a catalyst) in a 4-liter reaction vessel equipped with a condenser, the mixture is heated and allowed to reflux. A sample was removed, filtered, and titrated with HCl and NaOH. The reaction was considered complete at 0.0~ amine HCl and 1.8%
!
amine. The final analysis showed an effective gram molecular weiqht of 831.17.
Examples 2-4 A 3~ clay slurry, the sodium form of Wyoming bentonite for Examples 2 and 3 and hectorite for Example 4, was heated to 60C with stirring. An isopropyl alochol solution of organic cationic compound, ethanol methyl di(hydrogenated tallow) ammonium chloride [E~fil2HT] - (Armak Co. Division of Akzona Corp.) at 80% activity in Example 2 and AM2HT, prepared in Example 1, for Examples 3 and 4 was added to the clay slurry and stirred for 20 minutes. The orgânoclay was collected on a vacuum filter. The filter cake was washed with 60C water and dried at 60C. The dried oryanoclay was ground using a hammer mill to reduce the particle size and sieved through a U.S. Standard 200 mesh screen.
Examples 5-8 ~0.63 bbl of diesel oil, 8 pounds emulsifier (Invermul, NL Industries~, Inc.), 8 pounds filtration control, amine lignite (Duratone~HT, NL Industries, Inc.) 4 pounds lime, 0.11 bbl. of water was stirred for 20 minutes.
22 pounds of calcium chloride, 325 pounds of barite (Baroid, NL Industries, Inc.) and 5 pounds of the two bentonite clay thickeners prepared in Examples 2 and 3 in addition to two commercial products, dimethyl~di(hydrogenated-tallow) ammonium chloride [2M2HT]/ bentonite and benzyl methyl di(hydrogenated-tallow) ammonium chloride [BM2HT]/ bentonite.
The mixed fluid was tested at 95E. for standard rheology data and the results are shown in Table 1~ None of the Examples settled following stirring:
Table 1 Yield 10 sec. 10 min.
Point Gel Gel Example Gellant #/ 2 #/ #/
No. Compound 100ft 100ft2 100ft2 EM2H'r/bentonite 18 9 13 6 AM2~3T/bentonite 20 11 14 7 2M2HT/bentonite 30 16 19 40 8 BM2~3T/bentonite 24 14 18 ~L~L6~6~32 The unstirred batches of Examples 5-8 were rolled at 150F for 16 hours and no settlinq was noted in any Example.
The batches were tested at 80F for standard rheology data as in Example 5. The results are shown in Table 2 below.
None of the Examples settled.
Table 2 Yield 10 sec. 10 min.
Point Gel Gel Example #/ ~/ #/
No. 100ft2 lOOft2 100ft Examples 9-13 350 ml. batches of of fluids consistin~ of 0.60 bbl o~ diesel oil, 8 pounds emulsifier (Invermul , NL
Industries, Inc.), 8 pounds amine lignite filtration control aid (Duratone~, NL Industries, Inc.), 5 pounds lime, 0.20 bbl of ll.0 lb. per gallon, aqueous calcium chloride, aqueous 320 pounds of barite (Baroid~, NL Industries, Inc.) was admixed, stirred for 15 minutes in a Hamilton Beach mixer and cooled to 28F in an ice bath. A 6 lb/bbl concentration of the clays EM2HT/bentonite, AM2~T/bentonite and A~12HT/hectorite produced in Examples 2, 3, and 4 respectively in addition to two commercial clays 2M2~T/bentonite and BM2HT/bentonite described in Examples 7 and 8 were stirred into the cold fluid batches over a 5 minute period at low shear with a Lightnin mixer.
The cold examples in a viscometer cup, were placed on a Fann 35 viscometer and stirred at 600 rpm while the temperature rose to 7QF. The batches were then placed in a preheated cup jackets set at 125F and allowed to heat to 110DF. The plastic viscosity, yield point and 10-sec gel were measured at every 5F increment between 30 to 70F and at every 10F
increment between 70 to 110F. The results of the measure-ments are presented in Fiqure 1.
Examples ~-13 at 115F were stirred for 15 minutes in a Hamilton Beach mixer and cooled to 8nF and tested as with Example 5. The results are presented in Table 3 below.
