WO2000026321A1 - Antifoaming agents for drilling fluids used in the drilling of subterranean wells - Google Patents
Antifoaming agents for drilling fluids used in the drilling of subterranean wells Download PDFInfo
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- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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Abstract
The disclosure describes an antifoaming agent for drilling fluids used in the drilling of subterranean wells. The antifoaming agent comprises a high purity polyoxyalkylene glycol ether, nonionic water-soluble surfactant based on alkylene oxides having from 2 to about 4 carbon atoms, a water soluble polyoxyalkylene glycol ether homopolymer based on alkylene oxides having from 2 to about 4 carbon atoms, carbon black and an ester alcohol based on the reaction of a polyhydric alcohol and a monocarboxylic acid or a hydroxy-carboxylic, such as a hydroxy-monocarboxylic acid and an alcohol.
Description
ANTIFOAMING AGENT FOR DRILLING FLUIDS USED IN THE DRILLING OF SUBTERRANEAN WELLS
RELATED APPLICATION:
This application is based on provisional application U.S. Serial No. 60/106,092 filed on October 29, 1998. FIELD OF THE INVENTION:
The field of the invention comprises antifoaming agents for drilling fluids used in the drilling of subterranean wells. BACKGROUND OF THE INVENTION:
Drilling fluids, sometimes referred to as drilling muds, are complex mixtures of chemicals employed in drilling subterranean wells and preform a variety of functions. These drilling fluids generally comprise a liquid or slurry pumped down the drill string which exists through openings in the drill bit immediately adjacent the penetrated formation. The drilling fluid then flows upwardly in the annulus between the drill string and the wall of the hole to the surface and functions in a variety of ways. The drilling fluid both cools and lubricates the drill bit, and because injected into the hole under pressure, delivers power to the drill bit, carries cuttings upwardly out of the drill hole during circulation, suspends cuttings in the bore hole when circulation stops, prevents blow outs, minimizes water loss into permeable formations along the length of the bore hole, and acts as a lubricant between the drill string and the bore hole wall.
The simplest drilling fluid comprises a mixture of drilled solids and water, sometimes referred to as "native" drilling mud. In some instances, the solids obtained consist of clays, which when finally ground, function as a drilling fluid or drilling mud. These drilling fluids tend to function reasonably well for controlling normal pressures at shallow depths in many oil and gas wells.
Native drilling mud or fluids provide almost no control over the loss of water into permeable formations and tend to wash out, or enlarge the diameter of the hole, and accumulate shale balls on the bit. These difficulties prompted the addition of a wide variety of chemicals to the drilling fluid.
The standard drilling fluid therefore comprises a native drilling fluid combined with clays such as bentonite, and/or sodium hydroxide, chrome, lignosulfonates, lignite, weighting materials such as barium sulfate, hematite, calcium carbonate, silica and polymeric compounds. The bentonite, along with the drilled solids and sometimes sub-bentonitic clays or mixtures, acts as a gelling agent which minimizes or prevents cuttings from the drill operation from settling
to the bottom of the well, especially during those periods which require stopping the drilling operation to add extra sections of drill pipe to the bit in order to increase the depth of the drilled hole.
The drilling fluid also creates a filter cake that imparts low permeability to the face of the permeable formation, the ideal filter cake comprising a relatively thin and hard layer as opposed to thick viscous coatings. The latter interfere with the drilling operation in that they have a tendency to entrain drilled solids moving up the annulus of the bore hole. Pressure in the bore hole exceeds the pressure in the permeable formation and thereby creates the filter cake which further results in liquid from the drilling fluid moving into the permeable formation. This leaves a layer of the filter cake on the surface of the hole. Liquid permeating this filter cake and the formation is called filtrate. Large amounts of filtrate passing across the formation face result in the deposition of a thick filter cake whereas small mounts of filtrate passing across the face result in a thin filter cake. The thin filter cake avoids or minimizes the problem of decreasing the bore hole diameter, a cause of concern, since this decreases the flow of drilling fluid upwards and out of the well, slowing down the removal of cuttings from the bore hole.
The ideal filter cake, would also limit the filtrate loss into the formation. Materials such as carboxy-methyl cellulose, lignite, lignosulfonates and asphalt-based materials generally aid in the formation of thin filter cakes. In addition to the inconvenience of having to continually add water to the drilling fluid because of filtrate loss, drillers have also found that excessive filtrate pumped into the formation not only interfered with electric logging of the well, but also causes swelling of the permeable formation which can reduce the permeability of a productive formation to the extent that the formation will not produce oil or gas, or only provide minimal production. The addition of sodium hydroxide, however, or equivalent caustic material to raise the pH of the drilling fluid tends to reduce the swelling of clays as well as glycerine-based additives. Completion fluids comprise liquid materials used during the completion phase of a well such as perforating a productive formation and like. Completion fluids differ from drilling fluids in that they do not have to carry large quantities of cuttings upwardly in the annulus of the well bore, only relatively small amounts of cuttings such as cement, iron casing and rubber. Completion fluids therefore do not normally contain gelling agents and do not have to provide a great deal of lubrication because of considerably less friction between the inside of a casing and a work string as compared to a bore hole wall an a drill string.
