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WO2000056835A1 - Fluides sous forme d'emulsions inverses, adaptes pour le forage - Google Patents

Fluides sous forme d'emulsions inverses, adaptes pour le forage Download PDF

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Publication number
WO2000056835A1
WO2000056835A1 PCT/US2000/007860 US0007860W WO0056835A1 WO 2000056835 A1 WO2000056835 A1 WO 2000056835A1 US 0007860 W US0007860 W US 0007860W WO 0056835 A1 WO0056835 A1 WO 0056835A1
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Prior art keywords
invert emulsion
fluid
acid
oleaginous liquid
alkenyl group
Prior art date
Application number
PCT/US2000/007860
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English (en)
Inventor
Arvind D. Patel
Original Assignee
M-I L.L.C.
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Filing date
Publication date
Application filed by M-I L.L.C. filed Critical M-I L.L.C.
Priority to AU39184/00A priority Critical patent/AU3918400A/en
Publication of WO2000056835A1 publication Critical patent/WO2000056835A1/fr

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    • 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

Definitions

  • Invert emulsion fluids i.e. emulsions in which the non-oleaginous fluid is the dispersed phase and the oleaginous fluid is the continuous phase, are employed in drilling processes for the
  • the invert emulsion fluids are conventionally utilized for such purposes as providing stability to the drilled hole, forming a thin filter cake, lubricating the drilling bore and downhole, and penetrating salt beds without sloughing or enlargement of the drilled hole.
  • Invert emulsion fluids generally consist of a three-component system, namely an oleaginous liquid such as oil which serves as a continuous phase, a non-oleaginous liquid such as water which serves as a discontinuous phase, and an emulsifying agent.
  • the emulsifying agent serves to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid.
  • a full description of such invert ⁇ 5 emulsions may be found in Composition and Properties of Drilling and Completion Fluids. 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, the contents of which are hereby incorporated by reference.
  • organophilic clay as a suspending agent in oil based drilling fluids should be well known to one of skill in the art. Generally, organophilic clays are made in a cation
  • lime or other alkaline materials are added to conventional invert emulsion fluids to maintain a reserve alkalinity when the invert emulsion fluid is to be used in drilling. See, for example, API Bulletin RP 13B-2, 1990, p. 22 which describes a standard test for determining excess lime in drilling mud. See also, for example, U.S. Patent No. 5,254,531 which employs lime along with an ester oil, a fatty acid, and an amine and EP 271943 which employs lime along with oil, water, and an ethoxylated amine. In some areas acidic gases such as CO 2 or H 2 S are encountered during drilling.
  • invert emulsions that is typically encountered during drilling are the need to increase the density of the drilling fluid. Conventionally this is done by the addition of solid weighting agents or by the use of brines of salts that form basic or neutral aqueous solutions.
  • brines of salts that form acidic aqueous solutions for example a transition metal halide solution
  • the transition metal ion would precipitate out due to the formation of hydroxide complexes.
  • acidic brine solutions is desired due to their higher density imparted by the metal cation.
  • an invert emulsion could be invented which did not fail or weaken when subjected to acidic gases such as CO or H S or mixed with acidic aqueous solutions or brines.
  • acidic gases such as CO or H S or mixed with acidic aqueous solutions or brines.
  • the invert emulsion could be employed as a drilling fluid in potentially acidic environments without apprehension of adverse affects before, during or after drilling.
  • a new invert emulsion fluid which comprises an oleaginous liquid, a non-oleaginous liquid, and a protonated amine having the structure R-N + -H 3 B " wherein R represents a C 1 -C 22 alkyl group or a Cj 2 -C 2 alkenyl group, a C 3 -C 8 cycloalkyl group substituted with a C 9 -C ⁇ 4 alkyl or alkenyl group, or a C 9 -C ⁇ 4 alkyl or alkenyl group substituted with a C -C 8 cycloalkyl group and B " is the conjugate base of a water soluble acid and the protonated amine is in an amount sufficient to stabilize the invert emulsion.
  • invert emulsion is an emulsion in which a non-oleaginous fluid is the dispersed phase and an oleaginous fluid is the continuous phase.
