CA1105348A - Oil base fluids with organophilic clays having enhanced dispersibility - Google Patents
Oil base fluids with organophilic clays having enhanced dispersibilityInfo
- Publication number
- CA1105348A CA1105348A CA314,094A CA314094A CA1105348A CA 1105348 A CA1105348 A CA 1105348A CA 314094 A CA314094 A CA 314094A CA 1105348 A CA1105348 A CA 1105348A
- Authority
- CA
- Canada
- Prior art keywords
- clay
- oil
- ammonium compound
- carbon atoms
- methyl benzyl
- 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
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/36—Water-in-oil emulsions
Abstract
ABSTRACT:
An oil-base emulsion fluid comprising an oil phase, from about 2 to about 50% by volume water and from 1 to 30 lbs.
per barrel of an organophilic clay gellant comprising the reaction product of a smectite-type clay having a cation ex-change capacity of at least 75 milliequivalents per 100 grams and from 80 to 120 milliequivalents per 100 grams of clay of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms and 60 to 75% alkyl groups having 18 carbon atoms.
An oil-base emulsion fluid comprising an oil phase, from about 2 to about 50% by volume water and from 1 to 30 lbs.
per barrel of an organophilic clay gellant comprising the reaction product of a smectite-type clay having a cation ex-change capacity of at least 75 milliequivalents per 100 grams and from 80 to 120 milliequivalents per 100 grams of clay of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms and 60 to 75% alkyl groups having 18 carbon atoms.
Description
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Th'is invention relates to oil-base emulsion fluids con-taining novel clay complexes, and more particularly to oil-base emulsion drilling fluids and oil-base emulsion packer fluids containing the same.
It is well known that organic compounds which conta'in a cation will react under favorable conditions by ion-exchange with clays which contain a negative layer-lattice and exchange-able cations to form organophilic clay products. If the organic cation contains at least one alkyl group containing at least 10 carbon atoms, the resulting organophilic clays have the property of swelling in certain organic liquids.
- Since the commercial introduction of these organophilic clays in the early 1950's under the trademark BENTONE, lt has become w'ell known to gain the maximum gelling (thickening) efficiency from these organophilic clays by adding a low -molecular weight polar organic material to the composition.
Such polar organic materials have been variously called dis-persants, dispersion aids, solvating agents, dispersion agents and the like.
The most efficient and accepted polar materials for use as dispersants have been found to be low molecular weight alcohols and ketones, particularly methanol and acetone. These dispersants, however, have very low flash points and require the use of flame-proof apparatus. Higher boiling, h1gh~ flash point dispersants may be used but these are less efficient'and often produce gels having poor secondary properties, such as mechanical stability or storage stability.
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Th'is invention relates to oil-base emulsion fluids con-taining novel clay complexes, and more particularly to oil-base emulsion drilling fluids and oil-base emulsion packer fluids containing the same.
It is well known that organic compounds which conta'in a cation will react under favorable conditions by ion-exchange with clays which contain a negative layer-lattice and exchange-able cations to form organophilic clay products. If the organic cation contains at least one alkyl group containing at least 10 carbon atoms, the resulting organophilic clays have the property of swelling in certain organic liquids.
- Since the commercial introduction of these organophilic clays in the early 1950's under the trademark BENTONE, lt has become w'ell known to gain the maximum gelling (thickening) efficiency from these organophilic clays by adding a low -molecular weight polar organic material to the composition.
Such polar organic materials have been variously called dis-persants, dispersion aids, solvating agents, dispersion agents and the like.
The most efficient and accepted polar materials for use as dispersants have been found to be low molecular weight alcohols and ketones, particularly methanol and acetone. These dispersants, however, have very low flash points and require the use of flame-proof apparatus. Higher boiling, h1gh~ flash point dispersants may be used but these are less efficient'and often produce gels having poor secondary properties, such as mechanical stability or storage stability.
-2-ll~s348 -The use of organophilic clays as thickeners in petroleum oil for use as oil-base drilling fluids and oil-base packer fluids is well known. Such uses are disclosed in U.S. Patent 2,531,812, ~.S. Patent 2,531,427, U.S. Patent 2,966,506, and U.S. Patent 3,831,678. The organophilic clays, however, have been poor gellants for organic systems when incorporated into the system at temperatures less than 55F or when mixed under low shear; some clays have required several hours to achieve significant gelling.
Accordingly, there is a need for an organophilic clay gellant which is easy to disperse in the oil phase of an oil-base emulsion fluid and which achieves essentially com-plete gellation at low shear in short periods of time.
An oil-base emulsion fluid has been unexpectedly dis-covered which comprises an oil phase, a dispersed aqueous phase and about 1 to about 30 lbs. per barrel of an organo-philic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms, and 60 to 75%
alkyl groups having 18 carbon atoms and a smectite-type clay having a cation exchange capacity of at least 75 milliequi-valents per 100 grams of said clay, and wherein the amount of said ammonium compound is from 80 to 120 milliequivalents per 100 grams of said clay, 100% active clay basis.
The clays used to prepare the organophilic clay thickeners of this invention are smectite-type clays which have a cation exchange capacity of at least 75 milliequivalents per 100 grams of clay. Particularly desirable types of clay are the naturally occurring Wyoming variety of swelling bentonite and like clays, and hectorite, a swelling magnesium-lithium-silicate clay.
The clays, especially the bentonite type clays, are pre-ferably converted to the sodium form if they are not already in this form. This can conveniently be done by preparing 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 solùble sodium ~ompound such as sodium carbonate, sodium hydroxide and the like, followed by shearing the mixture in a pugmill or extruder.
Smectite-type clays prepared synthetically by either a pneumatolytic or, preferably a hydrothermal synthesis process can also be used to prepare the present organophilic clays.
