CA2405049C - Method of generating gas bubbles in oleaginous liquids - Google Patents

Method of generating gas bubbles in oleaginous liquids Download PDF

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CA2405049C
CA2405049C CA002405049A CA2405049A CA2405049C CA 2405049 C CA2405049 C CA 2405049C CA 002405049 A CA002405049 A CA 002405049A CA 2405049 A CA2405049 A CA 2405049A CA 2405049 C CA2405049 C CA 2405049C
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fluid
silicone oil
centistokes
oleaginous liquid
liquid
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CA2405049A1 (en
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Julie B. M. A. Morgan
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Masi Technologies LLC
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/21—Mixing gases with liquids by introducing liquids into gaseous media
    • B01F23/211—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/49—Mixing drilled material or ingredients for well-drilling, earth-drilling or deep-drilling compositions with liquids to obtain slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
    • B01F23/2373—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media for obtaining fine bubbles, i.e. bubbles with a size below 100 µm

Abstract

Disclosed is a method of generating microbubbles in oleaginous liquids which comprises adding a silicone oil to the oleaginous liquid and thereafter subjecting the liquid to mechanical forces in the presence of gas. Also disclosed are oil base well drilling and servicing fluids having a low shear rate viscosity as measured with a Brookfield Viscometer at 0.5 rpm of at least 10,000 centipoise and having incorporated therein microbubbles generated by the disclosed method, and a method of drilling a well wherein there is circulated within the wellbore during drilling the oil base, microbubble-containing fluid disclosed.

Description

METHOD OF GENERATING GAS BUBBLES IN OLEAGINOUS LIQUIDS
Background of the Invention There is disclosed in U.S. Patent 6,156,708 oleaginous base, re-circulateable, well drilling and servicing fluids containing colloidal gas aphrons (microbubbles). Such fluids comprise an oleaginous continuous phase, one or more viscosifiers that impart an elevated low shear rate viscosity to the fluid of at least 10, 000 centipoise, one or more aphron-generating surfactants, and aphrons.
The book by Felix Sebba entitled "Foams and Biliquid Foams - Aphrons", John Wiley & Sons, 1987 is an excellent source on the preparation and properties of aphrons in aqueous fluids. Aphrons are made up of a core which is often spherical of an internal phase, usually liquid or gas, encapsulated in a thin liquid shell of the continuous phase liquid. This shell contains surfactant molecules so positional that they produce an effective barrier against coalescence with adjacent aphrons.

Summary of the Invention I have now determined that gas bubbles and microbubbles can be generated in oleaginous liquids by incorporating into the oleaginous liquid a silicone oil and encapsulating a gas therein.
Thus, it is an object of the invention to provide a method of incorporating microbubbles into oleaginous liquids.
It is another object of the invention to provide oil base well drilling and servicing fluids containing microbubbles therein.
It is still another object of the invention to provide a method driiling a well wherein the novel drilling fluid of this invention is used as the re-circulateable drilling fluid.
These and other objects of the invention will be apparent to one skilled in the art upon reading the specification and claims hereof.
While the invention is susceptible of various modifications and alternative forms, specific embodiments thereof will hereinafter be described in detail and shown by way of example. It should be understood, however, that it is not intended to limit the invention to the particular forms disclosed, but, on the contrary, the invention is to cover all modifications and alternatives falling within the spirit and scope of the invention as expressed in the appended claims.

The compositions can comprise, consist essentially of, or consist of the stated materials. The method can comprise, consist essentially of, or consist of the stated steps with the stated materials.