  • novel invert emulsion fluids of the present invention are useful in a similar manner as conventional invert emulsion fluids which includes utility in preparation for drilling, drilling, completing and working over subterranean wells such as oil and gas wells.
  • conventional invert emulsion fluids are described in, for example, Composition and Properties of Drilling and Completion Fluids. 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, the contents which are incorporated by reference, as well as, U.S. Patent No. 5,254,531 and EP 271943 which are incorporated by reference.
  • the advantage of the instant invert emulsion fluids is that due to the protonation of the amine it will normally not be necessary to add significant amounts of lime or another basic material to the invert emulsion fluid when an acidic substance such as CO 2 or H S comes into contact with the fluid.
  • Another advantage of the invert emulsion fluids of the present invention is that brines including acidic transition metal salts may be used to increase the density of the drilling fluid without the addition of solids or the formation of undesirable metal hydroxide precipitates.
  • Oleaginous liquid means an oil which is a liquid at 25°C and immiscible with water.
  • Oleaginous liquids typically include substances such as diesel oil, mineral oil, synthetic oil, glycerides of fatty acids, aliphatic esters, aliphatic ethers, aliphatic acetal, dialkylcarbonates, or other such hydrocarbons or mixtures of these compounds that may be used in the formulation of a drilling fluid.
  • the amount of oleaginous liquid in the invert emulsion fluid may vary depending upon the particular oleaginous fluid used, the particular non-oleaginous fluid used, and the particular application in which the invert emulsion fluid is to be employed. However, generally the amount must be sufficient to form a stable emulsion when utilized as the continuous phase. Typically, the amount of oleaginous liquid is at least about 30 percent by weight per volume of drilling fluid, preferably at least about 40 percent by weight per volume of drilling fluid, more preferably at least about 50 percent by volume of the total fluid. As used herein, the term "non-oleaginous liquid" mean any substance which is a liquid at
  • Non-oleaginous liquids are immiscible with oleaginous liquids but capable of forming emulsions therewith.
  • Typical non- oleaginous liquids include aqueous substances such as sea water or brine containing inorganic or organic dissolved salts, as well as, mixtures of water with water-miscible organic compounds.
  • the amount of non-oleaginous liquid in the invert emulsion fluid may vary depending upon the particular non-oleaginous fluid used and the particular application in which the invert emulsion fluid is to be employed.
  • the amount of non-oleaginous liquid is at least about 1 percent by volume, preferably at least about 3 percent by volume, more preferably at least about 5 percent by volume of the total fluid.
  • the amount should not be so great that it cannot be dispersed in the oleaginous phase. Therefore, typically the amount of non- oleaginous liquid is less than about 90 percent by volume, preferably less than about 80 percent by volume, more preferably less than about 70 percent by volume of the total fluid.
  • amine refers to compounds having the structure R-NH wherein R represents a Cj -C 2 alkyl group, a Cj 2 -C alkenyl group, a C 3 -C 8 cycloalkyl group substituted with a C 9 -C] 4 alkyl or alkenyl group, or a C 9 -C ⁇ 4 alkyl or alkenyl group substituted with a C 3 -C 8 cycloalkyl group.
  • Preferable R groups include straight or branched dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, as well as, mixtures and unsaturated derivatives thereof.
  • Preferable unsaturated derivatives include soyaalkylamine (Armeen STM available from Akzo Chemicals Inc.) and tallowalkylamine (Armeen TTM available from Akzo Chemicals Inc.). Many of the other above amines are also commercially available from Akzo Chemicals Inc. under the tradename ArmeenTM.
  • the aforementioned amines of the formula R-NH are protonated for use in this invention.
  • protonated means that the amine is substantially converted to the structure R-N + -H 3 B " .
  • protonation occurs due to reaction of the amine with an acid.
  • an equilibrium may be established between the protonated amine and the conjugate base of the acid, and unprotonated amine and acid.
  • Such a condition can be represented by the equation:
  • the equilibrium established will depend upon the relative strength of the acid.
  • the protonated amine be present in a concentration so as to stabilize the invert emulsion.