Representative of such clays are montmorillonite, bentonite, beidellite, hectorite, saponite and stevensite. These clays may be synthesized hydrothermally by forming an aqueous re-action mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as r the case may be, sodium flouride or alternate exchangeable cation or mixture thereof in the proportions for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approximately 100 to 325C, preferably -`~
274 to 300C, for a sufficient period of time to form the desired product. Hydrothermal processes for preparing synthetic smectites are described in the following U.S. patents, Granquist
Accordingly, there is a need for an organophilic clay gellant which is easy to disperse in the oil phase of an oil-base emulsion fluid and which achieves essentially com-plete gellation at low shear in short periods of time.
An oil-base emulsion fluid has been unexpectedly dis-covered which comprises an oil phase, a dispersed aqueous phase and about 1 to about 30 lbs. per barrel of an organo-philic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms, and 60 to 75%
alkyl groups having 18 carbon atoms and a smectite-type clay having a cation exchange capacity of at least 75 milliequi-valents per 100 grams of said clay, and wherein the amount of said ammonium compound is from 80 to 120 milliequivalents per 100 grams of said clay, 100% active clay basis.
The clays used to prepare the organophilic clay thickeners of this invention are smectite-type clays which have a cation exchange capacity of at least 75 milliequivalents per 100 grams of clay. Particularly desirable types of clay are the naturally occurring Wyoming variety of swelling bentonite and like clays, and hectorite, a swelling magnesium-lithium-silicate clay.
The clays, especially the bentonite type clays, are pre-ferably converted to the sodium form if they are not already in this form. This can conveniently be done by preparing 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 solùble sodium ~ompound such as sodium carbonate, sodium hydroxide and the like, followed by shearing the mixture in a pugmill or extruder.
Smectite-type clays prepared synthetically by either a pneumatolytic or, preferably a hydrothermal synthesis process can also be used to prepare the present organophilic clays.
Representative of such clays are montmorillonite, bentonite, beidellite, hectorite, saponite and stevensite. These clays may be synthesized hydrothermally by forming an aqueous re-action mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as r the case may be, sodium flouride or alternate exchangeable cation or mixture thereof in the proportions for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approximately 100 to 325C, preferably -`~
274 to 300C, for a sufficient period of time to form the desired product. Hydrothermal processes for preparing synthetic smectites are described in the following U.S. patents, Granquist
3,252,757; Neumann ~,586,478; Orlemann 3,666,407; Neumann 3,671,190;
Hickson 3,844,978; Hickson 3,844,979; Granquist 3,852,405; and Granquist 3,855,147.
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The organic compounds useful in the practice of this invention are quaternary ammonium salts containing one methyl radical, one benzyl radical, and a mixture of alkyl radicals having from 14 to 20 carbon atoms, wherein 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, 100% basis. The salt anion is preferably selected from the group consisting of chloride and bromide, and mixtures thereof, and is more preferably chloride, although other anions such as acetate, hydroxide, nitrate, etc., may be present in the guaternary ammonium salt to neutralize the quaternary ammonium cation. The methyl benzyl dialkyl ammonium salt may be represented by the formula:
. I ~ +
R2 - N _ R4 M where _ R3 Rl CH3, R2 = C6H5CH2, R3 and ~ ~ are alkyl groups containing a mixture of 14 to 20 carbon atoms wherein 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, based on 100%; and where M is preferably selected from the group consisting of Cl , Br , NO2 , OH , C2H3O2 , and mixtures thereof.
The preferred quaternary amine for use in the practice of this invention is methyl benzyl dihydrogenated tallow ammoniom chloride. Commercially prepared hydrogenated tallow typically analyzes 2.0% C14, 0.5% C15, 29.0% C16, 1.5% C17, 66.0% C1~, and 1.0~ C20 alkyl radicals.
The alkyl radicals may be derived from other natural oils including various vegetable oils, such as corn oil,-soybean oil, cottonseed oil, castor oil, and the like, and various animal oils or fats. The alkyl radicals may be petrochemically derived such as from alpha olefins.
Many processes are known to prepare methyl benzyl dialkyl ammonium salts. Generally, one skilled in the art would prepare a dialkyl secondary amine, for example, by the hydroqenation of nitriles, see U.S. Patent 2,355,356; form the methyl dialkyl tertiary amine by reductive alkylation using formaldehyde as the source of methyl radical, see Shapiro et. al., U.S. Patent Number 3,136,819; and thereafter form the quaternary amine halide by adding benzyl chloride or - benzyl bromide to the tertiary amine, see Shapiro et. al., U.S. Patent Number 2,775,617.
The organophilic clays of this invention can be prepared by mixing the clay, quaternary ammonium compound and water together, preferably at a temperature within the range from 100F (38C) to 180F (82C), more preferably 1400F
(60C) to 170F (77C) for a period of time sufficient for the organic compound to coat the clay particles, followed by filtering, washing, drying and grinding. In using the organophilic clays in emulsions, the drying and grinding steps may be eliminated. When admixing the clay, quaternary ammonium compound and water together in such concentrations that a slurry is not formed, then the filtration and washing steps can be eliminated.
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Preferably the clay is dispersed in water at a concen-tration from about 3~ to 7%, the slurry optionally centri-fuged to remove non-clay impurities which constitute about 10% to about S0% of the starting clay composition, the slurry ~
agitated and heated to a temperature in the range from 140F : - -(60C) to 170F (77C) the quaternary amine salt added in the desired milliequivalent ratio, preferably as a liquid in isopropanol or dispersed in water, and the agitation continued to effect the reaction. ~ ;~
The amount of the methyl benzyl dialkyl ammonium salt added to the clay for purposes of this invention must be sufficient to impart to the organophilic clay the enhanced dispersion characteristics desired. The milliequivalent ratio is defined as the number of milliequivalents of the organic compound in the organoclay per 100 grams of clay, 100% active clay basis. The organophilic clays of this invention must have a milliequivalent ratio from 80 to 120 and preferably 85 to 95. At lower milliequivalent ratios, the organophilic clays produced are not effective gellants for oil-base emulsion drilling fluids and oil-base emulsion packer fluids. At higher milliequivalent ratios, the organophilic clays are poorer gellants.