Otherwise, completion fluids must have characteristics similar to drilling muds in that they
cannot damage potentially productive formations and they also have to be sufficiently dense to offset pressures encountered at the bottom of the well hole especially in permeable formations and the like.
The foregoing shows that the improvement of "native" muds involved the addition of other materials to the drilling fluids, but not without some side effects. One of these comprises foaming, which if not controlled, whether in a drilling fluid or a completion fluid or a workover fluid, severely interferes with well drilling operations. The lower density drilling fluid that results from foam formation in the well prevents the fluid from effectively suspending cuttings and having them brought to the surface so that drilling can proceed efficiently. Accordingly, it would be an advantage to provide a composition as well as a process that minimized or eliminated foaming in drilling fluids. SUMMARY OF THE INVENTION:
Accordingly, the present invention comprises a composition, product produced by the process of forming the composition, as well as the product produced by introducing the composition/product by process into a drilling fluid, and a process that substantially obviates one or more of these and other problems due to the limitations and disadvantages of the related art.
The written description that follows sets forth additional features and advantages of the invention and which practice of the invention will also reveal. The composition, product produced by the process, and the process of the invention avoid or minimize the foregoing difficulties and achieve other advantages as more particularly pointed out in the written description and the claims hereof.
To achieve these and other advantages, and in accordance with the purpose of the invention, as embodies and broadly described, the invention comprises an antifoaming agent composition of matter for minimizing or eliminating foam produced in drilling fluids used in the drilling of subterranean wells. The antifoaming agent broadly comprises a high purity polyoxyalkylene glycoi ether nonionic water-soluble surfactant in combination with a water-soluble polyoxyalkylene glycoi ether homopolymer, carbon black, and an ester alcohol. The invention also comprises a product produced by the process of forming the composition, a product produced by introducing the composition/product by process into a drilling fluid, and a process for minimizing or eliminating foam produced in drilling fluids used in the drilling of subterranean wells by introducing the composition or product into such wells.
The invention also comprises a process for minimizing or eliminating foam produced in
drilling fluids by adding the foregoing composition or product to a drilling fluid.
Drilling fluids as used in the written description and the claims, includes not only conventional drilling fluids or drilling muds as known in the art but also completion fluids and workover fluids. Subterranean wells, again as the written description and the claims employ this term, include oil wells, gas wells, water wells, or any drilling of an opening in the earth by means of drilling equipment that relies on the introduction of drilling fluids into the bore hole in order to facilitate the drilling operation. DETAILED DESCRIPTION OF THE INVENTION:
The present invention comprises an antifoaming agent composition for drilling fluids used in the drilling of subterranean wells comprising a high purity polyoxyalkylene glycoi ether nonionic water-soluble surfactant, a water-soluble polyoxyalkylene glycoi ether homopolymer, carbon black and ester alcohol. The antifoaming agent also comprises a product made by the process of combining a high purity polyoxyalkylene glycoi ether nonionic water-soluble surfactant with a water-soluble polyoxyalkylene glycoi ether homopolymer, carbon black, and an ester alcohol. In some instances the ester alcohol can hydro lyze to form a carboxylic acid that may react with any of the active hydroxyl containing compounds in the combination of ingredients such as the polyoxyalkylene glycoi ether homopolymer and in some instances the high purity polyoxyalkylene glycoi ether nonionic water-soluble surfactant. In those instances, where this might occur, the composition comprises a highly complex mixture of reactive products that does not lend itself to exact analysis and accordingly, the invention also comprises a product produced by the process of combining the foregoing compounds as well as the product produced by introducing the composition of product produced by the foregoing process into a drilling fluid.
The high purity polyoxyalkylene glycoi ether nonionic water-soluble surfactant is based on alkylene oxides having from 2 to about 4 carbon atoms. The surfactant is substantially within the molecular weight range of from about 750 to about 4000 especially from about 1500 to about 3500 preferably from about 1700 to about 2200, and is substantially free of impurities, Especially preferred surfactants comprise those having a molecular weight of about 1900.
The surfactant has an HLB of from about 0.5 to about 10 especially from about 1 to about 5 and preferably from about 2 to about 4 where the most preferred surfactant has an HLB of about 3, and a cloud point of from about 10°C to about 40°C, especially from about 20°C to about 30°C and preferably from about 25 °C to about 28 °C when measured as a 1% aqueous solution. The most preferred surfactants have a cloud point of from about 22 ° C to about 25 ° C when measured as a 1 %
aqueous solution. The surfactants also have a clear point of from about 8°C to about 30 °C, especially from about 10°C to about 25°C and preferably from about 13 °C to about 21 °C when measured as a 10% aqueous solution. The most preferred surfactant has a clear point of from about 15 ° to about 19 °C, again when measured as a 10% aqueous solution. The surfactant also preferably is sub free at the clear point.