  • the type of counter- ion, B " is not particularly critical so long as it does not adversely affect the performance and characteristics of the resulting emulsion as is disclosed herein.
  • the counter-ion include the conjugate bases of the water soluble acids described below.
  • the protonated amines of the present invention function in the instant invention as a surfactant to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid.
  • a suspending agent is chemically associated with the solid components of a drilling fluid or mud.
  • organophilic clay is a suspending agent used in oil based muds. Organophilic clay is made by a process of cation exchange prior to formulation of the drilling fluid in which normally hydrophilic clay is reacted with quaternary ammonium salts to form a product that can be dispersed in oil. The function of such organophilic clays and other suspending agents is to enable the invert emulsion to suspend particles in the drilling fluid.
  • the amount of protonated amine should be sufficient to enable the non-oleaginous liquid to form a stable dispersion of fine droplets in the oleaginous liquid. That is to say the protonated amine should be present in a concentration sufficient to stabilize the invert emulsion and thus serve as the basis for the formulation of a useful invert emulsion drilling fluid. While this amount may vary depending upon the nature and amount of the oleaginous liquid and non-oleaginous liquid, typically the amount of protonated amine is at least about 0.1 percent by weight per volume of drilling fluid, preferably at least about 5 percent by weight per volume of drilling fluid, more preferably at least about 10 percent by weight per volume of drilling fluid of the total fluid. Correspondingly, the amount should not be so great to interfere with the stability of the invert emulsion fluid or the performance of the invert emulsion as a drilling fluid.
  • the term “acid” or “water soluble acid” refers to water-soluble, i.e. at least 10 percent by volume of the acid dissolves in water, compounds which are suitable to protonate the amine and render a stable non-oleaginous fluid in oleaginous fluid emulsion.
  • the term acid refers to both inorganic acids such as sulfuric, nitric, hydrofluoric, hydrochloric and phosphoric acid and organic acids such as citric, acetic, formic, benzoic, salicyclic, oxalic, glycolic, lactic, glutaric acid, and carbonic acid.
  • Fatty acids such as oleic, palmitic, and stearic acid are not within the definition of acid as used herein because such acids are not water-soluble.
  • Compounds that generate acidic solutions upon dissolution in water are also considered “acids" as the term is used herein.
  • acids may include, acetic anhydride, hydrolyzable esters, hydrolyzable organosulfonic acid derivatives, hydrolyzable organophosphoric acid derivatives, phosphorus trihalide, phosphorous oxyhalide, acidic metal salts, sulfur dioxide, nitrogen oxides, carbon dioxide, and similar such compounds.
  • the acidic solution is formed by the dissolution of an acidic metal salt in water.
  • the resulting solution is capable of protonating the amine and render a stable non-oleaginous fluid in oleaginous fluid emulsion.
  • the acidic solution is a brine formed by the dissolution of a neutral metal salt and an acidic metal salt in water.
  • an acidic solution may be formed by the dissolution of an acid compound and a neutral salt.
  • brines such as zinc bromide brine or zinc bromide and calcium bromide brine
  • these brines are acidic enough to protonate the amines of this invention to form invert emulsions.
  • Other transition metal salts may demonstrate utility in this invention, for instance acidic metal salt brines may be formed by the dissolution of a variety of first row transition metal salts in aqueous solution with or without other acids.
  • the preferred acidic metal salts are transition metal salts of neutral or acid anions, especially preferred are the first row transition metal slats due to the high cost of second and third row transition metal salts.
  • the anion of these salts may include halide, sulfate, sulfite, nitrate, hyrdosulfate and the like.
  • halide sulfate, sulfite, nitrate, hyrdosulfate and the like.
  • the amount of acid must be sufficient to protonate the amine without rendering the invert emulsion fluid so acidic that it is unstable. As one skilled in the art will appreciate, the amount of acid will necessarily vary tremendously with the strength of the acid and the particular amine to be protonated. Nevertheless, one skilled in the art having the benefit of this specification may readily determine the necessary amount of acid via routine experimentation.
  • the method of preparing the drilling fluids of the present invention is not particularly critical so long as an invert emulsion is formed.