In the practice of the present invention, there must be present in the oll-base emulsion fluid an oil phase, a dis-persed aqueous phase, and from about 1 to about 30 lbs.
per barrel of the organophilic clay gellant.
The oil phase useful in preparing the emulsion fluids of this invention may suitably be crude petroleum and .
llas34s fractions thereof, as, for example, diesel oil, kerosene, fuel oil, light lubricating oil fractions, heavy naptha having a boiling range between about 300 to 600F and the like.
The preferred material is diesel oil resulting from a crude distillatlon of a crude petroleum oil.
The aqueous phase of the invention is water including aqueous solutions of inorganic salts such as sodium chloride, calcium chloride and the like. While the addition of these salts is optional, their presence aids in drilling through formations containing hydratable clays by increasing the osmotic pressure of the water phase. A complete dlscussion of the effects of these salts may be found in U.S. Patent 3,561,548.
s The exact amount of water incorporated into the fluid is determined by several factors including Eluid weight re-quirements, flow properties desired, bottom-hole temperatures ; expected to be encountered and the operational requirements placed on the fluid during drilling, coring, or completion operations. In general, it has been found preferably to employ water in the amount of 2 to 50% by volume. These amounts of water render the oil-base fluid fire-resistant because of the "snuffer" action of the steam bucket released when the oil is exposed 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-base fluids.
Conventional emulsifiers may be employed in the compo-sitions of the invention to emulsify the water in the oil . .
phase. The amount of emulsifier employed is primarily depen-dent upon the amount of water present and the extent of emulsi-fication desired. Generally from 2 to 30 lbs. per barrel and preferably from 5 to 20 lbs. per barrel have been found satis-factory to achieve the necessary gel strengths and filtration control. The emulsifiers may be selected from conventionally used emulsifiers such as EZ r1uL~ emulsifier and INVERMUL~
oil mud concentrate, both trademarks of N L Industries, Inc.
Baroid Division. ~ -The compositions may optionally contain conventional weighting agents such as BAROID~ barite for controlling fluid density between 7.S and 22 lb/gal. as well as fluid loss control agents (filtrate reducers) such as those described in Jordan et al, U.S. Patent Number 3,168,475 and Andrews et al, ; U.S. Patent Number 3,494!865.
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 minimum concentration of organophilic clay needed to gel any particular composition is dependent upon several factors such as the type of organophilic clay used, the characteristics of the oil phase, and the maximum temperature to which the composition is to be raised. The maximum concentration of organophilic clay which can be used is limited only in that the composition must be sufficiently fluid to be pumpable.
The concentration of organophilic clay within the range of about 1 to about 30 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 emulsion drilling fluids whereas amounts from about 6 to about 30 lbs. per barrel have been found adequate for the preparation of oil-base emulsion packer fluids. It has been found that when the organophilic clay is mixed into the oil-base emulsion fluid, essentially complete gelling is achieved at low shear mixing.
The resulting oil-base emulsion fluid is a stable oil-base ' emulsion 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 inven-tion by adding to an oil medium the organophilic clay and water optionally containing the inorganic salts in any order. 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 emulsion in the oil phase of the fluid prior to usage of the fluid. Once prepared, the packer fluid is transferred, such as by pumping, into a well bore, at least one portion of which is to be insulated.
The oil-base emulsion drilling fluid can be prepared and used either before drilling 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 llQ53g8 prepared, the emulsion drilling fluid is transferred, such as ;
by pumping, into a well bore and circulated to the bit and through the borehole in contact with the walls thereof.- r The following examples are given to illustrate the in-vention, but are not deemed to be limiting thereof. All percentages given are based upon welght 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 For Testing Fluids, 6th Ed., April 1976.
The smectite-type clays used are hectorite and Wyoming bentonite. The hectorite clay was slurried in water and cen-trifuged to remove essentially all of the non-clay impurities.
The Wyoming bentonite clay was slurried in water, centrifuged to remove essentially all of the non-clay impurities, and ion-exchanged to the sodium form by passing the slurry through a bed of cation exchange resin in the sodium form. Several samples of methyl benzyl dihydrogenated tallow ammonium chloride supplied by ENENCO, Inc. were used to prepare the organoclays in the examples. The molecular weight of these samples ranged from 619 to 644, and the percent activity in isopropanol varied from 60% to 81.5%.
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The conventionally refined oil and the solvent refined oils had the following properties:
Conventionally Solvent Refined Refined Gravity, API @ 60 F20 30.4 Viscosity, SUS @ 100 F 500 400 Viscosity, SUS @ 210 F 53 58 Viscosity Index 12 98 Index of Refraction1.5085 1.4811 Flash Point, F 390 460 Pour Point, F -5 5 Example 1 The organophilic clays listed in Table I were prepared by heating the clay slurry to a temperature within the range from 150F (66C) to 170F (77C), adding while stirring the clay slurry, the indicated amount of the indicated quaternary ammonium chloride which had been previously melted for conven-ience in handling, and continuing the stirring for approximately 45 minutes, followed by filtering, washing, drying at 140F
(60C), and grinding.
These organophilic clays were evaluated in the conventionally refined oil in the ease of dispersion test described which dramatically indicates the improved ease of dispersion of these thickeners as compared to similar organophilic clay thickners.