The surfactant also has a pH from about 4.5 to about 7.2, especially from about 5.0 to about 8, and preferably from about 5.3 to about 6.8. The most preferred surfactant has a pH from about 5.5 to about 6.5.
Additionally, a surfactant has a hydroxyl number of from about 40 to about 70, especially from about 45 to about 65 preferably from about 50 to about 62. The most preferred surfactant has a hydroxyl number of from about 53 to about 59.
Lastly, as supplied, the surfactant has from about 0.0 to about 1.5 weight percent water, especially from about 0.0 to about 1.0 weight percent of water and preferably from about 0.0 to about 0.5 weight percent of water, the most preferred surfactant contains from about 0.0 to about 0.2 weight percent water.
The surfactant is present in an amount from about 40% to about 95%, especially from about 50% to about 90% and preferably from about 70% to about 80% by weight of the antifoaming agent.
The polyoxyalkylene glycols of the present invention, whether copolymers or homopolymers, preferably comprise water soluble polymers. Preferably, these copolymers and/or homopolymers are water soluble at the operating temperature of the antifoaming agent when used for controlling foam produced in a drilling fluid for the drilling of subterranean wells.
The high purity polyoxyalkylene glycoi ether nonionic water-soluble block polymers comprise polyoxyalkylene glycoi ether all-block, block-heteric, heteric-block or heteric-heteric block copolymers where the alkylene units have from 2 to about 4 carbon atoms, i.e., those alkylene units based on alkylene oxides having from 2 to about 4 carbon atoms. The surfactants contain hydrophobic and hydrophilic blocks where each block is especially based on oxy-ethylene groups or oxypropylene groups or mixtures of these groups. The surfactant is substantially free of impurities such as homopolymers as well as non-surfactant copolymers that may form during the manufacture of the surfactant, and also substantially free of starting materials and catalysts, if employed in the polymerization of the alkylene oxides used for manufacturing the surfactant.
The term "substantially free of impurities" or "substantially free of surfactant starting
materials, homopolymers and non-surfactant copolymers of said starting materials" (which can appear as impurities in the surfactant) means that the surfactant contains no more than about 9% to about 10% by weight of these impurities as well as other impurities and especially no more than about 2% to about 3% by weight of the impurities and preferably no more than about 0.1% to about 2% by weight of these impurities. The foregoing amounts of impurities are based on the weight percent of the impurity that may be present in the surfactant as distinguished from the composition product produced u the process of the invention.
Of the various polyether-polyol block-copolymers available, the preferred materials comprise polyoxyalkylene glycoi ethers which in the case of surfactants contain hydrophobic and hydrophilic blocks, each block preferably being based on at least oxyethylene groups or oxypropylene groups or mixtures of these groups.
The most common method of obtaining these materials is by reacting an alkylene oxide such as ethylene oxide with a material that contains at least one reactive hydrogen. Alternative routes include the reaction of the active hydrogen material with a preformed polyglycol or the use of ethylene chlorohydrin instead of an alkylene oxide.
The reacting active hydrogen material must contain at least one active hydrogen, preferably alcohols, and optionally acids, amides, mercaptans, alkyl phenols and the like. Primary amines can be used as well.
Especially preferred materials are those obtained by block polymerization techniques. By the careful control of monomer feed and reaction conditions, a series of compounds, e.g., surfactants, can be prepared in which such characteristics as the hydrophile-lipophile balance (HLB), wetting and foaming power can be closely and reproductively controlled. The chemical nature of the initial component employed in the formation of the initial polymer block generally determines the classification of the materials. The initial component does not have to be hydrophobic. In the case of surfactants, hydrophobicity will be derived from one of the two polymer blocks. The chemical nature of the initial component in the formation of the first polymer block generally determined the classification of the materials. Typical starting materials or initial components include monohydric alcohols such as methanol, ethanol, propanol, butanol and the like as well as dihydric materials such as glycoi, glycerol, higher polyols, ethylene diamine and the like. The various classes of materials, suitable for practice of this aspect of the present invention that are surfactants, have been described by Schmolka in "Non-ionic Surfactants," Surfactant Science Series Vol. 2, Schick, M.J. Ed. Marcel Dekker, Inc., New York, 1967, Chapter 10 which
is incorporated herein by reference.
The first and simplest copolymer is that in which each block is homogeneous which is to say a single alkylene oxide is used in the monomer feed during each step in the preparation. These materials are referred to as all-block copolymers. The next classes are termed block-heteric and heteric-block, in which one portion of the molecule is composed of a single alkylene oxide while the other is a mixture of two or more such materials, one of which may be the same as that of the homogeneous block portion of the molecule. In the preparation of such materials, the hereto portion of the molecule will be totally random. The properties of these copolymers will be entirely distinct form those of the pure block copolymers. The other class is that in which both steps on the preparation of the different repeating units involve the addition of mixtures of alkylene oxides and is defined as a heteric-heteric block copolymer.