-14- ~ ~6~03Z
( Table 3 Yield 10 sec. 10 min.
Point Gel Gel Example#/ 2 `' #/ 2 ~/ 2 No. lnOft 100ft _ Oft Example 14-17 Fluids consisting of 0.41 bbl of diesel oil and 12 pounds of gellant clays prepared in Example 2 and 3 in addition to commercial clays 2M2HT/ bentonite and BM2HT/
bentonite were admixed and stirred for five minutes in a ~amilton Beach mixer at low speed. Fluids consis~ing of 0.41 bbl of diesel oil, 18 pounds asphalt (Baroid Asphalt, NL Industries, Inc.) and 275 pounds of barite, (Baroid~ NL
Industries, Inc.) were prepared and admixed with the prepared fluids above to form 350 ml batches which stirred for 15 minutes in a Hamilton Beach mixer.
350 ml samples of Examples 14 through 17 were tested for rheological properties as in Example 5 at 93F.
The results are presented in Table 4 below.
- Table~4 Yield lO sec. lO min.
Point Gel Gel ExampleGellant #/ #/ #/
No. Compound lOOft2 lOOft2 lOOft2 l4 EM2HT/bentonite 26 7 54 AM2HT/bentonite 30 ll 48 16 2M2HT/bentonite 54 34 74 17 BM2HT/bentonite 25 ll 40 350 ml samples of Examples 14 through 17 were hot rolled at 150F for 16 hoursO After cooling the batches to 80F, settling of solids were checked prior to measurement of rheological properties as in Example 5 at 93F. The results are shown in Table 5 below~
Table 5 Yield 10 sec. 10 min.
Point Gel Gel Example #/ #/ #/
No. lOOft2 ; lOOft2 lOOfk2 _ _ . . . ..
Example 14 shows improved results when mixed in a non-aqueous fluid. These results~show improvements in forming a gel quickly and remaining low at 10 minute gel indicating a maintenance of pumpability.
Mud cake and filtrates were stirred back into the respective samples and the batches were aged for 16 hours at 350~F. Each batch was cooled to 80F and checked for solids settling. The batches were stirred for 5 minutes and tested as with Example 5. The results are shown in Table 6 below.
Table 6 Yield 10 sec. 10 minO
Point Gel Gel Example ~ #/
No. lOOft2 lOOft2 lOOft2 lOS 31 83 Example 18-21 350 ml batches of fluids consisting of 0.69 bbl of diesel oil, 6 pounds emulsifier tEZ mul~, NL Industries, Inc.), 0.12 bbl of water, 225 pounds of barite, (Bario ~, NL Industries, Inc.), 24 pounds of calcium chloride and 6 pounds of gellant clays EM2HT/bentonite and AM2~T/bentonite prepared in Example 2 and 3 respectively in addition to 2M2HT/bentonite and BM2HT/bentonite were admixed and stirred for 20 rninutes in a Hamilton Beach mixer.
350 ml batch of Examples 18 through 21 were tested for rheological properties as in Example 5 at 88F~ The results are presented in Table 7 below.
~L~6~32 Table7 10 sec. 10 min.
Point Gel Gel Example Gellant ` #/ 2 / 2 / 2 Wo. Gellant Compound lOOft 100ft lOOft 18 EM2HT/bentonite 9 4 5 19 Al~l2HT/bentonite 8 S 6 2M2HT/bentonite 9 5 6 1021 ~M2HT/bentonite 8 4 5 350 ml sample of Example 18 through 21 were hot rolled at 150F for 16 hours. After cooling the batches to 80F, settling of solids was checked prior to measurement of rheological properties as in Example 5 at 84F. The results are shown in Table 8 below.
Table ~
Yield 10 sec.lO min.
Point Gel Gel Example#/ 2 #/ 2 No.100ft lOOft 100ft 201~ 11 5 8 lg 11 5 5 21 g Mud cake and filtrate were stirred back into the respective samples and the batches were aged for 16 hours at 350F.
Each batch was cooled to 80F, checked for solids settling and electrical stability. The batches were stirred for 5 minutes and tested as with Example 5. HT-HP filtrates were conducted on each batch at 350 F. The results are shown in Table 9 below.