The data in Table I indicates the sharp increase in the ease of dispersion of organophilic clays prepared from methyl benzyl dihydrogenated tallow ammonium chloride and the smectite-type clays when the amount of this quaternary ammonium compound was in the range of 30 to 120 milliequivalents per 100 grams of 11~i;~48 clay. The data also illustrates the much superior dispersion characteristics of the inventive organophilic clays as compared with organophilic clays prepared from somewhat similar but different quaternary ammonium compounds.
Example 2 The 102.6 milliequivalent ratio bentonite clay thickener of Example l was evaluated as a thickener/suspending agent in an oil-base emulsion drilling fluid at a concentration of 4 pounds per barrel (42 gallons). The drilling fluid had the following composition: 154 parts diesel oil, 129 parts water, 68 parts calcium chloride, 8 parts DURATONE HT'~ fluid loss control additive, 15 parts INVERMUL2 emulsifier, and 2 parts EZ MUL'~ emulsifier. Standard rheology data were obtained on the drilling fluids after mixing with the organophilic clay for 15 minutes with a MULTI-MIXER'~. The results given in Table II
indicate that this organophilic clay is an excellent thickener for oil-base emulsion drilling fluids.
ExamPle 3 The change in physical properties with increasing tempera-ture for a typical oil-base fluid was compared with fluids made according to the invention. The base emulsion fluid was prepared by adding 15 lb/barrel INVERMUL~ emulsifiers, 2 lb/barrel EZ MUL~ emulsifier, and DURATONE HT fluid loss con-trol additive, to 220 lb/barrel diesel oil and stirring in a mixer for 2 minutes whereupon 38 lb/barrel water was added and the fluid stirred an additional 8 minutes. BARIOD~ barite and calcium chloride powder were added in amounts of 325 lb/barrel and l9 lb/barrel and the fluid stirred another 10 minutes. The ... ... ...
5~4~3 resulting fluid had a density of 14 lb/gal with an 85/15 oil/water volume ratio in the liquid phase.
A portion of the base fluid was divided into two 350 ml aliquats and placed in steel beakers which were packed around with salted ice in a larger container. The samples were stirred at low shear with a MULTI-MIXER~ until the fluid cooled to 25F.
A 15 lb/barrel sample of a 95.5 milliequivalent ratio bentonite clay thickener prepared according to Example 1 was stirred in the fluid for 10 minutes. The cold fluid sample was stirred at 600 rpm and gradually heated to 1300F. The same procedure was repeated with a fluid made with 15 lb/barrel of a dimethyldioctadecyl ammonium bentonite clay. The results are set forth in Table III.
The results indicate that the inventive fluids started yielding around 35F while the conventional fluid did not yield until around 65F.
Example 4 The procedure of Example 3 was repeated with 6 lb/barrel of a bentonlte clay thickener having an average milliequivalent ratio of between 82 and 88 and the comparative dimethyldioctadecyl ammonium bentonite clay of Example 3, except that the temperature was maintained at 85F while the yield point and 10 second gel strengths were measured over a 45 minute time period. The results are set forth in Table IV.
' The results indicate that the inventive fluid yielded within the first four minutes while the comparative material continued to yield slowly over the entire stirring period and not achieving maximum yield until hot rolled and restirred at high speed.
The invention being thus described, it will be obvious that the same 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.
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Hickson 3,844,978; Hickson 3,844,979; Granquist 3,852,405; and Granquist 3,855,147.
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The organic compounds useful in the practice of this invention are quaternary ammonium salts containing one methyl radical, one benzyl radical, and a mixture of alkyl radicals having from 14 to 20 carbon atoms, wherein 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, 100% basis. The salt anion is preferably selected from the group consisting of chloride and bromide, and mixtures thereof, and is more preferably chloride, although other anions such as acetate, hydroxide, nitrate, etc., may be present in the guaternary ammonium salt to neutralize the quaternary ammonium cation. The methyl benzyl dialkyl ammonium salt may be represented by the formula:
. I ~ +
R2 - N _ R4 M where _ R3 Rl CH3, R2 = C6H5CH2, R3 and ~ ~ are alkyl groups containing a mixture of 14 to 20 carbon atoms wherein 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, based on 100%; and where M is preferably selected from the group consisting of Cl , Br , NO2 , OH , C2H3O2 , and mixtures thereof.
The preferred quaternary amine for use in the practice of this invention is methyl benzyl dihydrogenated tallow ammoniom chloride. Commercially prepared hydrogenated tallow typically analyzes 2.0% C14, 0.5% C15, 29.0% C16, 1.5% C17, 66.0% C1~, and 1.0~ C20 alkyl radicals.
The alkyl radicals may be derived from other natural oils including various vegetable oils, such as corn oil,-soybean oil, cottonseed oil, castor oil, and the like, and various animal oils or fats. The alkyl radicals may be petrochemically derived such as from alpha olefins.
Many processes are known to prepare methyl benzyl dialkyl ammonium salts. Generally, one skilled in the art would prepare a dialkyl secondary amine, for example, by the hydroqenation of nitriles, see U.S. Patent 2,355,356; form the methyl dialkyl tertiary amine by reductive alkylation using formaldehyde as the source of methyl radical, see Shapiro et. al., U.S. Patent Number 3,136,819; and thereafter form the quaternary amine halide by adding benzyl chloride or - benzyl bromide to the tertiary amine, see Shapiro et. al., U.S. Patent Number 2,775,617.
The organophilic clays of this invention can be prepared by mixing the clay, quaternary ammonium compound and water together, preferably at a temperature within the range from 100F (38C) to 180F (82C), more preferably 1400F
(60C) to 170F (77C) for a period of time sufficient for the organic compound to coat the clay particles, followed by filtering, washing, drying and grinding. In using the organophilic clays in emulsions, the drying and grinding steps may be eliminated. When admixing the clay, quaternary ammonium compound and water together in such concentrations that a slurry is not formed, then the filtration and washing steps can be eliminated.