The block copolymer is typified by a monofunctional starting material such as a monohydric alcohol, acid, mercaptan, secondary amine or N-substitutes amides. These materials can generally be illustrated by the following formula: I - [Am - Bn]x [1] where I is the starting material molecule as described before. The A portion is a repeating unit comprising an alkylene oxide unit in which at least one hydrogen can be replaced by an alkyl group or an aryl group, and m is the degree of polymerization which is usually greater than about 6. The B moiety is the other repeating unit such as oxyethylene with n again being the degree of polymerization. The value of x is the functionality of I. Thus, where I is a monofunctional alcohol or amine, x is I; where I is a polyfunctional starting material such as a diol (e.g., propylene glycoi), x is 2 as is the case with the Pluronic® surfactants. Where I is a tetrafunctional starting material such as ethylenediamine, x will be 4 as is the case with Tetronic® surfactants. Preferred copolymers of this type are the polyoxypropylene-polyoxyethylene block copolymers. Multifunctional starting materials may also be employed to prepare the homogeneous block copolymers.
In the block-heteric and heteric-block materials either A or B will be a mixture of oxides withe the remaining block being a homogeneous block. Where the copolymer is a surfactant, one block will be the hydrophobe and the other the hydrophile and either of the two polymeric units will serve as the water solubilizing unit, and the other as the organophile, but the characteristics will differ depending on which is employed. Multifunctional starting materials can also be employed in materials of this type.
The heteric-heteric block copolymers are prepared essentially the same way as discussed previously with the major difference being that the monomer feed for the alkylene oxide in each step is composed of a mixture of two or more materials. The blocks will therefore be random copolymers of the monomer feed. In the case of surfactants, the solubility characteristics will be determined by the relative ratios of potentially water soluble and water insoluble materials.
These copolymers, as represented by formula (I), are prepared so that the weight ratio of A to B repeating units will also vary from about 0.4:1 to about 2.5:1, especially from about 0.6:1 to about 1.8:1 to about 1.2:1.
In one embodiment, these copolymers have the general formula: RX(CH2CH2[CH2]yO)nH (2) where R is usually a typical surfactant hydrophobic but may also be a polyether such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutylene group, or a mixture of polyoxypropylene, polyoxyethylene and polyoxypropylene groups. In the above formula X is either oxygen or nitrogen or another functionality capable of linking the polyoxyalkylene chain to R, and Y has a value of 0, 1 , or 2. In most cases, n, the average number of alkylene oxide units must be greater than about 5 or about 6. This is especially the case where it is desired to impart sufficient water solubility to make the materials useful.
In one embodiment, these copolymers have the general formula:
RX(CH2 CH2O)nH (3) R is usually a typical surfactant hydrophobic group but may also be a polyether such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutylene group, or a mixture of these groups. In the above formula X is either oxygen or nitrogen or another functionality capable of linking the polyoxyethylene chain to R. In most cases, n, the average number of oxyethylene units in the oxyethylene group, must be greater than about 5 or about 6. This is especially the case where it is desired to impart sufficient water solubility to make the materials useful.
The preferred polyoxyalkylene glycoi ethers are the nonionic polyetherpolyol block- copolymers. However, other nonionic block-copolymers useful in the invention can be modified block copolymers using the following as starting materials: (a) alcohols, (b) fatty acids, (c) alkylphenol derivatives, (d) glycerol and its derivatives, (e) fatty amines, (f) -1,4-sorbitan derivatives, (g) castor oil and derivatives, and (h) glycoi derivatives.
Especially preferred surfactants comprise those having a very narrow molecular weight distribution, i.e., the molecular weight of the copolymers does not vary more than from about plus
or minus about 10% of the stated numerical value, especially plus or minus about 7%, and preferably, no more than plus or minus about 3% of the states numerical value for the molecular weight. Stated otherwise, where the numerical value of the molecular weight, which is an average molecular weight, is given at a fixed value, the molecular weight distribution will not vary more than the foregoing percentages. For example, where a range of molecular weights for the copolymer is given, as between about 1700 to about 2200, any one value which is an average value falling within this range comprises the molecular weight of the particular copolymer of interest. Since the foregoing range of molecular weights of from about 1700 to about 2200 include a molecular weight of about 1900, copolymers of the present invention having a molecular weight of about 1900,based on a bell curve distribution, will have a maximum molecular weight for the copolymer of about 1900 but with minor amounts of copolymer on a molecular weight range of from about 1710 to about 1900 and similarly minor amounts of the copolymer in a molecular weight range of about 1900 to about 2090 where the deviation is plus or minus about 10%o. Substantially, no other copolymer less than about 1710 molecular weight or greater than about 2090 molecular weight will be present in the copolymer. This narrow molecular weight distribution also defines a surfactant copolymer of the present invention characterized as a "high quality" copolymer or surfactant.