  • the components may be mixed together in any order under agitation condition.
  • a representative method of preparing said invert emulsion fluids comprises mixing an appropriate quantity of oleaginous fluid and an appropriate quantity of amine together with continuous, mild agitation. A non-oleaginous fluid and acid is then added while mixing until an invert emulsion is formed. If weight material, such as those described below, are to be added, then the weight material is typically added after the invert emulsion fluid is formed.
  • INVERT EMULSION TEST A small portion of the emulsion is placed in a beaker which contains an oleaginous fluid. If the emulsion is an invert emulsion, the small portion of the emulsion will disperse in the oleaginous fluid. Visual inspection will determine if it has so dispersed. Alternatively, the electrical stability of the invert emulsion may be tested using a typical emulsion stability tester.
  • invert emulsion drilling fluids and muds formulated in accordance with the present invention should include those commonly expected of a useful invert emulsion drilling fluid. Such properties include measurable properties typical of a drilling fluid including: plastic viscosity; yield point; apparent viscosity; "GELS” ; API filtrate loss; or high temperature high pressure fluid loss.
  • surfactants and wetting agents conventionally used in invert emulsion fluids may optionally be incorporated in the fluids of this invention.
  • Such surfactants are, for example, fatty acids, soaps of fatty acids, amido amines, polyamides, polyamines, oleate esters, imidazoline derivatives, oxidized crude tall oil, organic phosphate esters, alkyl aromatic sulfates and sulfonates, as well as, mixtures of the above.
  • surfactants are employed in an amount which does not interfere with the fluids of this invention being used as drilling fluids.
  • Suspending agents also referred to herein as viscosifying agents, for example, organophilic clays, may optionally be employed in the invert drilling fluid compositions of the present invention.
  • other viscosifying agents such as oil soluble polymers, polyamide resins, polycarboxylic acids and fatty acid soaps and combinations of the above noted suspending agents may also be employed.
  • the amount of viscosifying agent used in the composition will necessarily vary depending upon the end use of the composition. Usually such viscosifying agents are employed in an amount which is at least about 0.1 percent by weight per volume of drilling fluid, preferably at least about 2 percent by weight per volume of drilling fluid, more preferably at least about 5 percent by weight per volume of drilling fluid of the total fluid.
  • VG-69TM and VG-PLUSTM are organoclay materials and Versa HRPTM is a polyamide resin material manufactured and distributed by M-I L.L.C. which are suitable viscosifying agents.
  • the invert emulsion drilling fluids of this invention may optionally contain a solid weight material.
  • the quantity and nature of the solid weight material depends upon the desired density and viscosity of the final composition.
  • the preferred solid weight materials include, but are not limited to, barite, iron oxides, calcium carbonate and the like.
  • the solid weight material is typically added in order to obtain a drilling fluid density of less than 24 pounds per gallon, preferably less than 21 pound per gallon, and most preferably less than 19.5 pounds per gallon.
  • the invert emulsion drilling fluids of the present invention may also be weighted by the use of acidic metal salt brines.
  • acidic metal salt brines Like solid weight materials, the quantity and nature of the acidic metal salt brine depends upon the desired density and viscosity of the final composition.
  • acidic metal salt brines may be formed by the dissolution of an acidic metal salt in aqueous solution with or without other acids.
  • the preferred acidic metal salts are transition metal salts of neutral or acid anions.
  • such anions include halide, sulfate, sulfite, nitrate, hyrdosulfate and the like.
  • the acidic metal salt is selected from the group including zinc chloride, zinc bromide, the hydrates of these salts, and their mixtures.
  • the acidic metal salt is zinc bromide.
  • a third embodiment includes a mixture of a neutral salt, such as calcium halide, or alkali metal halide, nitrate or sulfate, and an acidic metal salt is selected from the group including zinc chloride, zinc bromide, the hydrates of these salts, and their mixtures.
  • a mixture of zinc bromide and calcium bromide is used to generate a brine solution.
  • the concentration of the salt in solution can be varied.
  • a mixture of zinc bromide and calcium bromide is used to achieve a solution having a density of 19.2 pounds per gallon.