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Preferably the clay is dispersed in water at a concen-tration from about 3~ to 7%, the slurry optionally centri-fuged to remove non-clay impurities which constitute about 10% to about S0% of the starting clay composition, the slurry ~
agitated and heated to a temperature in the range from 140F : - -(60C) to 170F (77C) the quaternary amine salt added in the desired milliequivalent ratio, preferably as a liquid in isopropanol or dispersed in water, and the agitation continued to effect the reaction. ~ ;~
The amount of the methyl benzyl dialkyl ammonium salt added to the clay for purposes of this invention must be sufficient to impart to the organophilic clay the enhanced dispersion characteristics desired. The milliequivalent ratio is defined as the number of milliequivalents of the organic compound in the organoclay per 100 grams of clay, 100% active clay basis. The organophilic clays of this invention must have a milliequivalent ratio from 80 to 120 and preferably 85 to 95. At lower milliequivalent ratios, the organophilic clays produced are not effective gellants for oil-base emulsion drilling fluids and oil-base emulsion packer fluids. At higher milliequivalent ratios, the organophilic clays are poorer gellants.
In the practice of the present invention, there must be present in the oll-base emulsion fluid an oil phase, a dis-persed aqueous phase, and from about 1 to about 30 lbs.
per barrel of the organophilic clay gellant.
The oil phase useful in preparing the emulsion fluids of this invention may suitably be crude petroleum and .
llas34s fractions thereof, as, for example, diesel oil, kerosene, fuel oil, light lubricating oil fractions, heavy naptha having a boiling range between about 300 to 600F and the like.
The preferred material is diesel oil resulting from a crude distillatlon of a crude petroleum oil.
The aqueous phase of the invention is water including aqueous solutions of inorganic salts such as sodium chloride, calcium chloride and the like. While the addition of these salts is optional, their presence aids in drilling through formations containing hydratable clays by increasing the osmotic pressure of the water phase. A complete dlscussion of the effects of these salts may be found in U.S. Patent 3,561,548.
s The exact amount of water incorporated into the fluid is determined by several factors including Eluid weight re-quirements, flow properties desired, bottom-hole temperatures ; expected to be encountered and the operational requirements placed on the fluid during drilling, coring, or completion operations. In general, it has been found preferably to employ water in the amount of 2 to 50% by volume. These amounts of water render the oil-base fluid fire-resistant because of the "snuffer" action of the steam bucket released when the oil is exposed 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-base fluids.
Conventional emulsifiers may be employed in the compo-sitions of the invention to emulsify the water in the oil . .
phase. The amount of emulsifier employed is primarily depen-dent upon the amount of water present and the extent of emulsi-fication desired. Generally from 2 to 30 lbs. per barrel and preferably from 5 to 20 lbs. per barrel have been found satis-factory to achieve the necessary gel strengths and filtration control. The emulsifiers may be selected from conventionally used emulsifiers such as EZ r1uL~ emulsifier and INVERMUL~
oil mud concentrate, both trademarks of N L Industries, Inc.
Baroid Division. ~ -The compositions may optionally contain conventional weighting agents such as BAROID~ barite for controlling fluid density between 7.S and 22 lb/gal. as well as fluid loss control agents (filtrate reducers) such as those described in Jordan et al, U.S. Patent Number 3,168,475 and Andrews et al, ; U.S. Patent Number 3,494!865.
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 minimum concentration of organophilic clay needed to gel any particular composition is dependent upon several factors such as the type of organophilic clay used, the characteristics of the oil phase, and the maximum temperature to which the composition is to be raised. The maximum concentration of organophilic clay which can be used is limited only in that the composition must be sufficiently fluid to be pumpable.
The concentration of organophilic clay within the range of about 1 to about 30 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 emulsion drilling fluids whereas amounts from about 6 to about 30 lbs. per barrel have been found adequate for the preparation of oil-base emulsion packer fluids. It has been found that when the organophilic clay is mixed into the oil-base emulsion fluid, essentially complete gelling is achieved at low shear mixing.
The resulting oil-base emulsion fluid is a stable oil-base ' emulsion 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 inven-tion by adding to an oil medium the organophilic clay and water optionally containing the inorganic salts in any order. 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 emulsion in the oil phase of the fluid prior to usage of the fluid. Once prepared, the packer fluid is transferred, such as by pumping, into a well bore, at least one portion of which is to be insulated.
The oil-base emulsion drilling fluid can be prepared and used either before drilling 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 llQ53g8 prepared, the emulsion drilling fluid is transferred, such as ;
by pumping, into a well bore and circulated to the bit and through the borehole in contact with the walls thereof.- r The following examples are given to illustrate the in-vention, but are not deemed to be limiting thereof. All percentages given are based upon welght 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 For Testing Fluids, 6th Ed., April 1976.
The smectite-type clays used are hectorite and Wyoming bentonite. The hectorite clay was slurried in water and cen-trifuged to remove essentially all of the non-clay impurities.
The Wyoming bentonite clay was slurried in water, centrifuged to remove essentially all of the non-clay impurities, and ion-exchanged to the sodium form by passing the slurry through a bed of cation exchange resin in the sodium form. Several samples of methyl benzyl dihydrogenated tallow ammonium chloride supplied by ENENCO, Inc. were used to prepare the organoclays in the examples. The molecular weight of these samples ranged from 619 to 644, and the percent activity in isopropanol varied from 60% to 81.5%.