Table 9 Yield 10 sec.lO min.
Point Gel Gel Example~/ 2 #/ 2#/ 2 No.lOOft lOOft lOOft l9 10 4 5 Example 22-27 350 ml batches of packer fluids consisting of 0.63 bbl of diesel oil, 8 pounds emulsifier (Invermul~ NL
Industries, Inc.), 0.11 bbl of water, 325 pounds of barite, (Baroid~3~L Industries, Inc.), 8 pounds filtration aid (Duratone, NL Industries, Inc.), 22 pounds of calcium chloride, 4 pounds lime and 9 pounds of gellant clays EM2HT/bentonite, AM2HT/bentonite, and A~2HT/hectorite prepared in Example 2, 3 and 4 respectively in addition to three commercial clays, dimethyl di(hydro~enated-tallow) ammonium chloride, 2~2HT/bentonite; benzyl methyl di-(hydrogenated-tallow) ammonium chloride, BM2HT/bentonite;
ana dimethyl di(hydrogenated-tallow) ammonium chloride, 2~2HT/hectorite were admixed and stirred for 20 minutes in a Hamilton Beach mixer.
350 ml sample of Examples 22 through 27 were tested for rheological properties as in Example 5 at 92 F.
The results are presented in TablelO.
Table lO
Yield10 sec. 10 min.
Point Gel Gel Example ~/ ~/ 2 2 No. Gellant Compound lOOft2100ft _ 100ft 2522 EM2HT/bentonite 36 11 16 23 AM2HT/bentonite 42 18 23 24 A~2HT/hectorite 55 23 27 2M2HT/bentonite 60 22 33 26 BM2HT/bentonite 51 24 28 3G27 BM2HT/hectorite 65 32 39 Mud cake and and filtrate were stirred back into each batch and the batches were aged at 350F for 16 hours. Each batch was cooled to 80F, checked for solids settling and electrical stability. The batches were admixed, stirred for 10 minutes and tested as with Example 5 at 90F. The results are shown in Table 10 below.
... . ~
~L6L3~3Z
f Table ll .
Yield 10 sec. 10 min.
Point Gel Gel Example / 2 #~ #/
No. lOOft lOOft2 lOOft2 350 ml batches of Examples 23, 24, 25 and 37 were aged for 16 hours at 300F, 400F and 450F. The batches were tested as above at 99F and the results are shown in Tablel2 .
Table 12 Yield 10 sec. 10 min.
Point Gel Gel ExampleTemperature #/ #/ #/ 2 No. F lOOft2 lOO~t2lOOft It will be obvious to one skilled in the art that the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are ; intended to be included within the scope of the following claims.
Claims (18)
1. An oil-base fluid comprising an oil phase and from about 1 to 50 lbs. per barrel of an organophilic clay gellant comprising the reaction product of an organic cationic compound and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay, wherein said organic cation has the formula:
wherein R1 is selected from the group consisting of a .beta., .gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a .beta., .gamma.-unsaturated alkyl groups having less than 7 aliphatic carbon atoms , a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof; X is selected from a group consisting of phosphorous and nitrogen; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100% active clay basis.
wherein R1 is selected from the group consisting of a .beta., .gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a .beta., .gamma.-unsaturated alkyl groups having less than 7 aliphatic carbon atoms , a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof; X is selected from a group consisting of phosphorous and nitrogen; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100% active clay basis.
2, An oil-base packer fluid comprising an oil phase, and from about 6 to 50 lbs. per barrel of an organophilic clay gellant comprising the reaction product of an organic cationic compound and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay, wherein said organic cation has the formula:
wherein R1 is selected from the group consisting of a .beta., .gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a .beta., .gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof; X is selected from a group consisting of phosphorous and nitrogen; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100%
active clay basis.
wherein R1 is selected from the group consisting of a .beta., .gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a .beta., .gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof; X is selected from a group consisting of phosphorous and nitrogen; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100%
active clay basis.