  • One skilled in the art should readily be able to formulate any such solution.
  • One method of doing this is to form a saturated aqueous solution of the selected salt or mixture of salts and measuring the density of the decanted solids free solution. The density of the saturated salt solution can be lowered by systematically diluting with small portions of water until the desired density is obtained. If a higher density solution is desired, a more soluble form of the metal salt may be selected or a combination of salts may be utilized. It should be noted that in some cases environmental concerns regarding the toxicity of the metal ion in solution should be considered when selecting the salt to be used to form the brine.
  • Fluid loss control agents such as modified lignite, polymers, oxidized asphalt and gilsonite may also be added to the invert drilling fluids of this invention. Usually such fluid loss control agents are employed in an amount which is at least about 0.1 percent by weight per volume of drilling fluid, preferably at least about 1 percent by weight per volume of drilling fluid, more preferably at least about 5 percent by weight per volume of drilling fluid of the total fluid.
  • the following examples are submitted for the purpose of illustrating the performance characteristics of the drilling fluid compositions of this invention. These tests were conducted substantially in accordance with the procedures in API Bulletin RP 13B-2, 1990 which is incorporated herein by reference. The following abbreviations may be used in describing the results of experimentation: "E.S.” is electrical stability of the emulsion as measured by the test described in
  • PV plastic viscosity which is one variable used in the calculation of viscosity characteristics of a drilling fluid, measured in centipoise (cp) units.
  • Yp yield point which is another variable used in the calculation of viscosity characteristics of drilling fluids, measured in pounds per 100 square feet (lb/100ft 2 ).
  • AV is apparent viscosity which is another variable used in the calculation of viscosity characteristic of drilling fluid, measured in centipoise (cp) units.
  • GELS is a measure of the suspending characteristics, or the thixotropic properties of a drilling fluid, measured in pounds per 100 square feet (lb/ 100 ft 2 ).
  • API F.L is the term used for API filtrate loss in milliliters (ml).
  • HTHP is the term used for high temperature high pressure fluid loss, measured in milliliters (ml) according to API bulletin RP 13 B-2, 1990.
  • Alkylamine JM-T Acetate The emulsifier Alkylamine JM-T acetate was not commercially available at the time of these experiments. Based on a knowledge of the art and the teachings of U.S. Patent No. 2,900,336, a chemically equivalent compound was prepared by mixing about 8.5 g of Alkylamine JM-T with about 2.0g glacial acetic acid (1 :1.05 mol ratio) for about 2 minutes.
  • Bentonite Gel Slurry A bentonite gel slurry was prepared by mixing about 75 ml of distilled water with about 0.75 g Wyoming bentonite (M-I GELL Supreme) for about 15 minutes.
  • EUenberger Field Crude Oil was not commercially available at the time of the these experiments. Based on a knowledge of the art and the teachings of U.S. Patent No. 2,900,336, diesel #2 was utilized as a substitute for the asphaltene-free and processed EUenberger Field crude oil utilized in U.S. Patent No. 2,900,336.
  • Preparation of Invert Emulsion The alkylamine JM-T acetate (8.25 g) was dissolved in about 225 ml of diesel #2. The diesel solution was added to the bentonite gel slurry and mixed on a Hamilton Beach mixer for about 15 minutes. The resulting mixture was allowed to stand at room temperature and separated into two layers (a predominately diesel layer and a predominately water layer) upon standing for about 20-30 minutes.
  • 2,900,336 fail to give an invert emulsion that may be used in the formulation of a drilling fluid. Further a drilling fluid formulated in accordance with the teachings of U.S. Patent No. 2,900,336 does not exhibit measurable properties of typical of a drilling fluid including: plastic viscosity; yield point; apparent viscosity; "GELS” ; API filtrate loss; or high temperature high pressure fluid loss.
  • Adogen - 151TM (Tall Oil Primary amine available from 10
  • the above formulation was prepared according to the following procedure: First, oil and organophilic clay were mixed in a glass jar on a Hamilton Beach mixer for 15 minutes. Then, Adogen-151TM was added and mixed for 10 minutes. Brine was then added and mixed for 15 minutes. CaCO 3 was then added and mixed for 15 minutes.