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The conventionally refined oil and the solvent refined oils had the following properties:
Conventionally Solvent Refined Refined Gravity, API @ 60 F20 30.4 Viscosity, SUS @ 100 F 500 400 Viscosity, SUS @ 210 F 53 58 Viscosity Index 12 98 Index of Refraction1.5085 1.4811 Flash Point, F 390 460 Pour Point, F -5 5 Example 1 The organophilic clays listed in Table I were prepared by heating the clay slurry to a temperature within the range from 150F (66C) to 170F (77C), adding while stirring the clay slurry, the indicated amount of the indicated quaternary ammonium chloride which had been previously melted for conven-ience in handling, and continuing the stirring for approximately 45 minutes, followed by filtering, washing, drying at 140F
(60C), and grinding.
These organophilic clays were evaluated in the conventionally refined oil in the ease of dispersion test described which dramatically indicates the improved ease of dispersion of these thickeners as compared to similar organophilic clay thickners.
The data in Table I indicates the sharp increase in the ease of dispersion of organophilic clays prepared from methyl benzyl dihydrogenated tallow ammonium chloride and the smectite-type clays when the amount of this quaternary ammonium compound was in the range of 30 to 120 milliequivalents per 100 grams of 11~i;~48 clay. The data also illustrates the much superior dispersion characteristics of the inventive organophilic clays as compared with organophilic clays prepared from somewhat similar but different quaternary ammonium compounds.
Example 2 The 102.6 milliequivalent ratio bentonite clay thickener of Example l was evaluated as a thickener/suspending agent in an oil-base emulsion drilling fluid at a concentration of 4 pounds per barrel (42 gallons). The drilling fluid had the following composition: 154 parts diesel oil, 129 parts water, 68 parts calcium chloride, 8 parts DURATONE HT'~ fluid loss control additive, 15 parts INVERMUL2 emulsifier, and 2 parts EZ MUL'~ emulsifier. Standard rheology data were obtained on the drilling fluids after mixing with the organophilic clay for 15 minutes with a MULTI-MIXER'~. The results given in Table II
indicate that this organophilic clay is an excellent thickener for oil-base emulsion drilling fluids.
ExamPle 3 The change in physical properties with increasing tempera-ture for a typical oil-base fluid was compared with fluids made according to the invention. The base emulsion fluid was prepared by adding 15 lb/barrel INVERMUL~ emulsifiers, 2 lb/barrel EZ MUL~ emulsifier, and DURATONE HT fluid loss con-trol additive, to 220 lb/barrel diesel oil and stirring in a mixer for 2 minutes whereupon 38 lb/barrel water was added and the fluid stirred an additional 8 minutes. BARIOD~ barite and calcium chloride powder were added in amounts of 325 lb/barrel and l9 lb/barrel and the fluid stirred another 10 minutes. The ... ... ...
5~4~3 resulting fluid had a density of 14 lb/gal with an 85/15 oil/water volume ratio in the liquid phase.
A portion of the base fluid was divided into two 350 ml aliquats and placed in steel beakers which were packed around with salted ice in a larger container. The samples were stirred at low shear with a MULTI-MIXER~ until the fluid cooled to 25F.
A 15 lb/barrel sample of a 95.5 milliequivalent ratio bentonite clay thickener prepared according to Example 1 was stirred in the fluid for 10 minutes. The cold fluid sample was stirred at 600 rpm and gradually heated to 1300F. The same procedure was repeated with a fluid made with 15 lb/barrel of a dimethyldioctadecyl ammonium bentonite clay. The results are set forth in Table III.
The results indicate that the inventive fluids started yielding around 35F while the conventional fluid did not yield until around 65F.
Example 4 The procedure of Example 3 was repeated with 6 lb/barrel of a bentonlte clay thickener having an average milliequivalent ratio of between 82 and 88 and the comparative dimethyldioctadecyl ammonium bentonite clay of Example 3, except that the temperature was maintained at 85F while the yield point and 10 second gel strengths were measured over a 45 minute time period. The results are set forth in Table IV.
' The results indicate that the inventive fluid yielded within the first four minutes while the comparative material continued to yield slowly over the entire stirring period and not achieving maximum yield until hot rolled and restirred at high speed.
The invention being thus described, it will be obvious that the same 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.
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Claims (14)
1. An oil-base emulsion fluid which comprises an oil phase, a dispersed aqueous phase and from about 1 to about 30 lbs. per barrel of an organophilic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms, and 60 to 75% alkyl groups having 18 carbon atoms and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay, and wherein the amount of said ammonium compound is from 80 to 120 milliequivalents per 100 grams of said clay, 100% active clay basis.
2. The composition of Claim 1 wherein the smectite-type clay is selected from the group consisting of hectorite and sodium bentonite.
3. The composition of Claim 1 wherein the methyl benzyl dialkyl ammonium compound is methyl benzyl dihydrogenated tallow ammonium chloride.
4. The composition of Claim 1 wherein the amount of said ammonium compound is from 85 to 95 milliequivalents per 100 grams of clay.
5. The composition of Claim 1 which includes 2 to 30 lbs. per barrel of water-in-oil emulsifier.
6. An oil-base emulsion drilling fluid which comprises an oil phase, from about 2 to about 50% by volumn water, and from about 1 to about 10 lbs. per barrel of an organophilic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms, and 60 to 75% alkyl groups having 18 carbon atoms, and a smectite-type clay selected from the group consisting of hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 85 to 95 milliequivalents per 100 grams of said clay, 100% active clay basis.
7. The composition of Claim 6 wherein the methyl benzyl dialkyl ammonium compound is methyl benzyl dihydrogenated tallow ammonium chloride.
8. An oil-base emulsion packer fluid which comprises an oil phase, from about 2 to about 50% by volume water, and from about 6 to about 30 lbs. per barrel of an organophilic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms, and 60 to 75% alkyl groups having 18 carbon atoms, and a smectite-type clay selected from the group consisting of hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 85 to 95 milliequivalents per 100 grams of said clay, 100% active clay basis.