The antifoaming agent also contains a water-soluble polyoxyalkylene glycoi ether homopolymer based on alkylene oxides having from 2 to about 2 carbon atoms where the polyoxyalkylene glycoi ether homopolymer is substantially in the molecular weight range from about 600 to about 3500, especially from about 900 to about 3100 and preferably from about 1200 to about 2800. The most preferred glycoi homopolymer in this regard has a molecular weight from about 1500 to about 2500 and comprises polypropylene glycoi.
The water-soluble polyoxyalkylene glycoi ether homopolymer also has a cloud point from about 25°C to about 65°C, especially from about 30°C to about 60°C, and preferably from about
35 °C to about 50 °C measured as a one percent aqueous solution. The most preferred glycoi ether homopolymer in this regard has a cloud point of from about 40 °C to about 44 °C.
The molecular weight, as used to describe the homopolymer as well as the copolymer glycols refers to the weight average molecular weight. The homopolymer is present in an amount from about 2% to about 35% especially from about 10 to about 25% and preferably from about 15% to about 20% by way of the antifoaming agent. Polypropylene glycoi ether homopolymers are especially preferred in this regard.
The antifoaming agent also contains carbon black in an amount from 1 to about a 10% especially from about 2 to about 8% and preferably from about 3 to about 6% by weight of the antifoaming agent. Rayborn, et al., U.S. Patent No. 5,114,597, incorporated herein by reference, describes the carbon blacks used according to the present invention. The carbon black comprises carbon black produced by a furnace process ranging in size from about 8m2/gm to about 200m2/gm especially about 20m2/gm to about 175 m2/gm and preferably from about 50m2/gm to about 150m2/gm. The most preferred carbon black has a surface area of from about 90m2/gm to about 120m2gm as determined by the nitrogen adsorption method for carbon black and/or from about 35 cc/100 gm to about 200 cc/100 gm as measured by DBP (dibutylphthalate) absorption. A preferred carbon black used according to the present invention comprises carbon black in the particle size range of from about 70 m2/gm to about 120 m /gm as determined by the nitrogen adsorption method and/or from about 75 cc/100 gm to about 125 cc/100 gm as determined by the DBP (dibutylphthalate) absorption method.
The antifoaming agent also includes an ester alcohol based on the reaction of a polyhydric alcohol and a monocarboxylic acid, or a hydroxy-carboxylic acid (which for purposes of the present invention includes hydroxy-monocarboxylic acids), and a monohydric or polyhydric alcohol, [both, hereinafter, an "alcohol"] is a straight or branched chain aliphatic alcohol having up to about 12 carbon atoms, especially an alcohol having from 2 to about 12 carbon atoms and preferably from about 3 to about 10 carbon atoms. Either alcohol can also comprise a cycloaliphatic alcohol or a straight chain or branched alkyl substituted cycloaliphatic alcohol having from about 5 to about 14 carbon atoms where the alkyl substituent has from 1 to about 4 carbon atoms. The monocarboxylic acid or hydroxy/carboxylic comprises a straight chain or branched chain aliphatic acid having up to about 12 carbon atoms especially from about 2 ro about 10 carbon atoms and preferably from about 3 to about 10 carbon atoms and may also comprise a cycloaliphatic acid or straight or branched chain alkyl substituted cycloaliphatic acid having from about 5 to about 14 carbon atoms and especially from about 6 to about 4 carbon atoms. The ester alcohol is present in an amount from about 1% to about 10% by weight and especially from about 2 to about 8% and preferably from about 3 to about 6% by weight of the antifoaming agent.
The ester alcohol comprises a compound as described above having at least one carboxylate group and at least one unreacted hydroxy group in the molecule and preferably one carboxylate group and from 1 to about 3 unreacted hydroxy groups in the molecule.
The ester alcohol, as described herein can be produced by the reaction of a monocarboxylic
acid and a polyol, or a hydroxy-carboxylic acid, as defined herein, especially a hydroxy- monocarboxylic acid, and a monohydric or polyhydric alcohol, and in those instances where the hydroxy group or groups in the carboxylic acid or polyol molecule will react with the carboxyl group, reaction conditions are controlled to minimize this or the hydroxyl groups are chemically blocked to prevent complete esterification. Upon completion of the esterification reaction, the blocking groups are removed. In other instances, the ester alcohol can be synthesized by reacting a carboxylic acid and an alcohol and subsequently hydroxylating the ester in order to obtain one or more hydroxy groups on the ester molecule.
In any event, the ester synthesis methods are well known to an organic chemist with ordinary skill in the art as well as controlling the reaction to minimize carboxylate formation and placement and removal of blocking groups.