Preferred Embodiments of the Invention In its broadest aspects, the present invention is directed to a method of incorporating microbubbles in oleaginous liquids preferably for use as oil base well drilling and servicing fluids (hereinafter sometimes referred to as "OBWDAS" fluids).
The method comprises adding a silicone oil to the oleaginous liquid and thereafter subjecting the silicone oil-containing oleaginous liquid to mechanical forces in the presence of a gaseous phase. The base oleaginous liquid may be any organic, water insoluble liquid which can be viscosified to the desired extent. Exemplary oleaginous liquids known in the art include petroleum oils or fractions thereof, vegetable oils, and various synthetic organic liquids such as olefins (alpha and internal unsaturation), oligomers of unsaturated hydrocarbons, carboxylic acid esters, phosphoric acid esters, ethers, polyalkyleneglycols, diglymes, acetals, and the like.
Microbubbles are generated in the oleaginous liquid by incorporating a silicone oil in the oleaginous liquid and thereafter subjecting the silicone-containing oleaginous liquid to mechanical forces in the presence of a gaseous phase to generate the microbubbles.
The microbubbles can be generated by means known in the art. In addition to the methods disclosed by Felix Sebba in his book referenced previously, methods are disclosed in Michelsen et al. U.S. Patent No.
5,314,644, Yoon et al. U.S. Patent No. 5,397,001, Kolaini U.S. Patent No.
5,783,118, Wheatley et al. U.S. Patent No. 5,352,436, and U.S. Patents No.
4,162,970; 4,112,025; 4,717,515; 4,304,740; and 3,671,022.
High shear mixing wherein a vortex is created in the presence of a gas will entrap gas bubbles iri the silicone-containing oleaginous liquid.
Mixing wherein the silicone-containing oleaginous liquid is pumped through an orifice in the presence of a gas wherein the liquid is subjected to a large pressure drop of at least 500 psi, such as from 500 to 5000 psi or more, will generate microbubbles in the oleaginous liquid.
When the silicone-containing oleaginous liquid is used as a well drilling and servicing .
fluid, microbubbles will also be produced by the pressure drop and cavitation as the fluid is pumped through the drill bit.
The gas used to create the microbubbles may be any gas which is not appreciably soluble in the oleaginous liquid. Thus the gas may be air, nitrogen, carbon dioxide, and the like, including air encapsulated in the fluid during mixing.
The silicone oils useful in the invention are well known in the art and available commercially from such companies as GE Silicones, HULS AMERICA, INC., DOW
CORNING, and CK WITCO. The silicone oils are basically siloxane polymers which have a backbone of Si-O linkages. Dimethyl silicone fluids, i.e., polydimethylsiloxanes, are available in various viscosity grades from about 0.5 centistokes at 25 C to about 2,500,000 centistokes having average molecular weights from about 100 to about 500,00, preferably from about 5 centistokes to about 100,000 centistokes. Also available are polydialkylsiloxanes, polydiphenylsiloxanes, poly(dimethyl/diphenyl)siloxanecopolymers, and polymethyl-alkylsiloxanes, such as polyinethyloctylsiloxane and polymethyloctadecylsiloxane.
The concentration of silicone oil required is generally from about 0.5 ppb (0.06 g/cm3) to about 20 ppb (2.4 g/cm3), preferably from about 1 ppb (0.12 g/cm3) to about 10 ppg (1.2 g/cm3). An indication of the volume of microbubbles generated can be obtained by determining the density reduction which occurs upon generating the microbubbles in the fluid. Foaming of the fluid, which is undesirable, may occur if the concentration of silicone oil is excessive. We have determined that the concentration of silicone oil can be increased, without any adverse effect on the fluid, as the LSRV increases. Thus the concentration of silicone oil, which can be determined by routine testing, is the amount required to generate sufficient microbubbles to give the density reduction desired but which is, preferably, insufficient to create a long-lasting foam on the surface of the fluid. The concentration of aphrons in the fluid is preferably from about 5% by volume to about 25%, most preferably from about 5% to about 20% by volume.
The density of the fluids can be adjusted, as required, by the addition of weight materials or the addition of soluble salts to the fluids as is well known in the art.
Preferably the weight material is added to the fluid before generation or incorporation of microbubbles therein, thus adjusting the final density of the microbubble-containing fluid to the desired density by the concentration of microbubbles therein.
As indicated, the concentration of microbubbles in the fluid should be less than about 25% by volume at atmospheric pressure. However, on circulation of the fluid in a borehole, the volume of the microbubbles is believed to decrease as the hydrostatic pressure of the fluid increases. Indeed the microbubbles may compress in size to almost no volume depending on the depth of the borehole. The measured density under pressure should be very close to the density of the fluid without any microbubbles. The microbubles do not disappear, however.
They are still present, and additional microbubbles will be generated at the face of the bit due to the pressure drop and cavitation. The microbubbles are extremely small, have very high surface area, and are highly energized.
As soon as the fluid exits the bit and starts back up the annulus, some pressure drop begins to occur and the microbubbles will begin to expand. As the fluid moves up the borehole and it encounters a loss to the formation, the microbubbles are filtered into the pore throats, microfractures, or other types of loss zone. These loss zones are areas where pressure drops occur. The microbubbles in these loss zones then expand and aggregate and hence seal the loss zones. The "% microbubbles by volume" in these micro environments is highly variable and will depend on the specific pressure and pressure drop within the loss zones.
Thus it is believed that the micro environment density is completely different than the density of the fluid in the borehole.
The density reduction at atmospheric pressure which occurs on entraining up to about 25% by volume of a gas in the fluids of the invention is sufficient to provide the quantity of microbubbles needed in the borehole while allowing the fluid to be recirculatable without causing pump problems.
Additionally, the fluid may contain other functional materials known in the art such as emulsifiers, wetting agents, and the like.
Without being limited hereby, it is believed that the microbubbles present in the fluid effectively seal the formation during drilling or well servicing operations thus preventing the excessive loss of fluid to the formations being drilled or serviced.
The fluids of this invention can be used in conventional drilling and well servicing operations as conducted in the art. Thus in drilling an oil and/or gas well the fluid is circulated from the surface down the drill pipe, coiled tubing, or the like through the bit and up the annulus between the drill pipe and the sides of the borehole back to the surface. The microbubbles in the fluid seal the borehole surface preventing the loss of excessive amounts of fluid to the formations being drilled.
It is preferred that the microbubble-containing fluid of the present invention be utilized in a drilling process wherein the drill bit is a cavitating liquid jet assisted drill bit. Exemplary cavitating liquid jet assisted drill bits are set forth in Johnson, Jr. et al. U.S. Patent No. 4, 262,757 and Johnson, Jr.
et al. U.S. Patent No. 4,391,339. Preferably the cavitating jet nozzle in the cavitating liquid jet assisted drill bit includes a pin received at a central position which lowers the pressure of the pressurized drilling fluid such that cavitation bubbles form in the fluid. See for example Henshaw U.S. Patent No. 5,086,974 and Henshaw U.S. Patent No. 5,217,163.
Similarly, the fluids of the invention can be in well servicing operations such as completion operations, workover operations, sand control operations, frac pack operations, and the like. The fluids can be used as spotting fluids to release pipes and tools stuck in the filter cake on the sides of a borehole by differential sticking.
The stability of the microbubbles in the oleaginous liquid can be increased by increasing the viscosity of the oleaginous liquid, preferably the low shear rate viscosity (hereinafter sometimes referred to as "LSRV"). The LSRV
for the purposes of this invention is the viscosity measured on a Brookfield Viscometer at shear rates less than about 1 sec-1, such as at 0.3 to 0.5 rpm.
The LSRV of the microbubble-containing oleaginous liquid should be at least 10,000 centipoise, preferably at least about 20,000 centipoise, and most preferably at least about 40,000 centipoise. Since the stability of the microbubbles is enhanced as the LSRV increases, a LSRV of several hundred thousand may be desired.
The viscosity of the oleaginous liquid can be increased with various viscosifiers/gellants such as organophilic clays, colloidal fumed silicas, resins, polymers, dimer acids, fatty amine salts of anionic polysaccharides, fatty acid salts of cationic polysaccharides, oil-dispersible/soluble latex-type products, and mixtures thereof as is known in the art.
The organophilic clays useful as viscosifiers to increase the LSRV of the oleaginous fluids of this invention are well known in the art. They comprise reaction products or organic onium compounds with naturally occurring or synthetic clays. The clay portion of the organophilic clay gellants are crystalline, complex inorganic silicates, the exact composition of which cannot be precisely defined since they vary widely from one natural source to another. However, these clays can be described as complex, inorganic silicates, such as aluminum silicates and magnesium silicates, containing, in addition to the complex silicate lattice, varying amounts of cation-exchangeable ions, such as calcium, magnesium, and sodium. Hydrophilic clays which are preferred in this invention are the water-swelling smectite clays, such as montmorillonite, hectorite, saponite and particularly bentonite clay from Wyoming which contains exchangeable sodium ions. Attapulgite clay and saponite clay can also be used as the clay portion of the organophilic clay. The clays may be used in the impure form as such or may be purified by centrifuging an aqueous slurry of the clay.
The organic onium compounds reacted with the smectite clays are desirably acidic salts of primary, secondary and tertiary amines, preferably quaternary ammonium compounds. The onium compounds should contain at least one alkyl, alkylene or alkylidiene radical having at least ten carbon atoms, preferably about 16 to 22 carbon atoms. Typical quaternary ammonium compounds are dimethyl dihydrogenated tallow ammonium chloride, trimethyl hydrogenated tallow ammonium chloride, dimethyl benzyl octadecyl ammonium chloride and methyl benzyl dioctodecyl ammonium chloride. A typical acid salt of an amine is the acid salt of cocoamine. Other organic onium compounds, such as organic phosphonium compounds, can be used. Organic modified clays and their preparation are more fully described in U.S. Pat. Nos. 2,531,427;
2,531,812; 2,966,506; 3,929,849; 4,287,086; 4,105,578.
The preferred organophilic clays for use in the drilling fluids of the present invention are dimethyldihydrogenated tallow ammonium bentonite, di-methylbenzyl-hydrogenated tallow ammonium bentonite, and methylbenzyl-dihydrogenated tallow ammonium bentonite.
Schumate et al. U.S. Patent No. 5,021,170 discloses that a sulfonated, ethylene/propylene/5-phenyl-2-norborene terpolymer (EPDM polymer) and an organophilic clay viscosifier synergistically increase the viscosity and suspension characteristics of invert emulsion drilling fluids, particularly such fluids which have a low aromatic content hydrocarbon as the oleaginous liquid phase. The EPDM polymer is generally described in U.S. Patent No. 4,442,011.
Basically, the EPDM polymers have about 5 to about 30 milliequivalents of sulfonate group per hundred grams of the sulfonate polymer, wherein the sulfonate group is neutralized with a metallic cation or an amine or ammonium counterion. The EPDM polymers have about 0.5 to about 20% by weight phenyl norbornene, or preferably about 1 to about 10%, most preferably about 2 to about 8%. The preferred polymers contain about 10 to about 80% by weight ethylene and about 1 to about 10% by weight of 5-phenyl-2-nobornene monomer, the balance of the polymer being propylene. Preferably, the polymer contains from about 30 to about 70% by weight ethylene, e.g., 50 weight percent, and 2 to about 8% phenyl-2-norborene monomer, e.g., 5.0 weight percent.
A typical ethylene/propylene/5-phenyl-2-norborene terpolymer has a Mooney viscosity (ML, 1+8, 212 F) of about 16 and has an ethylene content of about 50 weight percent and a 5-phenyl-2-norbornene content of about 5 weight percent.
The terpolymers have a number average molecular weight (Mn), as measured by Gel Permeation Chromatograph (GPC), of about 5,000 to about 300,000, more preferably of about 10,000 to about 80,000. The Mooney viscosity of the terpolymer is about 5 to about 90, more preferably about 10 to about 80, most preferably about 15 to about 50.
The gelling agent comprised of the terpolymer and the clay will generally be present in the drilling fluid in an amount of from about 0.5 pounds to about 10 pounds per 42 gallon barrel (ppb) of fluid.
Oehler et al. U.S. Patent No. 4,816,551 discloses that certain amide resins provide more shear thinning fluids with improved thixotropy in fluids containing an organophilic clay viscosifier, particularly in low viscosity mineral oils. The amide resins are the reaction products of a dibasic dimerized or trimerized fatty acid, a dialkanolamine, and a dialkylenepolyamine.
Dibasic acids may be the dimerized fatty acids, commercial products prepared by dimerization of unsaturated fatty acids containing at least 8, preferably about 10 or more to about 18 carbon atoms, including 9-dodecanoic(cis), 9-tetradodecanoic(cis), 9-octadecanoic(cis), octadecatetranoic acids, and the like. The typical molecule would contain two carboxyl groups and about 36 carbon atoms in a branched chain configuration. The dibasic trimerized fatty acid may be used which is also a commercial material and similarly prepared, containing about 54 carbon atoms, if at least one of the carboxyl groups is blocked or made inactive by being in the form of an ester group, a salt and the like, i.e., the trimerized fatty acid as used in this invention is a dibasic acid. Mixtures of dimerized acids and trimerized acids may be used.
The dialkanolamines include hydroxyalkylamines, for example, materials wherein the alkanol groups contain 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms; including for example diethanol amine, di-n-propanol amine, di-iso-propanol amine, dibutanol amine, dipentanolamine, dihexanol amine, and the like, and combinations thereof. Preferred are diethanol amine and dipropanol amine. Alkyl hydroxyalkyl-amines including ethylhydroxyethyl amine, propylhydroxyethyl amine, butylhydroxy-propyl amine, and the like can also be used.
The polyalkylene polyamines include materials wherein the alkylene groups contain about 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms:
"poly" refers to an integer from about 2 to 20, and at least 3 nitrogen atoms.
These materials may be represented by the general formula H H H
R,,,, - "4x---W--~ Rõ-, wherein R' is an alkylene group containing 1 to 6 carbon atoms, R"" is hydrogen or an alkyl group containing 1 to 6 carbon atoms, an x is an integer from 1 to 20. Typical useful materials include diethylene triamine, triethylene tetraamine, tetramethylene pentaamine, polyamine HH, polyamine HPA, and the like. Preferred are diethylene triamine and triethylene tetraamine.
The products may be represented by the general formula HO-R"-N-R"' Y HO-R" IV-R"' Y HO-R"-N-R"' Y