9. The composition of Claim 8 wherein the methyl benzyl dialkyl ammonium compound is methyl benzyl dihydrogenated tallow ammonium chloride.
10. An oil-base emulsion fluid which comprises an oil phase, a dispersed aqueous phase, a water-in-oil emulsifier and from 1 to 30 lbs. per barrel of an organophilic clay gellant comprising the reaction product of an ammonium compound have the formula:
wherein R1 = CH3,R2 = C6H5CH2, R3 and R4 are alkyl groups containing a mixture of 14 to 20 carbon atoms where-in 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, based on 100% and where M- is selected from the group consisting of Cl-, Br-, NO2, OH-, and C2H3O2-, and a smectite-type clay selected from the group consisting of hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 80 to 120 milliequivalents per 100 grams of said clay, 100% active clay basis.
wherein R1 = CH3,R2 = C6H5CH2, R3 and R4 are alkyl groups containing a mixture of 14 to 20 carbon atoms where-in 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, based on 100% and where M- is selected from the group consisting of Cl-, Br-, NO2, OH-, and C2H3O2-, and a smectite-type clay selected from the group consisting of hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 80 to 120 milliequivalents per 100 grams of said clay, 100% active clay basis.
11. In a method of insulating casing in a wellbore which comprises pumping an oil-base emulsion packer fluid in an annular space within said wellbore and thereafter gelling said packer fluid, the improvement which comprises a packer fluid having an oil phase, about 2 to about 50% by volume water, about 2 to 30 lbs. per barrel water-in-oil emulsifier and from about 6 to about 30 lbs. per barrel of an organo-philic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35% alkyl groups having 16 carbon atoms, and 60 to 75% alkyl groups having 18 carbon atoms, and a smectite-type clay selected from hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 85 to 95 milliequivalents per 100 grams of said clay, 100% active clay basis.
12. The process of Claim 11 wherein the methyl benzyl dialkyl ammonium compound is methyl benzyl dihydrogenated tallow ammonium chloride.
13. A process of drilling a well with a rotary bit which comprises forming a borehole with said bit while circulating through said bit and through said hole in contact with the walls thereof, an oil-base emulsion drilling fluid comprising an oil phase, about 2 to about 50% by volume water, about 2 to about 30 lbs. per barrel water-in-oil emulsifier and from about 1 to about 10 lbs. per barrel of an organophilic clay gellant comprising the reaction product of a methyl benzyl dialkyl ammonium compound, wherein the compound contains 20 to 35%
alkyl groups having 16 carbon atoms, and 60 to 75% alkyl groups having 18 carbon atoms, and a smectite-type clay selected from hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 85 to 95 milliequivalents per 100 grams of said clay, 100% active clay basis.
alkyl groups having 16 carbon atoms, and 60 to 75% alkyl groups having 18 carbon atoms, and a smectite-type clay selected from hectorite and sodium bentonite, and wherein the amount of said ammonium compound is from 85 to 95 milliequivalents per 100 grams of said clay, 100% active clay basis.
14. The process of Claim 13 wherein the methyl benzyl dialkyl ammonium compound is methyl benzyl dihydrogenated tallow ammonium chloride.
V9B(15-28) V9A(22-29)
V9B(15-28) V9A(22-29)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84760377A | 1977-11-01 | 1977-11-01 | |
| US847,603 | 1977-11-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105348A true CA1105348A (en) | 1981-07-21 |
Family
ID=25301033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA314,094A Expired CA1105348A (en) | 1977-11-01 | 1978-10-24 | Oil base fluids with organophilic clays having enhanced dispersibility |
Country Status (13)
| Country | Link |
|---|---|
| JP (2) | JPS6023797B2 (en) |
| AR (1) | AR229229A1 (en) |
| AU (1) | AU529615B2 (en) |
| BR (1) | BR7807159A (en) |
| CA (1) | CA1105348A (en) |
| DE (1) | DE2847147C2 (en) |
| FR (1) | FR2407252A1 (en) |
| GB (1) | GB2008171B (en) |
| IT (1) | IT1101284B (en) |
| NL (1) | NL188656C (en) |
| NO (1) | NO146364C (en) |
| SE (1) | SE437847B (en) |
| SG (1) | SG27382G (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO146364C (en) * | 1977-11-01 | 1982-09-15 | Nl Industries Inc | OIL-BASED LIQUIDS WITH ORGANOPHILE CLAYS WITH IMPROVED DISPERSERATING PROPERTIES FOR DRILLING |
| CA1137739A (en) * | 1979-09-27 | 1982-12-21 | Donald J. Mintz | Thickener composite from a water swellable material, oil-surfactant phase and a polymer |
| US4503170A (en) * | 1979-09-27 | 1985-03-05 | Exxon Production Research Co. | Shear thickening fluid |
| CA1139928A (en) * | 1979-09-27 | 1983-01-25 | Evelyn N. Drake | Shear thickening fluid |