3. In a method of insulating casing in a wellbore which comprises pumping an oil-base packer fluid in an annular space within said wellbore and thereafter gelling said packer fluid, the improvement comprises a packer fluid having an oil phase, and from about 6 to about 50 lbs. per barrel of an organophilic clay gellant comprising the reaction product of an organic cationic compound and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay, wherein said organic cation has the formula:
wherein R1 is selected from the group consisting of a .beta.,.gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a .beta.,.gamma.-unsaturated alkyl group having less thna 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof; X is selected from a group consisting of phosphorous and nitrogen; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100% active clay basis.
wherein R1 is selected from the group consisting of a .beta.,.gamma.
-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 8 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a .beta.,.gamma.-unsaturated alkyl group having less thna 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms and mixtures thereof; X is selected from a group consisting of phosphorous and nitrogen; and wherein the amount of said organic cationic compound is from 90 to 140 milliequivalents per 100 grams of said clay, 100% active clay basis.
4. The gellant of Claim 1 or 2 wherein said smectite-type clay is selected from the group consisting of hectorite and sodium bentonite.
5. The gellant of Claim 1 or 2 wherein R1 is a .beta.,.gamma.-unsaturated group selected from a group consisting of cyclic groups, acyclic alkyl groups having less than 7 carbon atoms, acyclic alkyl groups substituted with aromatic groups, aromatic groups substituted with aliphatic groups and mixtures thereof.
6. The gellant of Claim 1 or 2 wherein R1 is a hydroxyalky group selected from a group consisting of cyclic groups, acyclic aliphatic groups and mixtures thereof, said aliphatic groups having the hydroxyl substitu-tion on C2 to C6.
7. The gellant of Claim 1, wherein R2 has from 12 to 22 carbon atoms.
8. The gellant of Claim 7 wherein R2 is a long chain fatty acid group.
9. The gellant of Claim 1 or 2 wherein the amount of said organic cation is from 100 to 130 milli-equivalents per 100 grams of said clay, 100% active clay basis.
10. The fluid of Claim 1 wherein said fluid comprises additionally a dispersed aqueous phase comprising from about 2 to about 50% by volume water.
11. The fluid of Claim 10 wherein said fluid comprises additionally a water-in-oil emulsifier.
12. The fluid of Claim 11 wherein said emulsifier comprises from about 2 to about 30 lbs. per barrel of said fluid.
13. The packer fluid of Claim 2 wherein said fluid comprises additionally a dispersed aqueous phase comprising from about 2 to about 50% by volume water.
14. The packer fluid of Claim 13 wherein said fluid comprises additionally a water-in-oil emulsifier.
15. The packer fluid of Claim 14 wherein said emulsifier comprises from about 2 to about 30 pounds per barrel of said fluid.
16. The fluid of Claim 1 wherein said fluid is non-aqueous.
17. The fluid of Claim 2 wherein said fluid is non-aqueous.
18. The fluid of Claim 1 wherein said gellant comprises about 1 to about 10 pounds per barrel of said fluid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31305081A | 1981-10-19 | 1981-10-19 | |
| US313,050 | 1981-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160032A true CA1160032A (en) | 1984-01-10 |
Family
ID=23214159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000390140A Expired CA1160032A (en) | 1981-10-19 | 1981-11-16 | Oil base fluids containing organophilic clays |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5876485A (en) |
| AU (1) | AU551121B2 (en) |
| BR (1) | BR8107427A (en) |
| CA (1) | CA1160032A (en) |
| EG (1) | EG15460A (en) |