R R ~
~=O L-0 L-0 R,,,,-IV (R'--V)x R'-N R, wherein R is an alkylene group containing 20, preferably about 30 to 54 carbon atoms; R' is an alkylene group containing 1 to 6 carbon atoms, R" is an alkylene group containing 1 to 6 carbon atoms, R"' is an alkylene group containing 1 to 6 carbon atoms, R"" is a direct bridge, covalent bond, between N and Y or is a hydrogen or alkyl radical containing 1 to 6 carbon atoms, Y is hydrogen or hydroxy, and x is an integer from 1 to 20.
Cooperman et al. U.S. Patent No. 5,710,110 discloses that 0.01 to about 5% by weight of certain amine additive reaction products in combination with one or more rheologically active clay-based materials provide improved anti-settling properties for both oil and invert oil emulsion based drilling fluids. Such rheologically active clay-based materials include organoclays, smectite-type clays including Wyoming bentonite, beneficiated sodium and calcium bentonite and hectorite, and attapulgite clay. Organoclays and method of making them are described, for example, in U.S. Pat. Nos. 5,075,033, 5,130,028, and 5,151,155. Smectite-type clays are cation-exchangeable clays described at length and by chemical formula in U.S. Pat. No. 5,350,562. Bentonite, a particularly useful clay for this invention, is described at length in Carr.
Industrial Minerals and Rocks. 6th Edition (1994) in a chapter entitled Bentonite, authored by Drs. Elzea and Murray of Indiana University.
Attapulgite clays are well known natural clays which possess cation exchange capacity but of a lower amount than smectite-type clays such as bentonite and hectorite.
The amine additive reaction products comprise one or more reaction products of one or more polyalkoxylated aliphatic amino compounds having a chemical structure represented by the following formula:

R
(~z&O)xH
R~ N
(CH2CxO)YH
i wherein R, is a straight chain alkyl group derived from fatty sources having to 18 carbon atoms, R is selected from the group consisting of hydrogen, methyl and ethyl, both x and y are at least 1, and the sum of x+y is from 2 to 15 and one or more organic compounds selected from the group consisting of maleic anhydride, phthalic anhydride and mixtures thereof.
An increase in anti-settling properties is achieved from this mixture combination within broad ranges of amines to rheologically active clay.
Alternative ways of preparing a drilling fluid according to this invention are to add such cation exchangeable clay-based material to the drilling fluid separately from the above mentioned amine reaction products, to add the amine additive to the drilling fluid when the fluid is being used to drill through domains containing rheologically active clays, or to add the amine alone if the drilling fluid already contains such clay-based materials.
Exemplary polymers useful as viscosifiers in the fluid of this invention are set forth in the following references.
Peiffer et al. U.S. Statutory Invention Registration No. H837 discloses the use of a water insoluble, hydrocarbon soluble polymeric complex formed from a sulfonate (anionic) polymer and a water insoluble vinyl pyridine (cationic) polymer as a viscosifier for oil-based drilling muds.
Peiffer et al. U.S. Patent No. 4,978,461 discloses the use of a thermoplastic terpolymer of p-methylstyrene/metal neutralized styrene sulfonate/styrene as viscosii=lcation agents for oil-based drilling muds.
Patel et al. U.S. Patent No. 4,740,319 discloses the use of latices comprising a polymer which is the reaction product of a first monomer selected from the group consisting of styrene, butadiene, isoprene, and mixtures thereof and a second functional monomer which contains a radical selected from the group consisting of amide, amine, sulfonate, carboxylic acid, dicarboxylic acid, and combinations thereof, provided that at least one of the functional monomers is a nitrogen containing material selected from the group consisting of amides and amines.
Turner et al. U.S. Patent No. 4,425,461 discloses the use of a mixture of a water insoluble neutralized sulfonate thermoplastic polymer and a water insoluble neutralized sulfonate elastomeric polymer as viscosification agents for oil-based drilling muds.
Commercially available polymers include HYBILDTM 201 (BP Chemicals), HYVISTM (Unocal), and others.
In addition to the silicone oil, the microbubble-containing oleaginous fluids of this invention may contain surfactants such as those disclosed in U.S.
Patent 6,156,708. The surfactant may also have one or more stabilizers incorporated therein, such as alkyl alcohols, fatty alkanolamides, and alkyl betaines. Generally the alkyl chain will contain from about 10 to about 18 carbon atoms. The aphron-generating surfactant may be anionic, non-ionic, or cationic depending on compatibility with the viscosifier.
The fluorosurfactants include, but are not limited to, (i) fluorinated telomers, (ii) amphoteric fluorosufactants, (iii) polyfluorinated amine oxide, (iv) fluoroalkyl ethylthiopolyacrylamides, (v) perfluoroalkyl ethylthiopoly-acrylamides, (vi) derivatives of 1-propanaminium, 2-Hydroxy-N,N,N-trimethyl-3-gamma-omega-perfluoro-(C6-C20-alkyl) thio, chloride, (vii) fluoroalkyl sodium sulfonate, and (viii) sodium salts of 1-propanesulfonic acid, 2-methyl-, 2-{[1-oxo-3[gamma,-omega,-perfluoro-C16-C26-alkyl) thio} propyl} amino}
derivative.

A particularly preferred fluorosurfactant is a mixture of fluoroaliphatic polymeric esters sold by 3M Company under the tradename FLUORADTM FC
740.
D'Arrigo U.S. Patent No. 4,684,479 discloses surfactant mixtures comprising (a) a member selected from the group consisting of glycerol monoesters of saturated carboxylic acids containing from about 10 to about 18 carbon atoms and aliphatic alcohols containing from about 10 to about 18 carbon atoms; (b) a sterolaromatic acid ester; (c) a member selected from the group consisting of sterols, terpenes, bile acids and alkali metal salts of bile acids; (d) a member selected from the group consisting of sterol esters of aliphatic acids containing from 1 to about 18 carbon atoms; sterol esters of sugar acids; esters of sugar acids and aliphatic alcohols containing from about 10 to about 18 carbon atoms; esters of sugars and aliphatic acids containing from about 10 to about 18 carbon atoms; sugar acids; saponins; and sapogenins; and (e) a member selected from the group consisting of glycerol, glycerol di- or triesters of aliphatic acids containing from about 10 to about carbon atoms and aliphatic alcohols containing from about 10 to about 18 carbon atoms; said components being present in said mixture in a weight ratio a:b:c:d:e of 2-4:0.5-1.5:0.5-1.5:0-1.5:0-1.5.
As indicated, the microbubble-containing oleaginous liquids of the invention are useful as oil and gas well driiiing and servicing fluids.
Optionally, the OBWDAS fluids may contain water as a dispersed phase, various emulsifying agents, wetting agents, weighting agents, fluid loss control agents, water soluble salts, and the like as is known in the art.
The following examples are presented to demonstrate the invention but should not be construed as limiting the scope of the invention. The silicone oils evaluated are as follows: polydimethylsiloxane having nominal viscosities of 1,000, 10,000, or 100,000 centistokes. Abbreviations used in the table or this specification are as follows: cp = centipoise ; g = grams; ml = milliliters;
cm3 = cubic centimeters; v = volts; OS = off-scale, > 2000 v; sec = seconds; ppb = pounds per barrel; min-minutes; rpm = revolutions per minute; ctsk =
centistokes; ppg = pounds per gallon; LSRV = low shear rate viscosity measured on a Brookfield Viscometer at 0.3-0.5 rpm. The Fann Rheology were determined at ambient temperature (22 C) using the procedure set forth in the American Petroieum Institute Bulletin RP13-B.
Example 1 Fluids were prepared by mixing together on a high shear blender 340 ml of Iso-Teq internal olefin oil, 9.3 g of VEN-GEL 420 organophilic attapulgite, 4.3 g of Claytone II
organophilic bentonite, 1.4 g of propylene carbonate, 2.0 g of aluminum stearate, 10 ml of water, and the concentration of the silicone oils set forth in Table I. Upon cooling to ambient temperature the Brookfield and Fann rheologies were obtained. The fluids were thereafter hot rolled at 185 F for 16 hours, cooled, and the Brookfield and Fann rheologies, emulsion stability, and density before and after mixing were obtained. The % density reduction, which is a measure of the concentration of microbubbles in the fluids, was calculated as follows:

% Density Reduction - 100 Density Before Mixing - Density After Mixing Density Before Mixing Table I

All Fluids Contain 350 ml Iso-Teq Oil, 9.3 g VEN-GEL 420 Organophilic Attapulgite, 4.3 g CLAYTONE 11 Organophilic Bentonite, 1.4 g Propylene Carbonate, 2.0 g Aluminum Stearate, 10 ml Water, and the Concentration of Silicone Oil Set Forth in the Table Fluid I-1 1-2 1-3 1-4 1-5 I-6 1-7 1-8 Silicone Oil Viscosity, ctsk (xl0"3) 1 1 1 10 100 100 100 100 Silicone Oil, g 2 3 4 3 1 2 3 4 INiTIAL RHEOLOGY
Brookfield Rheology 0.3 rpm (x10"3), cp 46 52 82.7 58 103 82 44.7 70.7 0.5 rpm (x10"3), cp 30.8 36.4 59.6 32.4 47.6 47.6 28.8 52.8 100rpm,cp 444 310 528 234 444 496 414 416 Faim Rheology 600 rpm 55 42 58 39 50 61 56 60 300 rpm 44 32 48 29 40 51 43 49 Plastic Viscosity 11 10 10 10 10 10 13 11 Yield Point 33 22 38 19 30 41 30 38 Brookfield Rheology 0.3 rpm (x10"3), cp 115 96.7 106 153 125 108 141 94.7 0.5 rpm (x10-3), cp 72.8 70 75.2 103 68.8 87.2 72 69.2 100 rpm, cp 818 1210 1218 962 932 686 984 956 Fann Rheology 600rpm 100 99 115 86 91 103 105 117 300 rpm 82 85 98 71 69 80 90 95 Table I (cont'd) Plastic Viscosity 18 14 17 15 22 23 15 22 Yield Point 64 71 81 56 47 57 75 73 sec. Gel Strength 53 52 76 45 43 53 60 73 10 min. Gel Strength 56 48 60 43 52 52 57 50 10 Emulsion Stability, v OS OS OS OS OS OS OS OS
Density (before mixing), ppg 6.6 6.8 6.7 6.8 6.7 6.7 6.7 6.7 Density (after mixing), ppg 5.8 5.5 5.7 5.9 5.7 5.9 5.7 5.8 % Density Reduction 12.1 19.1 14.9 13.2 14.9 11.9 14.9 13.4

Claims (68)

CLAIMS:
1. A method of generating gas bubbles suspended in oleaginous liquids which comprises adding a silicone oil to the oleaginous liquid and thereafter subjecting the oleaginous liquid to mechanical forces in the presence of a gas.
2. The method of claim 1 wherein the silicone oil is a polydimethylsiloxane oil having a nominal viscosity at 25°C of about 0.5 centistokes to about 2,500,000 centistokes.
3. The method of claim 1 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, carboxylic acid esters, phosphoric acid esters, ethers, polyalkylene glycols, diglymes, acetals, and mixtures thereof.
4. The method of claim 2 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, carboxylic acid esters, phosphoric acid esters, ethers, polyalkylene glycols, diglymes, acetals, and mixtures thereof.
5. The method of claim 1 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, and mixtures thereof.
6. The method of claim 2 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, and mixtures thereof.
7. The method of claim 1 wherein the gas is selected from the group consisting of air, nitrogen, carbon dioxide, and mixtures thereof.
8. The method of claim 2 wherein the gas is selected from the group consisting of air, nitrogen, carbon dioxide, and mixtures thereof.
9. The method of claim 5 wherein the gas is selected from the group consisting of air, nitrogen, carbon dioxide, and mixtures thereof.
10. The method of claim 6 wherein the gas is selected from the group consisting of air, nitrogen, carbon dioxide, and mixtures thereof.
11. The fluid of claim 1 wherein subjecting the oleaginous liquid to mechanical forces comprises at least one of 1) mixing the silicone oil-containing oleaginous liquid wherein a vortex is created and 2) pumping the silicone oil-containing oleaginous liquid wherein the liquid is subjected to a pressure drop of at least 500 psi.
12. The method of claim 2 wherein subjecting the oleaginous liquid to mechanical forces comprises at least one of 1) mixing the silicone oil-containing oleaginous liquid wherein a vortex is created and 2) pumping the silicone oil-containing oleaginous liquid wherein the liquid is subjected to a pressure drop of at least 500 psi.
13. The method of claim 4 wherein subjecting the oleaginous liquid to mechanical forces comprises at least one of 1) mixing the silicone oil-containing oleaginous liquid wherein a vortex is created and 2) pumping the silicone oil-containing oleaginous liquid wherein the liquid is subjected to a pressure drop of at least 500 psi.
14. The method of claim 6 wherein subjecting the oleaginous liquid to mechanical forces comprises at least one of 1) mixing the silicone oil-containing oleaginous liquid wherein a vortex is created and 2) pumping the silicone oil-containing oleaginous liquid wherein the liquid is subjected to a pressure drop of at least 500 psi.
15. The method of claim 8 wherein subjecting the oleaginous liquid to mechanical forces comprises at least one of 1) mixing the silicone oil-containing oleaginous liquid wherein a vortex is created and 2) pumping the silicone oil-containing oleaginous liquid wherein the liquid is subjected to a pressure drop of at least 500 psi.
16. An oil base well drilling and servicing fluid comprising an oleaginous liquid as the continuous liquid phase having incorporated therein one or more viscosifiers such that the fluid has a low shear rate viscosity as measured with a Brookfield Viscometer at 0.5 rpm of at least about 10,000 centipoise, a silicone oil for generating microbubbles in the oleaginous liquid, and microbubbles, wherein the microbubbles are generated by subjecting the silicone oil-containing oleaginous liquid to mechanical forces in the presence of a gas.
17. The fluid of Claim 16 wherein a target density of the fluid is achieved by varying the concentration of microbubbles.
18. The fluid of Claim 17 wherein the silicone oil is a polydimethylsiloxane oil having a nominal viscosity at 25°C of about 5 centistokes to about 100,000 centistokes.
19. The fluid of Claim 18 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, and mixtures thereof.
20. The fluid of Claim 19 wherein the gas is selected from the group consisting of air, nitrogen, carbon dioxide, and mixtures thereof.
21. The fluid of Claim 20 wherein the mechanical forces comprise at least one of mixing the silicone oil-containing oleaginous liquid wherein a vortex is created and pumping the silicone oil-containing oleaginous liquid wherein the liquid is subjected to a pressure drop of at least 500 psi.
22. The fluid of Claim 16, 17, 18, 19, 20, or 21 wherein the low shear rate viscosity is at least about 40,000 centipoise, and wherein the fluid contains from about 5% to about 25% by volume of the microbubbles.
23. A method of drilling a well wherein there is circulated within the wellbore the fluid of Claim 16, 17, 18, 19, 20, or 21.
24. The method of drilling a well wherein there is circulated within the wellbore the fluid of claim 22.
25. A drilling or servicing fluid comprising:
an oleaginous liquid;
silicone oil; and microbubbles.
26. The fluid according to claim 25 wherein the oleaginous liquid comprises a continuous phase and further comprising a discontinuous aqueous phase.
27. The fluid according to claim 25 further comprising a viscosifier.
28. The fluid according to claim 27 wherein the viscosifier is selected from the group consisting of organophilic clays, colloidal fumed silicas, resins, polymers, dimer acids, fatty amine salts of anionic polysaccharides, fatty acid salts of cationic polysaccharides, oil-dispersible/soluble latex-type products, and mixtures thereof.
29. The fluid according to claim 27 wherein the low shear rate viscosity of the fluid as measured with a Brookfield Viscometer at 0.5 rpm is at least 20,000 centipoise.
30. The fluid according to claim 27 wherein the low shear rate viscosity of the fluid as measured with a Brookfield Viscometer at 0.5 rpm is at least 40,000 centipoise.
31. The fluid according to claim 25 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, carboxylic acid esters, phosphoric acid esters, ethers, polyalkylene glycols, diglymes, acetals, and mixtures thereof.
32. The fluid according to claim 25 wherein the silicone oil contains a polydimethylsiloxane.
33. The fluid according to claim 32 wherein the silicone oil has a nominal viscosity at 25°C of about 0.65 centistokes to about 2,500,000 centistokes.
34. The fluid according to claim 25 wherein the silicone oil contains a polydialkylsiloxane.
35. The fluid according to claim 34 wherein the silicone oil has a nominal viscosity at 25°C or about 0.65 centistokes to about 2,500,000 centistokes.
36. The fluid according to claim 25 wherein the silicone oil contains a polydiphenylsiloxane.
37. The fluid according to claim 36 wherein the silicone oil has a nominal viscosity at 25°C of about 0.65 centistokes to about 2,500,000 centistokes.
38. The fluid according to claim 25 wherein the silicone oil contains a poly(dimethyl/diphenyl)siloxanecopolymer.
39. The fluid according to claim 38 wherein the silicone oil has a nominal viscosity at 25°C of about 0.65 centistokes to about 2,500,000 centistokes.
40. The fluid according to claim 25 wherein the silicone oil contains a polymethyl-alkylsiloxane.
41. The fluid according to claim 40 wherein the silicone oil has a nominal viscosity at 25°C of about 0.65 centistokes to about 2,500,000 centistokes.
42. The fluid according to claim 25 wherein the microbubbles comprise less than 25% by volume of the fluid.
43. The fluid according to claim 25 wherein the microbubbles comprise less than 20% by volume of the fluid.
44. The fluid according to claim 25 wherein the fluid is recirculateable.
45. The fluid according to claim 25 wherein the microbubbles prevent loss of excess fluid into the formation.
46. The fluid according to claim 25 wherein the microbubbles effectively seal the formation.
47. A process for drilling or servicing a wellbore in a subterranean formation wherein a drilling or servicing fluid is circulated in the wellbore, comprising:

utilizing as the drilling or servicing fluid an oleaginous liquid, silicone oil and microbubbles.
48. The process according to claim 47 wherein the oleaginous liquid comprises a continuous phase and further comprising a discontinuous aqueous phase.
49. The process according to claim 47 wherein the drilling or servicing fluid further comprises a viscosifier.
50. The process according to claim 49 wherein the viscosifier is selected from the group consisting of organophilic clays, colloidal fumed silicas, resins, polymers, dimer acids, fatty amine salts of anionic polysaccharides, fatty acid salts of cationic polysaccharides, oil-dispersible/soluble latex-type products, and mixtures thereof.
51. The process according to claim 49 wherein the low shear rate viscosity of the fluid as measured with a Brookfield Viscometer at 0.5 rpm is at least 20,000 centipoise.
52. The process according to claim 49 wherein the low shear rate viscosity of the fluid as measured with a Brookfield Viscometer at 0.5 rpm is at least 40,000 centipoise.
53. The process according to claim 47 wherein the oleaginous liquid is selected from the group consisting of petroleum oils or fractions thereof, alpha olefins, internal olefins, oligomers of unsaturated hydrocarbons, carboxylic acid esters, phosphoric acid esters, ethers, polyalkylene glycols, diglymes, acetals, and mixtures thereof.
54. The process according to claim 47 wherein the silicone oil contains a polydimethylsiloxane.
55. The process according to claim 54 wherein the silicone oil has a nominal viscosity at 25°C
of about 0.65 centistokes to about 2,500,000 centistokes.
56. The process according to claim 47 wherein the silicone oil contains a polydialkylsiloxane.
57. The process according to claim 56 wherein the silicone oil has a nominal viscosity at 25°C
of about 0.65 centistokes to about 2,500,000 centistokes.
58. The process according to claim 47 wherein the silicone oil contains a polydiphenylsiloxane.
59. The process according to claim 58 wherein the silicone oil has a nominal viscosity at 25°C
of about 0.65 centistokes to about 2,500,000 centistokes.
60. The process according to claim 47 wherein the silicone oil contains a poly(dimethyl/diphenyl)siloxanecopolymer.
61. The process according to claim 60 wherein the silicone oil has a nominal viscosity at 25°C
of about 0.65 centistokes to about 2,500,000 centistokes.
62. The process according to claim 47 wherein the silicone oil contains a polymethyl-alkylsiloxane.
63. The process according to claim 62 wherein the silicone oil has a nominal viscosity at 25°C
of about 0.65 centistokes to about 2,500,000 centistokes.
64. The process according to claim 47 wherein the microbubbles comprise less than 25% by volume of the fluid.
65. The process according to claim 47 wherein the microbubbles comprise less than 20% by volume of the fluid.
66. The process according to claim 47 wherein the drilling or servicing fluid is recirculateable.
67. The process according to claim 47 wherein the microbubbles prevent loss of excess drilling or servicing fluid into the formation.
68. The process according to claim 47 wherein the microbubbles effectively seal the formation.
CA002405049A 2000-04-04 2001-04-04 Method of generating gas bubbles in oleaginous liquids Expired - Fee Related CA2405049C (en)