| US4391925A (en) | 1979-09-27 | 1983-07-05 | Exxon Research & Engineering Co. | Shear thickening well control fluid |
| CA1154945A (en) * | 1979-09-28 | 1983-10-11 | Charles R. Dawson, Jr. | Thickener from water-swellable material, oil surfactant and water |
| US4391637A (en) * | 1981-10-19 | 1983-07-05 | Nl Industries, Inc. | Rheological additive for non-aqueous fluid systems |
| US4412018A (en) * | 1980-11-17 | 1983-10-25 | Nl Industries, Inc. | Organophilic clay complexes, their preparation and compositions comprising said complexes |
| IT1194110B (en) * | 1981-10-19 | 1988-09-14 | Nl Industries Inc | FLUIDS BASED ON OILS CONTAINING ORGANOPHILE CLAYS CATIONIC |
| BR8107427A (en) * | 1981-10-19 | 1983-05-24 | Nl Industries Inc | OIL-BASED FLUID IN PARTICULAR OIL-BASED FILLING FLUID PROCESS TO INSULATE A TUBE FOR COATING IN A DRILLING POCO AND GELIFICANT |
| DE3149131A1 (en) * | 1981-12-11 | 1983-06-23 | Henkel KGaA, 4000 Düsseldorf | Synthetic layered silicates modified by quaternary ammonium compounds |
| JPS58124535A (en) * | 1982-01-21 | 1983-07-25 | Pola Chem Ind Inc | Preparation of emulsified composition |
| WO1983002951A1 (en) * | 1982-02-18 | 1983-09-01 | Richard Pawel Jachnik | Drilling fluids and methods of using them |
| NO830557L (en) * | 1982-02-18 | 1983-08-19 | Milchem Inc | DRILL FLUIDS AND PROCEDURES TO USE THEREOF |
| WO1983002950A1 (en) * | 1982-02-18 | 1983-09-01 | Richard Pawel Jachnik | Drilling fluids and methods of using them |
| DK69183A (en) * | 1982-02-18 | 1983-08-19 | Milchem Inc | DRILLING AND PROCEDURES FOR USE THEREOF |
| DK69083A (en) * | 1982-02-18 | 1983-08-19 | Milchem Inc | PROCEDURE FOR DRILLING UNDER THE SURFACE AND DRILL FOR USE IN EXERCISING THE PROCEDURE |
| WO1983002949A1 (en) * | 1982-02-18 | 1983-09-01 | Richard Pawel Jachnik | Drilling fluids and methods of using them |
| US4469639A (en) * | 1982-04-28 | 1984-09-04 | Georgia Kaolin Company, Inc. | Preparation of organically modified smectites by treatment with methyl benzyl dialkyl ammonium halide |
| US4568392A (en) * | 1982-06-06 | 1986-02-04 | Exxon Production Research Co. | Well treating fluid |
| US4425463A (en) * | 1982-09-13 | 1984-01-10 | Exxon Research And Engineering Co. | Drilling fluids based on a mixture of sulfonated thermoplastic polymer and an amine-treated clay |
| GB2151219A (en) * | 1983-11-05 | 1985-07-17 | Perchem Ltd | Organoclay materials |
| US4676997A (en) * | 1986-03-11 | 1987-06-30 | The Hill-And-Griffith Company | Sand casting pattern coating compositions |
| JP5428501B2 (en) * | 2009-04-28 | 2014-02-26 | 東ソー株式会社 | Structure directing agent for zeolite production |
| JP5718559B2 (en) * | 2009-09-16 | 2015-05-13 | クニミネ工業株式会社 | Process for producing organic bentonite and organic bentonite obtained thereby |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2816073A (en) * | 1956-07-16 | 1957-12-10 | Phillips Petroleum Co | Drilling fluid |
| JPS53133354A (en) * | 1977-04-27 | 1978-11-21 | Mitsubishi Electric Corp | Phase synchronizing circuit |
| NO146364C (en) * | 1977-11-01 | 1982-09-15 | Nl Industries Inc | OIL-BASED LIQUIDS WITH ORGANOPHILE CLAYS WITH IMPROVED DISPERSERATING PROPERTIES FOR DRILLING |
-
1978
- 1978-10-24 NO NO783580A patent/NO146364C/en unknown
- 1978-10-24 CA CA314,094A patent/CA1105348A/en not_active Expired
- 1978-10-30 DE DE2847147A patent/DE2847147C2/en not_active Expired
- 1978-10-30 GB GB7842507A patent/GB2008171B/en not_active Expired
- 1978-10-30 SE SE7811233A patent/SE437847B/en not_active IP Right Cessation
- 1978-10-31 JP JP53133354A patent/JPS6023797B2/en not_active Expired
- 1978-10-31 BR BR7807159A patent/BR7807159A/en unknown
- 1978-10-31 IT IT29342/78A patent/IT1101284B/en active
- 1978-10-31 AU AU41193/78A patent/AU529615B2/en not_active Expired
- 1978-10-31 FR FR7830908A patent/FR2407252A1/en active Granted
- 1978-11-01 NL NLAANVRAGE7810886,A patent/NL188656C/en not_active IP Right Cessation
- 1978-11-01 AR AR274320A patent/AR229229A1/en active
-
1982
- 1982-06-16 SG SG273/82A patent/SG27382G/en unknown
-
1984
- 1984-06-12 JP JP59119253A patent/JPS6042481A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2847147A1 (en) | 1979-05-03 |
| BR7807159A (en) | 1979-07-10 |
| SG27382G (en) | 1985-01-11 |
| GB2008171B (en) | 1982-03-31 |
| NL7810886A (en) | 1979-05-03 |
| JPS6023797B2 (en) | 1985-06-10 |
| FR2407252B1 (en) | 1984-01-20 |
| JPS6042481A (en) | 1985-03-06 |
| IT1101284B (en) | 1985-09-28 |
| AU4119378A (en) | 1980-05-08 |
| NO146364C (en) | 1982-09-15 |
| NO783580L (en) | 1979-05-03 |
| SE437847B (en) | 1985-03-18 |
| JPS5484882A (en) | 1979-07-06 |
| AR229229A1 (en) | 1983-07-15 |
| AU529615B2 (en) | 1983-06-16 |
| JPH0115550B2 (en) | 1989-03-17 |
| IT7829342A0 (en) | 1978-10-31 |
| FR2407252A1 (en) | 1979-05-25 |
| NL188656C (en) | 1992-08-17 |
| DE2847147C2 (en) | 1986-06-05 |
| NO146364B (en) | 1982-06-07 |
| GB2008171A (en) | 1979-05-31 |
| SE7811233L (en) | 1979-05-02 |
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