| FR (1) | FR2514663B1 (en) |
| GB (1) | GB2108175B (en) |
| IN (1) | IN158428B (en) |
| IT (1) | IT1194109B (en) |
| NO (1) | NO155811B (en) |
| SE (1) | SE8106797L (en) |
| SG (1) | SG24587G (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8407531D0 (en) * | 1984-03-22 | 1984-05-02 | Laporte Industries Ltd | Organophilic clay gellants |
| US4664820A (en) * | 1985-10-28 | 1987-05-12 | Nl Industries, Inc. | Preactivated organophilic clay gellant lubricating grease thickened with preactivated organophilic clay gellant and process for preparing preactivated organophilic clay gellants |
| DE4114906A1 (en) * | 1991-05-07 | 1992-11-12 | Henkel Kgaa | USE OF SELECTED OLEOPHILIC COMPOUNDS WITH QUARTZERIC NITROGEN TO IMPROVE THE OILABILITY OF FINE-PARTICULAR TONE AND THEIR USE AS VISCOSITY DEVICES |
| US5556832A (en) * | 1992-09-21 | 1996-09-17 | Union Oil Company Of California | Solids-free, essentially all-oil wellbore fluid |
| AU5133493A (en) * | 1992-09-21 | 1994-04-12 | Union Oil Company Of California | Solids-free, essentially all-oil wellbore fluid |
| US6258757B1 (en) | 1997-03-14 | 2001-07-10 | Halliburton Energy Services, Inc. | Water based compositions for sealing subterranean zones and methods |
| US6060434A (en) * | 1997-03-14 | 2000-05-09 | Halliburton Energy Services, Inc. | Oil based compositions for sealing subterranean zones and methods |
| US5913364A (en) * | 1997-03-14 | 1999-06-22 | Halliburton Energy Services, Inc. | Methods of sealing subterranean zones |
| US6328106B1 (en) | 1999-02-04 | 2001-12-11 | Halliburton Energy Services, Inc. | Sealing subterranean zones |
| US6271181B1 (en) | 1999-02-04 | 2001-08-07 | Halliburton Energy Services, Inc. | Sealing subterranean zones |
| US6762156B2 (en) | 2002-01-31 | 2004-07-13 | Halliburton Energy Services, Inc. | Reactive cement compositions for sealing hydrocarbon containing subterranean zones and methods |
| US9371480B2 (en) * | 2013-08-14 | 2016-06-21 | Elementis Specialties, Inc. | Slurry concentrate and associated methods of use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3472740A (en) * | 1967-03-28 | 1969-10-14 | Calgon Corp | Process for purifying dialkyl diallyl ammonium chloride and dialkyl dimethallyl ammonium chloride |
| US3537994A (en) * | 1967-07-25 | 1970-11-03 | Nat Lead Co | Organophilic clay greases |
| NO146364C (en) * | 1977-11-01 | 1982-09-15 | Nl Industries Inc | OIL-BASED LIQUIDS WITH ORGANOPHILE CLAYS WITH IMPROVED DISPERSERATING PROPERTIES FOR DRILLING |
-
1981
- 1981-11-16 AU AU77520/81A patent/AU551121B2/en not_active Ceased
- 1981-11-16 EG EG670/81A patent/EG15460A/en active
- 1981-11-16 SE SE8106797A patent/SE8106797L/en not_active Application Discontinuation
- 1981-11-16 JP JP56182414A patent/JPS5876485A/en active Pending
- 1981-11-16 FR FR8121404A patent/FR2514663B1/en not_active Expired
- 1981-11-16 CA CA000390140A patent/CA1160032A/en not_active Expired
- 1981-11-16 GB GB08134463A patent/GB2108175B/en not_active Expired
- 1981-11-16 BR BR8107427A patent/BR8107427A/en unknown
- 1981-11-16 NO NO813870A patent/NO155811B/en unknown
- 1981-11-16 IT IT25110/81A patent/IT1194109B/en active
-
1982
- 1982-07-02 IN IN499/DEL/82A patent/IN158428B/en unknown
-
1987
- 1987-03-09 SG SG245/87A patent/SG24587G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IT1194109B (en) | 1988-09-14 |
| IT8125110A0 (en) | 1981-11-16 |
| NO813870L (en) | 1983-04-20 |
| IN158428B (en) | 1986-11-15 |
| SE8106797L (en) | 1983-04-20 |
| EG15460A (en) | 1986-12-30 |
| SG24587G (en) | 1987-07-10 |
| JPS5876485A (en) | 1983-05-09 |
| FR2514663B1 (en) | 1987-01-30 |
| AU7752081A (en) | 1983-04-28 |
| NO155811B (en) | 1987-02-23 |
| GB2108175B (en) | 1985-08-07 |
| FR2514663A1 (en) | 1983-04-22 |
| BR8107427A (en) | 1983-05-24 |
| GB2108175A (en) | 1983-05-11 |
| AU551121B2 (en) | 1986-04-17 |
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