  • the above formulation was heat aged at 150° for 16 hours.
  • Example 3 The following formulation was prepared to demonstrate the utility of amine surfactant of this invention in 50/50 oil to water ratio oil base mud.
  • the mud was oil dispersible.
  • Jet-amine-PS TM (primary soya available from Jetco Chemical) 12.0
  • the above formulation was heat-aged at 150°F for 16 hours.
  • the following properties were measured after heat-aging.
  • SaraparTM - 147 oil 121 121 21 available from Shell Oil
  • Glacial acetic acid was then added to each of the above water-wet solids mix to neutralize the lime and protonate the amine surfactant. Upon protonating the amine surfactant, the formulations became water-in-oil invert emulsions. Electrical stability increased to 121, 138 and 110, respectively.
  • the above example demonstrates the use of amine surfactant in protonated form to make the invert emulsion of this invention.
  • the density of the zinc bromide brine solution was adjusted to achieve the desired density by either adding additional salt to increase the density or adding additional water to decrease the density.
  • the above formulations were prepared in a manner similar to Example 1 and heat aged at 150°F for 16 hours. The following heat aged properties were measured at room temperature.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

Nouveau fluide sous forme d'émulsion inverse, qui comporte un liquide oléagineux, un liquide non oléagineux, et une amine protonée de structure R-N+-H3 B- dans laquelle R représente un groupe alkyle C¿12?-C22 ou un groupe alcényle C12-C22, un groupe cycloalkyle C3-C8 substitué par un groupe alkyle ou alcényle C9-C14, ou un groupe alkyle ou alcényle C9-C14 substitué par un groupe cycloalkyle C3-C8 et B?-¿ représente la base conjuguée d'un acide hydrosoluble, l'amine protonée étant présente en quantité suffisante pour stabiliser l'émulsion inverse. Ces fluides sont acides et donc utiles dans des puits de forage dans lesquels des gaz acides tels que CO¿2? ou H2S sont susceptibles d'être rencontrés et de casser, c'est-à-dire de désémulsifier, le fluide de forage. Lesdits fluides peuvent également être utilisés en combinaison avec des solutions acides hypersalines pour augmenter la densité du fluide de forage.
PCT/US2000/007860 1999-03-24 2000-03-24 Fluides sous forme d'emulsions inverses, adaptes pour le forage WO2000056835A1 (fr)

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AU39184/00A AU3918400A (en) 1999-03-24 2000-03-24 Invert emulsion fluids suitable for drilling

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US27467799A 1999-03-24 1999-03-24
US09/274,677 1999-03-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059256A1 (fr) * 2000-02-10 2001-08-16 Halliburton Energy Services, Inc. Fluide de traitement de puits a emulsion inverse et procede

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900336A (en) * 1956-12-20 1959-08-18 Gulf Research Development Co Drilling fluids
US5254531A (en) * 1989-02-09 1993-10-19 Henkel Kommanditgesellschaft Auf Aktien Oleophilic basic amine compounds as an additive for invert drilling muds
WO1998005735A1 (fr) * 1996-08-02 1998-02-12 M-I L.L.C. Fluides a emulsion inverse, appropries au forage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900336A (en) * 1956-12-20 1959-08-18 Gulf Research Development Co Drilling fluids
US5254531A (en) * 1989-02-09 1993-10-19 Henkel Kommanditgesellschaft Auf Aktien Oleophilic basic amine compounds as an additive for invert drilling muds
WO1998005735A1 (fr) * 1996-08-02 1998-02-12 M-I L.L.C. Fluides a emulsion inverse, appropries au forage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE INTERNET [online] XP002139957, Database accession no. http://www.surface.akzonobel.com/p/index.htm *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059256A1 (fr) * 2000-02-10 2001-08-16 Halliburton Energy Services, Inc. Fluide de traitement de puits a emulsion inverse et procede
US6562764B1 (en) 2000-02-10 2003-05-13 Halliburton Energy Serv Inc Invert well service fluid and method

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