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Families Citing this family (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8512718B2 (en) 2000-07-03 2013-08-20 Foamix Ltd. Pharmaceutical composition for topical application
IL152486A0 (en) 2002-10-25 2003-05-29 Meir Eini Alcohol-free cosmetic and pharmaceutical foam carrier
US10117812B2 (en) 2002-10-25 2018-11-06 Foamix Pharmaceuticals Ltd. Foamable composition combining a polar solvent and a hydrophobic carrier
US7700076B2 (en) 2002-10-25 2010-04-20 Foamix, Ltd. Penetrating pharmaceutical foam
US9211259B2 (en) 2002-11-29 2015-12-15 Foamix Pharmaceuticals Ltd. Antibiotic kit and composition and uses thereof
US8900554B2 (en) 2002-10-25 2014-12-02 Foamix Pharmaceuticals Ltd. Foamable composition and uses thereof
US8119150B2 (en) 2002-10-25 2012-02-21 Foamix Ltd. Non-flammable insecticide composition and uses thereof
US7820145B2 (en) 2003-08-04 2010-10-26 Foamix Ltd. Oleaginous pharmaceutical and cosmetic foam
US9265725B2 (en) 2002-10-25 2016-02-23 Foamix Pharmaceuticals Ltd. Dicarboxylic acid foamable vehicle and pharmaceutical compositions thereof
US8119109B2 (en) 2002-10-25 2012-02-21 Foamix Ltd. Foamable compositions, kits and methods for hyperhidrosis
KR101108439B1 (en) 2002-10-25 2012-01-31 포믹스 리미티드 Cosmetic and pharmaceutical foam
US7704518B2 (en) 2003-08-04 2010-04-27 Foamix, Ltd. Foamable vehicle and pharmaceutical compositions thereof
US8486376B2 (en) 2002-10-25 2013-07-16 Foamix Ltd. Moisturizing foam containing lanolin
US20080138296A1 (en) 2002-10-25 2008-06-12 Foamix Ltd. Foam prepared from nanoemulsions and uses
US9668972B2 (en) 2002-10-25 2017-06-06 Foamix Pharmaceuticals Ltd. Nonsteroidal immunomodulating kit and composition and uses thereof
MXPA05008261A (en) * 2003-02-03 2011-10-24 Masi Technologies Llc Stabilized colloidal and colloidal-like systems.
GB2413582A (en) * 2003-02-03 2005-11-02 Masi Technologies Llc Stabilized colloidal and colloidal-like systems
US7575739B2 (en) 2003-04-28 2009-08-18 Foamix Ltd. Foamable iodine composition
US7199085B2 (en) * 2003-05-06 2007-04-03 Masi Technologies, Inc. Colloidal and colloidal-like systems in aqueous, clay-based fluids
US8486374B2 (en) 2003-08-04 2013-07-16 Foamix Ltd. Hydrophilic, non-aqueous pharmaceutical carriers and compositions and uses
US8795693B2 (en) 2003-08-04 2014-08-05 Foamix Ltd. Compositions with modulating agents
US7081437B2 (en) * 2003-08-25 2006-07-25 M-I L.L.C. Environmentally compatible hydrocarbon blend drilling fluid
US20080006604A1 (en) * 2005-04-07 2008-01-10 Keady John P Devices and methods for using electrofluid and colloidal technology
US9714371B2 (en) 2005-05-02 2017-07-25 Trican Well Service Ltd. Method for making particulate slurries and particulate slurry compositions
AU2006298442A1 (en) 2005-05-09 2007-04-12 Foamix Ltd. Saccharide foamable compositions
US7767628B2 (en) * 2005-12-02 2010-08-03 Clearwater International, Llc Method for foaming a hydrocarbon drilling fluid and for producing light weight hydrocarbon fluids
US20080260655A1 (en) 2006-11-14 2008-10-23 Dov Tamarkin Substantially non-aqueous foamable petrolatum based pharmaceutical and cosmetic compositions and their uses
BRPI0810971A2 (en) 2007-04-26 2015-07-21 Trican Well Service Ltd Fluid particulate drag control method and aqueous sludge composition method
US8282266B2 (en) * 2007-06-27 2012-10-09 H R D Corporation System and process for inhibitor injection
US8636982B2 (en) 2007-08-07 2014-01-28 Foamix Ltd. Wax foamable vehicle and pharmaceutical compositions thereof
US20090140444A1 (en) * 2007-11-29 2009-06-04 Total Separation Solutions, Llc Compressed gas system useful for producing light weight drilling fluids
WO2009070320A1 (en) * 2007-11-29 2009-06-04 Total Separation Solutions, Llc Method of making drilling fluids containing microbubbles
US9439857B2 (en) 2007-11-30 2016-09-13 Foamix Pharmaceuticals Ltd. Foam containing benzoyl peroxide
WO2010041141A2 (en) 2008-10-07 2010-04-15 Foamix Ltd. Oil-based foamable carriers and formulations
WO2009072007A2 (en) 2007-12-07 2009-06-11 Foamix Ltd. Carriers, formulations, methods for formulating unstable active agents for external application and uses thereof
CA2712120A1 (en) 2008-01-14 2009-07-23 Foamix Ltd. Poloxamer foamable pharmaceutical compositions with active agents and/or therapeutic cells and uses
US20090188721A1 (en) * 2008-01-30 2009-07-30 Smith Kevin W Membrane method of making drilling fluids containing microbubbles
JP2009179749A (en) * 2008-01-31 2009-08-13 Fujifilm Corp Norbornene-based polymer, film comprising the same, polarizing plate, and liquid crystal display
CA2643251C (en) * 2008-11-05 2014-06-03 Trican Well Service Ltd. Hydrocarbon fluid compositions and methods for using same
WO2010125470A2 (en) 2009-04-28 2010-11-04 Foamix Ltd. Foamable vehicle and pharmaceutical compositions comprising aprotic polar solvents and uses thereof
WO2011013009A2 (en) 2009-07-29 2011-02-03 Foamix Ltd. Non surfactant hydro-alcoholic foamable compositions, breakable foams and their uses
WO2011013008A2 (en) 2009-07-29 2011-02-03 Foamix Ltd. Non surface active agent non polymeric agent hydro-alcoholic foamable compositions, breakable foams and their uses
WO2011064631A1 (en) 2009-10-02 2011-06-03 Foamix Ltd. Surfactant-free, water-free, foamable compositions and breakable foams and their uses
US9849142B2 (en) 2009-10-02 2017-12-26 Foamix Pharmaceuticals Ltd. Methods for accelerated return of skin integrity and for the treatment of impetigo
US8174881B2 (en) 2009-11-24 2012-05-08 Micron Technology, Inc. Techniques for reducing disturbance in a semiconductor device
US20120129735A1 (en) * 2010-11-19 2012-05-24 Elementis Specialties, Inc. Non-aqueous drilling additive useful to produce a flat temperature-rheology profile
WO2012088056A2 (en) 2010-12-20 2012-06-28 3M Innovative Properties Company Methods for treating carbonate hydrocarbon-bearing formations with fluorinated amine oxides
BR112013017937A2 (en) * 2011-01-13 2018-09-18 3M Innovative Properties Co methods for treating fluorinated amine oxides hydrocarbon-containing silicyclic formations
CN103540299B (en) * 2012-07-12 2017-04-12 中国石油化工股份有限公司 Drilling fluid for low-pressure water-sensitive stratum
US9133385B2 (en) * 2012-09-30 2015-09-15 Halliburton Energy Services, Inc. Method for improving high temperature rheology in drilling fluids
US10106724B2 (en) 2012-11-19 2018-10-23 3M Innovative Properties Company Method of contacting hydrocarbon-bearing formations with fluorinated ionic polymers
CA2889374A1 (en) 2014-04-25 2015-10-25 Trican Well Service Ltd. Compositions and methods for making aqueous slurry
CA2856942A1 (en) 2014-07-16 2016-01-16 Trican Well Service Ltd. Aqueous slurry for particulates transportation
CA2880646A1 (en) 2015-01-30 2016-07-30 Trican Well Service Ltd. Composition and method of using polymerizable natural oils to treat proppants
MX2020012139A (en) 2016-09-08 2021-01-29 Vyne Pharmaceuticals Inc Compositions and methods for treating rosacea and acne.