Other ester synthesis methods useable according to the present invention include the reaction of an alkali metal salt of a carboxylic acid with an aliphatic or cycloaliphatic halide, the reaction of an acid chloride with an aliphatic or cycloaliphatic hydroxy compound, the reaction of diazoalkanes, e.g., diazomethane with a carboxylic acid, cleavage of ethers with acetic anhydride and the like. March, Advanced Organic Chemistry, 4th Edition (incorporated herein by reference) describes these and other esterification reactions and generally lists them on pages 1281-1282, and refers to the details of syntheses in other chapters in the text.
The description of the ester alcohol as the reaction product of an alcohol and an organic acid primarily describes the molecular structure of the ester alcohol and not the method of manufacture in all instances. Thus, as used throughout the application, the organic acids and the organic alcohols, do not necessarily comprise the starting materials for synthesizing the ester alcohol but specifically define a molecular segment of the ester alcohol that, upon hydrolysis, will yield the acid and the alcohol. The various monocarboxylic acids employed according to the present invention comprise formic acid, acetic acid, propionic acid or isopropionic acid, butyric acid, or isobutyric acid, pentanoic acid or isopentanoic acid, hexanoic acid, heptanoic acid, octanoic acid and the like. Cycloaliphatic acids include cyclopentanoic acid, clyclohexanoic acid, bicylco [2,2,l]-heptane-2- carboxylic acid, 8,4-formyl-l-napthalene carboxylic acid, napthalene carboxylic acid, phenol, benzoic acid, «-nathphyl-acetic acid, and for the manufacture of reverse esters, hydroxyacetic acid, hydroxyisobutyric acid, hydroxybutyric acid, hydroxycinnamic acid, hydroxy phenylacetic acid, hydroxy propionic acid, 1,3-dihydroxy-β-naphthoic acid, and 3-hydroxy-β-naphthoic acid.
In manufacturing the so-called "reverse esters," the foregoing hydrocarboxylic acids can be reacted with the alcohols as described herein, but also monohydric alcohols include: ethanol, propanol, isopropanol, pentanol, isopentanol, heptanol, cyclopentanol, bicyclo[2,2,l]-heptanol, benzyl alcohol, and the like. The various polyhydric alcohols suitable for the present invention include ethane diol, propane diol, isopropane, diol, glycerol, 2-ethyl 2-hydroxymethyl-l, 3-propane diol, 2-methyl- 2hydroxymethyl-l , 3-propane diol, 2,5-dimethyl-2, 5-hexanediol, 2-dimethyl-l, 3-propane diol, 2,2- dimethyl-1, 3-propane diol, butane diol, isobutane diol, butane triol, isobutane triol, pentane diol, isopentane diol, pentanetriol, isopentane triol, pentaerythritol, hexane diol, hexane triol, sorbitol, heptane diol, heptahydroxy heptane, 1,3-cyclopentane diol, 1,2, or 1,4, or 1,6, or 1,7 or 1,8 or 2,3 or 2,6 or 2,7 naphthalene diol, 2,3-dihydroxy benzyl alcohol, 4 or 3 or 2-hydroxybenzyl alcohol, diethylene glycoi, triethylene glycoi, dipropylene glycoi, tripropylene glycoi, catechol, resorcinol, pyrogallol, fluoroglucinol, 1,5-cyclooctanediol, 1,3,5-cyclooctane, diol, l,3-diethyl-2, 5- cyclooctanediol and the like. Some of the ester alcohols suitable for use in the present invention comprise 2,2-dimethyl- 1 ,
3-propanediol monoisobutyrate or monoisopropionate, 2-2-ethyl-2 hydroxymethyl- 1 , 3-propanediol monoisopentanoate, 1 ,2-cyclopentane diol monoisopropionate or monoisobutyrate, 1 ,6-naphthalene diol, monoisopentanoate, 1-2, cyclopentanediol, monoisobutyrate, 1 ,3-dihydroxy-β-naphthoic acid ethyl ester, 1-2, hydroxy-β-naphthoic acid phenol ester, 3-hydroxy-β-naphthoic acid, ethyl ester, 3 -hydroxy-β-naphthoic acid, hexadecyl ester, 3 -hydroxy-β-naphthoic acid-methyl ester, 2,5- dihydroxybenzyl alcohol, monoisobutyrate, hexyl hydroxy acetate, ethyl hydroxy isobutyrate, and 4, or 2, or 3-hydroxybenzyl alcohol monoisopropionate and the like.
The ester alcohol can also comprise mixtures that include not only the full ester but also unreacted alcohol or carboxylic acids. The full ester in this respect comprises products whereby all hydroxyl groups in the molecule are reacted to form a carboxylate group. These full esters comprise anywhere from about 5 to about 50%), especially from about 10% to about 45%, and especially from about 15%) to about 35%) by weight of the alcohol ester.
The full esters are based on the various carboxylic acids and alcohols as described herein, and in those instances, where hydroxy-carboxylic acids are used, the reaction product of those acids with monocarboxylic acid as described herein.