Family Cites Families (154)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1737623A (en) 1926-12-20 1929-12-03 Canada Gypsum And Alabastine C Process for the production of dense foam
US1824221A (en) 1928-10-24 1931-09-22 Masonite Corp Process and apparatus for disintegration of fibrous material
US2043633A (en) 1932-06-10 1936-06-09 Clauss B Strauch Composition and method for producing stabilized foam
US2224135A (en) 1936-12-01 1940-12-10 Masonite Corp Making board products and recovering water solubles from fibrous ligno-cellulose material
US2531427A (en) 1946-05-03 1950-11-28 Ernst A Hauser Modified gel-forming clay and process of producing same
US2531812A (en) 1948-01-16 1950-11-28 Ernst A Hauser Application of drilling fluids
US2713029A (en) 1952-05-07 1955-07-12 Masonite Corp Drilling mud addition agent
US2713030A (en) 1952-05-17 1955-07-12 Masonite Corp Drilling mud addition agent
US2818230A (en) 1954-02-08 1957-12-31 Shell Dev Method of correcting for lost circulation of drilling fluids
US2808887A (en) 1955-09-22 1957-10-08 Weldon C Erwin Method for loosening stuck drill pipe
US2974134A (en) 1957-12-02 1961-03-07 Universal Oil Prod Co Surface active glucose ethers
BE582883A (en) 1958-10-28
US3065170A (en) 1959-07-02 1962-11-20 Jersey Prod Res Co Drilling fluids for use in wells
US3208524A (en) 1960-09-26 1965-09-28 Exxon Production Research Co Process for controlling lost circulation
US3229777A (en) 1961-03-22 1966-01-18 Swift & Co Method of transporting water from a well as a substantially stable foam
US3251768A (en) 1962-07-18 1966-05-17 Exxon Production Research Co Drilling muds and similar fluids
US3269468A (en) 1962-07-20 1966-08-30 Continental Oil Co Foaming agents for use in air drilling of wells
US3301848A (en) 1962-10-30 1967-01-31 Pillsbury Co Polysaccharides and methods for production thereof
US3334052A (en) 1963-04-30 1967-08-01 Kurz Fredrik Wilhelm Anton Method of preparing a gel product containing air bubbles and the use thereof
US3246696A (en) 1963-10-25 1966-04-19 Pan American Petroleum Corp Method of freeing pipe stuck in a well
US3328295A (en) 1964-12-03 1967-06-27 Pan American Petroleum Corp Method for preventing differential sticking and reducing fluid loss
US3313362A (en) 1965-02-03 1967-04-11 Air Drilling Specialties Co Method of and composition for use in, gas drilling
US3390723A (en) 1965-06-16 1968-07-02 Halliburton Co Method of preparing and using a plugging or diverting agent
US3243000A (en) 1965-06-23 1966-03-29 Exxon Production Research Co Method and composition for drilling wells and similar boreholes
US3393738A (en) 1967-01-30 1968-07-23 Union Oil Co Method for storing gas in subterranean formations
US3509951A (en) 1967-08-11 1970-05-05 Specialty Research & Sales Inc Method of preventing drilling fluid loss during well drilling
US3819519A (en) 1968-11-27 1974-06-25 Chevron Res Foam circulation fluids
US3610340A (en) 1969-07-07 1971-10-05 Chevron Res Aqueous foamed well circulation fluids containing a base component and their use in the treatment of wells
US3671022A (en) 1969-10-06 1972-06-20 Air Reduction Method and apparatus for the microdispersion of oxygen in water
US3628615A (en) 1970-01-26 1971-12-21 Exxon Production Research Co Water-base well fluids for shale stability and use thereof
US3728259A (en) 1970-05-27 1973-04-17 Exxon Production Research Co Composition for drilling wells and method for preparing same
US3844361A (en) 1970-12-23 1974-10-29 J Jackson Closed circuit method of circulating a substantially solid free drilling fluid
US3743613A (en) 1971-02-05 1973-07-03 Dow Chemical Co Galactomannan gum based composition for sealing permeable formations
US3754561A (en) 1972-02-04 1973-08-28 Chevron Res Foam circulation fluids
US4112025A (en) 1972-10-30 1978-09-05 Houdaille Industries, Inc. Method of and apparatus for jet aeration
US3998742A (en) 1972-12-18 1976-12-21 Texaco Inc. Additive for reducing gel strength in aqueous drilling fluids
US3986964A (en) 1973-06-11 1976-10-19 Texas Brine Corporation Method of well drilling and composition therefor
US3953336A (en) 1973-09-07 1976-04-27 Amoco Production Company Drilling fluid
US3988246A (en) 1974-05-24 1976-10-26 Chemical Additives Company Clay-free thixotropic wellbore fluid
US4172801A (en) 1975-03-17 1979-10-30 Brinadd Company Clay-free wellbore fluid
US4287086A (en) 1975-05-02 1981-09-01 Nl Industries, Inc. Viscous organic systems containing an organophilic clay gellant without an organic dispersant therefor
US4036764A (en) 1975-10-14 1977-07-19 Union Oil Company Of California Method of foam drilling using a sulfoacetate foaming agent
US4013568A (en) 1975-12-11 1977-03-22 Union Oil Company Of California Composition and method for drilling formations containing geothermal fluid
US4008766A (en) 1976-03-01 1977-02-22 Mobil Oil Corporation Oil recovery by waterflooding employing a biopolymer-surfactant system
US4387032A (en) 1976-03-25 1983-06-07 Enterra Corporation Concentrates for fire-fighting foam
US4092252A (en) 1976-05-04 1978-05-30 Union Oil Company Of California Controlling corrosion in gas-containing aqueous drilling fluid
US4172800A (en) 1976-06-21 1979-10-30 Texaco Inc. Drilling fluids containing an admixture of polyethoxylated, sulfurized fatty acids and polyalkylene glycols
GB1580439A (en) 1976-07-29 1980-12-03 British Petroleum Co Fermentation process for the production of microbial biomass and a hetero-polysaccharide biopolymer
DE2634494C2 (en) 1976-07-31 1983-04-14 Bayer Ag, 5090 Leverkusen New injectors for liquid gassing
US4088583A (en) 1976-12-02 1978-05-09 Union Oil Company Of California Composition and method for drilling high temperature reservoirs
US4105578A (en) 1976-12-10 1978-08-08 N L Industries, Inc. Organophilic clay having enhanced dispersibility
US4217231A (en) 1977-03-28 1980-08-12 Standard Oil Company (Indiana) Low fluid loss foam
US4155410A (en) 1978-06-26 1979-05-22 Brinadd Company Method for correcting lost circulation
US4247405A (en) 1978-06-30 1981-01-27 Phillips Petroleum Company Viscosity-stabilized aqueous solutions
US4391339A (en) 1978-08-04 1983-07-05 Hydronautics, Incorporated Cavitating liquid jet assisted drill bit and method for deep-hole drilling
US4262757A (en) 1978-08-04 1981-04-21 Hydronautics, Incorporated Cavitating liquid jet assisted drill bit and method for deep-hole drilling
US4329448A (en) 1979-07-10 1982-05-11 Lever Brothers Company Microbial heteropolysaccharide
US4342866A (en) 1979-09-07 1982-08-03 Merck & Co., Inc. Heteropolysaccharide S-130
US4304740A (en) 1979-10-11 1981-12-08 Richard Cernoch Liquid aeration apparatus
US4301868A (en) * 1979-10-15 1981-11-24 Petrolite Corporation Method using hydrocarbon foams as well stimulants
US4269279A (en) 1980-01-14 1981-05-26 Nl Industries, Inc. Spheroidal plastic coated magnetizable particles and their use in drilling fluids
US4299825A (en) 1980-07-03 1981-11-10 Celanese Corporation Concentrated xanthan gum solutions
US4422947A (en) 1980-12-19 1983-12-27 Mayco Wellchem, Inc. Wellbore fluid
US4432881A (en) 1981-02-06 1984-02-21 The Dow Chemical Company Water-dispersible hydrophobic thickening agent
US4425241A (en) 1981-02-18 1984-01-10 Phillips Petroleum Company Drilling fluids
US4486333A (en) * 1981-04-10 1984-12-04 Felix Sebba Preparation of biliquid foam compositions
US4832833A (en) 1981-06-17 1989-05-23 Linnola Ltd. Formation of membrane-like material
CA1154704A (en) 1981-06-17 1983-10-04 James Keane Method of separating oil or bitumen from surfaces covered with same
US4704200A (en) 1981-06-17 1987-11-03 Linnola Limited Method of separating oil or bitumen from surfaces covered with same
US4698148A (en) 1981-06-17 1987-10-06 James Keane Removal of chlorine-based contaminants from materials contaminated the same
US4464269A (en) 1981-07-29 1984-08-07 Exxon Research & Engineering Co. Additive composition for release of stuck drill pipe
US4378049A (en) 1981-08-21 1983-03-29 Halliburton Company Methods, additives and compositions for temporarily sealing high temperature permeable formations
US4417985A (en) 1981-11-06 1983-11-29 James Keane Treatment of waters with broad spectrum contaminants
US4442011A (en) 1981-12-21 1984-04-10 Exxon Research And Engineering Co. Drilling mud viscosification agents based on sulfonated ionomers
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4561985A (en) 1982-06-28 1985-12-31 Union Carbide Corporation Hec-bentonite compatible blends
US4425461A (en) 1982-09-13 1984-01-10 Exxon Research And Engineering Co. Drilling fluids based on a mixture of a sulfonated thermoplastic polymer and a sulfonated elastomeric polymer
US4499210A (en) 1982-10-13 1985-02-12 Union Carbide Corporation Process and composition for producing open-cell cross linked polyolefin foam
US4442018A (en) 1982-11-01 1984-04-10 The United States Of America As Represented By The United States Department Of Energy Stabilized aqueous foam systems and concentrate and method for making them
CA1217933A (en) 1983-04-06 1987-02-17 Yuji Hori Fluid composition for drilling
US4503084A (en) 1983-05-31 1985-03-05 Merck & Co., Inc. Non-heated gellan gum gels
GB8317696D0 (en) 1983-06-29 1983-08-03 Shell Int Research Preparing xanthomonas heteroplysaccharide
US4485020A (en) 1983-08-16 1984-11-27 Phillips Petroleum Company Amine treatment of polysaccharide solution
US4740319A (en) 1984-04-04 1988-04-26 Patel Arvind D Oil base drilling fluid composition
US4549907A (en) 1984-12-20 1985-10-29 Celanese Corporation Thixotropic aqueous solutions containing a crosslinked polygalactomannan gum
US4614235A (en) 1985-04-15 1986-09-30 Exxon Chemical Patents Inc. Use of mono and polyalkylene glycol ethers as agents for the release of differentially stuck drill pipe
US4717515A (en) 1985-04-29 1988-01-05 Wilfley Weber, Inc. Apparatus for dispersing fluids in liquids
US4707281A (en) 1985-06-03 1987-11-17 Pfizer Inc. Drilling fluid additive containing high pyruvate xanthan
US5175278A (en) 1985-06-28 1992-12-29 Merck & Co., Inc. Heteropolysaccharide S-657
US4664843A (en) 1985-07-05 1987-05-12 The Dow Chemical Company Mixed metal layered hydroxide-clay adducts as thickeners for water and other hydrophylic fluids
US5094778A (en) 1985-07-05 1992-03-10 The Dow Chemical Company Mixed metal hydroxide containing a dispersant
US4684479A (en) 1985-08-14 1987-08-04 Arrigo Joseph S D Surfactant mixtures, stable gas-in-liquid emulsions, and methods for the production of such emulsions from said mixtures
US4816551A (en) 1985-11-19 1989-03-28 Mi Drilling Fluids Company Oil based drilling fluids
FR2600267A1 (en) 1986-06-19 1987-12-24 Rhone Poulenc Chimie BIOPOLYMER GRANULES WITH QUICK DISPERSABILITY AND DISSOLUTION
US4978461A (en) 1986-09-02 1990-12-18 Exxon Research And Engineering Company Low and high temperature drilling fluids based on sulfonated terpolymer ionomers
GB8622032D0 (en) 1986-09-12 1986-10-22 Shell Int Research Aqueous polysaccharide compositions
US4743383A (en) 1986-11-24 1988-05-10 Phillips Petroleum Company Drilling fluid additives for use in hard brine environments
US4861499A (en) 1987-10-13 1989-08-29 American Cyanamid Company Water-dispersible hydrophobic thickening agent
US5075033A (en) 1987-10-19 1991-12-24 Rheox, Inc. Processes for preparing organophilic clay gellants
US5021170A (en) 1987-12-18 1991-06-04 Baroid Technology, Inc. Oil-based well bore fluids and gellants therefor
US4876017A (en) 1988-01-19 1989-10-24 Trahan David O Use of polyalphalolefin in downhole drilling
DE3801476A1 (en) 1988-01-20 1989-08-03 Henkel Kgaa COMPOSITIONS FOR THE EXEMPTION OF FIXED DRILLING RESTAURANTS
US5167798A (en) 1988-01-27 1992-12-01 Virginia Tech Intellectual Properties, Inc. Apparatus and process for the separation of hydrophobic and hydrophilic particles using microbubble column flotation together with a process and apparatus for generation of microbubbles
US5026735A (en) 1988-06-08 1991-06-25 Minnesota Mining And Manufacturing Company Treatment of hazardous materials with aqueous air foam of polyhydroxy polymer
US5110487A (en) 1989-04-03 1992-05-05 Chevron Corporation Enhanced oil recovery method using surfactant compositions for improved oil mobility
EP0427107A3 (en) 1989-11-06 1992-04-08 M-I Drilling Fluids Company Drilling fluid additive
US4964465A (en) 1989-11-06 1990-10-23 Texaco Inc. Method employing liquidized sand for controlling lost circulation of drilling fluids
US5030366A (en) 1989-11-27 1991-07-09 Atlantic Richfield Company Spacer fluids
US5024276A (en) 1989-11-28 1991-06-18 Shell Oil Company Hydraulic fracturing in subterranean formations
US5362713A (en) 1989-12-13 1994-11-08 Weyerhaeuser Company Drilling mud compositions
US5156765A (en) 1990-05-15 1992-10-20 Fox Valley Systems, Inc. Aerosol foam marking compositions
US5106517A (en) 1990-05-29 1992-04-21 Baker Hughes Incorporated Drilling fluid with browning reaction anionic carbohydrate
US5127475A (en) 1990-06-01 1992-07-07 Hayes James R Downhole drilling spotting fluid composition and method
US5002672A (en) 1990-06-01 1991-03-26 Turbo-Chem International, Inc. Downhole drilling spotting fluid composition and method
US5141920A (en) 1990-06-11 1992-08-25 Baker Hughes Incorporated Hydrocarbon invert emulsions for use in well drilling operations
US5105884A (en) 1990-08-10 1992-04-21 Marathon Oil Company Foam for improving sweep efficiency in subterranean oil-bearing formations
US5130028A (en) 1990-09-17 1992-07-14 Rheox, Inc. Method of treating waste water for organic contaminants with water dispersible organically modified smectite clay compositions
WO1992004942A1 (en) 1990-09-19 1992-04-02 Atlantic Richfield Company High-stability foams for long-term suppression of hydrocarbon vapors
US5086974A (en) 1990-12-18 1992-02-11 Nlb Corp. Cavitating jet nozzle
US5129457A (en) 1991-03-11 1992-07-14 Marathon Oil Company Enhanced liquid hydrocarbon recovery process
US5151155A (en) 1991-05-09 1992-09-29 Rheox, Inc. Process for deinking wastepaper with organically modified smectite clay
US5247995A (en) 1992-02-26 1993-09-28 Bj Services Company Method of dissolving organic filter cake obtained from polysaccharide based fluids used in production operations and completions of oil and gas wells
US5310002A (en) 1992-04-17 1994-05-10 Halliburton Company Gas well treatment compositions and methods
US5957203A (en) 1992-08-31 1999-09-28 Union Oil Company Of California Ultra-high temperature stable gels
US5314644A (en) 1992-10-19 1994-05-24 Virginia Polytechnic Institute And State University Microbubble generator
WO1994009703A1 (en) 1992-11-02 1994-05-11 Drexel University Surfactant-stabilized microbubble mixtures, process for preparing and methods of using the same
US5372462A (en) 1993-01-07 1994-12-13 Marathon Oil Company Polymer enhanced foam for blocking fluid flow in soil
US5567741A (en) 1993-06-03 1996-10-22 Loctite (Ireland) Limited Aerated anaerobic compositions with enhanced bulk stability
EP0711179B2 (en) 1993-07-30 2010-09-01 IMCOR Pharmaceutical Co. Stabilized microbubble compositions for ultrasound
US5514644A (en) 1993-12-14 1996-05-07 Texas United Chemical Corporation Polysaccharide containing fluids having enhanced thermal stability
US5654260A (en) 1994-01-10 1997-08-05 Phillips Petroleum Company Corrosion inhibitor for wellbore applications
US5565416A (en) 1994-01-10 1996-10-15 Phillips Petroleum Company Corrosion inhibitor for wellbore applications
DK0695795T3 (en) 1994-08-04 2000-04-03 Sofitech Nv Foaming drilling fluids, method corresponding thereto
US5566760A (en) 1994-09-02 1996-10-22 Halliburton Company Method of using a foamed fracturing fluid
US5480589A (en) * 1994-09-27 1996-01-02 Nordson Corporation Method and apparatus for producing closed cell foam
US5513712A (en) 1994-11-08 1996-05-07 Marathon Oil Company Polymer enhanced foam drilling fluid
US5495891A (en) 1994-11-08 1996-03-05 Marathon Oil Company Foamed gel employed as a drilling fluid, a lost circulation fluid, or a combined drilling/lost circulation fluid
DK0714978T3 (en) 1994-11-28 2001-04-23 Rhodia Chimie Sa Gel of unpolar medium and its use in the preparation of water-based drilling fluids
US5529122A (en) 1994-12-15 1996-06-25 Atlantic Richfield Company Method for altering flow profile of a subterranean formation during acid stimulation
US5591700A (en) 1994-12-22 1997-01-07 Halliburton Company Fracturing fluid with encapsulated breaker
US5728652A (en) 1995-02-10 1998-03-17 Texas United Chemical Company, Llc. Brine fluids having improved rheological charactersitics
US5616541A (en) 1995-02-10 1997-04-01 Texas United Chemical Company, Llc. Low solids, high density fluids for well drilling
US5710110A (en) 1995-05-15 1998-01-20 Rheox, Inc. Oil well drilling fluids, oil well drilling fluid anti-settling and method of providing anti-setting properties to oil well drilling fluids
US5716910A (en) 1995-09-08 1998-02-10 Halliburton Company Foamable drilling fluid and methods of use in well drilling operations
US5706895A (en) 1995-12-07 1998-01-13 Marathon Oil Company Polymer enhanced foam workover, completion, and kill fluids
US5682951A (en) 1995-12-07 1997-11-04 Marathon Oil Company Foamed gel completion, workover, and kill fluid
US5881826A (en) 1997-02-13 1999-03-16 Actisystems, Inc. Aphron-containing well drilling and servicing fluids
US6156708A (en) * 1997-02-13 2000-12-05 Actisystems, Inc. Aphron-containing oil base fluids and method of drilling a well therewith
US6123159A (en) 1997-02-13 2000-09-26 Actisystems, Inc. Aphron-containing well drilling and servicing fluids of enhanced stability
US5804535A (en) 1997-06-09 1998-09-08 Texas United Chemical Company, Llc. Well drilling and servicing fluids and methods of increasing the low shear rate viscosity thereof
US5783118A (en) 1997-07-02 1998-07-21 Kolaini; Ali R. Method for generating microbubbles of gas in a body of liquid
US6148917A (en) 1998-07-24 2000-11-21 Actisystems, Inc. Method of releasing stuck pipe or tools and spotting fluids therefor
US5916849A (en) 1998-07-24 1999-06-29 Venture Innovations, Inc. Polysaccharide-containing well drilling and servicing fluids
US6127319A (en) 1998-07-24 2000-10-03 Actisystems, Inc. Oil-in-water emulsion

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