Thus, the ster alcohol will optionally contain the full ester and/or one of the alcohols as
noted herein in an amount from about 1% to about 50% by weight, especially from about 5% to about 45%) by weight and preferably from about 10% to about 30% by weight of the ester alcohol. The ester alcohol also can be prepared by using mixtures of organic acids and alcohols as described herein, especially the 2 component or 3 component mixtures. Additionally, rather than employing a single ester alcohol in the antifoaming agent of the present invention, various mixtures of ester alcohols as described herein can also be employed, especially the 2 component or 3 component mixtures.
Example
An antifoaming agent for drilling fluids was prepared comprising a high purity polyoxyalkylene glycoi ether, nonionic water soluble surfactant comprising a poly(oxyethylene- oxypropylene) glycoi obtained from Harcroft under the trade name "EPO 61" SD 71. The surfactant comprised 72%) by weight of the antifoaming agent. The surfactant was mixed with a polypropylene glycoi, obtained from Dow Chemical and sold under the trade name of polyol PM in an amount of 18% by weight of the antifoaming agent. The surfactant and the polypropylene glycoi were combined by mixing one with the other in a high-speed dispenser and shear pump until smooth and consistent. A high speed mechanical disperser suitable in this regard comprises a device known in the art as a ROTOSTAT® 200 XP-200 manufactured and sold by ADMIX, Inc. of Londonderry, New Hampshire, U.S.A. The mixing was conducted for a period of 'Λ hour.
Afterwards, carbon black was added to the foregoing mixture in an amount from about 1 to about 10 weight percent of the antifoaming agent. The carbon black used comprised one of those sold as Grades N-220, N-660 or N-330. The carbon black was stirred into the mixture of the surfactant and the polypropylene glycoi for a period of 1 hour, followed by the addition of an ester alcohol comprising 2,2,4-trimethyl-l, 3-pentanediol monoisobutyrate, stirred in until the mixture became homogeneous. This ester alcohol comprised a mixture of from about 50 to about 79% by weight of 2,2,4-trimethyl-l, 3-pentanediol monoisobutyrate, about 14 to about 32%) by weight of
2,2,4-trimethyl-l, 3-pentanediol diisobutyrate and the balance pentanediol.
The addition of the foregoing antifoaming agent in amounts described herein, to a conventional drilling fluid used during the drilling of a bore hole into the earth, substantially reduced foam formation in the bore hole, as compared to a similar drilling operation that did not employ the antifoaming agent.
The various numerical ranges describing the invention as set forth, throughout the specification also include any combination of the lower ends of the ranges with the higher ends of
the ranges set forth herein, including ter alia, ranges of concentrations of compounds, ratios of these compounds to one another, molecular weights, pH, ratios of polymer units or polymer blocks to one another, average number of polymer blocks in the polymer compounds of the invention, and the like, as well as all whole number and/or fractional number values and ranges encompassed within these ranges.
It will be apparent to those skilled in the art that various modifications and variations can be made to the composition and process of the invention as well as the product made by combining the various compounds of the composition or adding the composition or product to a drilling fluid without departing from the spirit or scope of the invention. It is intended that these modifications and variations of this invention are to be included as part of the invention provided they come within the scope of the appended claims and their equivalents.
Claims
1. An antifoaming agent comprising: a polyoxyalkylene glycoi ether nonionic water-soluble surfactant; a water-soluble polyoxyalkylene glycoi ether homopolymer; carbon black; and an ester alcohol.
2. The antifoaming agent of claim 1 wherein said surfactant is based on alkylene oxides having from two to about four carbon atoms, said surfactant having a molecular weight from about 750 to about 4000, and an HLB of from about 0.5 to about 10 and a cloud point from about 10°C to about 40 °C.
3. The antifoaming agent of claim 1 wherein said surfactant has no more than about 9 to about 10% impurities, wherein said impurities are unreacted surfactant starting materials, homopolymers and non-surfactant copolymers of said starting materials.
4. The antifoaming agent of claim 1 wherein said polyoxyalkylene glycoi ether based on alkylene oxides having from two to about four carbon atoms, said polyoxyalkylene glycoi ether homopolymer having a molecular weight from about 600 to about 3500 and having a cloud point offrom 25°C to about 60°C.
5. The antifoaming agent of claim 1 wherein said ester alcohol is based on the reaction of a polyhydric alcohol and a monocarboxylic acid, or a hydroxy-carboxylic acid and an alcohol where either alcohol is a straight or branched chain aliphatic alcohol having up to about 12 carbon atom, or a cycloaliphatic alcohol or a straight chain or branched chain alkyl substituted cycloaliphatic alcohol having from about 5 to about 14 carbon atoms, and where either acid comprises a straight chain or branched chain aliphatic acid having up to about 12 carbon atoms or a cycloaliphatic acid or straight or branched chain alkyl substituted cycloaliphatic acid having from about 5 to about 14 carbon atoms.
6. The antifoaming agent of claim 3 wherein said surfactant has no more than about 2% to about 3% by weight of said impurities, said surfactant copolymer comprises a copolymer of ethylene oxide and propylene oxide having a molecular weight from about 1500 to about 3500, an HLB of from about 1 to about 5, a pH of from about 4.5 to about 7.2, a hydroxyl number of from about 40 to about 70, a cloud point of from about 20 °C to about 30°C and a clear point of from about 10°C to about 25 °C and said polyoxyalkylene glycoi comprises polypropylene glycoi, said polypropylene glycoi having a molecular weight from about 900 to about 3100 and a cloud point from about 30°C to about 60°C, and wherein said alcohol used to produce said ester alcohol comprises a straight or branched chain aliphatic alcohol having from about three to about 10 carbon atoms and up to about three hydroxyl groups and said acid used to produce said ester alcohol comprises a straight or branched chain aliphatic acid having up to about 6 carbon atoms.
7. The antifoaming agent of claim 3 wherein said surfactant copolymer is an all block copolymer.
8. The antifoaming agent of claim 3 wherein said surfactant copolymer is a block- heteric copolymer.
9. The antifoaming agent of claim 3 wherein said surfactant copolymer is a heteric- heteric copolymer.
10. The antifoaming agent of claim 3 wherein said surfactant copolymer is a heteric- block copolymer.
11. The antifoaming agent of claim 7 wherein said ester alcohol comprises 2,2,4- trimethyl-l, 3-pentanediol monoisobutyrate.
12. The antifoaming agent of claim 8 wherein said ester alcohol comprises 2,2,4- trimethyl-l, 3-pentanediol monoisobutyrate.
13. The antifoaming agent of claim 9 wherein said ester alcohol comprises 2,2,4- trimethyl-l, 3-pentanediol monoisobutyrate.
14. The antifoaming agent of claim 10 wherein said ester alcohol comprises 2,2,4- trimethyl-l, 3-pentanediol monoisobutyrate.
15. A process of controlling foam produced in a drilling fluid for the drilling of subterranean wells comprising adding to said drilling fluid an antifoaming agent comprising: a polyoxyalkylene glycoi ether nonionic water-soluble surfactant in an amount from about 40%) to about 95%) by weight of said antifoaming agent; a water-soluble polyoxyalkylene glycoi ether homopolymer in an amount from about 2%> to about 35%o by weight of said antifoaming agent; carbon black in an amount from about 1%> to about 10%> by weight of said antifoaming agent; and an ester alcohol in an amount from about 1% to about 10%) by weight of said antifoaming agent.
16. The process of claim 15 wherein said surfactant is based on alkylene oxides having from two to about four carbon atoms, said surfactant having a molecular weight from about 750 to about 4000, and an HLB of from about 0.5 to about 10 and a cloud point from about 10 °C to about 40°C.
17. The process of claim 15 wherein said surfactant has no more than about 9 to about 10%> impurities, wherein said impurities are unreacted surfactant starting materials, homopolymers and non-surfactant copolymers of said starting materials.
18. The process of claim 15 wherein said polyoxyalkylene glycoi ether homopolymer is based on alkylene oxides having from two to about four carbon atoms, said polyoxyalkylene glycoi ether homopolymer having a molecular weight from about 600 to about 3500 and having a cloud point of from about 25 °C to about 60 °C.
19. The process of claim 15 wherein said ester alcohol is based on the reaction of a polyhydric alcohol and a monocarboxylic acid, or a hydroxy-carboxylic acid and an alcohol where either alcohol is a straight or branched chain aliphatic alcohol having up to about 12 carbon atoms, or a cycloaliphatic alcohol or a straight chain or branched chain alkyl substituted cycloaliphatic alcohol having from about 5 to about 14 carbon atoms, and where either acid comprises a straight chain or branched chain aliphatic acid having up to about 12 carbon atoms or a cycloaliphatic acid or straight or branched chain alkyl substituted cycloaliphatic acid having from about 5 to about 14 carbon atoms.
20. The process of claim 17 wherein said surfactant has no more than about 2% to about 3% by weight of said impurities, said surfactant copolymer comprises a copolymer of ethylene oxide and propylene oxide having a molecular weight from about 1500 to about 3500, an HLB of from about 1 to about 5, a pH of from about 4.5 to about 7.2, a hydroxyl number of from about 40 to about 70, a cloud point of from about 20 °C to about 30 °C and a clear point of from about 10 °C to about 25 °C, and said polyoxyalkylene glycoi comprises polypropylene glycoi said polypropylene glycoi having a molecular weight from about 900 to about 3100 and a cloud point from about 30 ° C to about 60 °C, and wherein said alcohol used to produce said ester alcohol comprises a straight or branched chain aliphatic alcohol having from about three to about 10 carbon atoms and up to about three hydroxyl groups and said acid used to produce said ester alcohol comprises a straight or branched chain aliphatic acid having from one to about 6 carbon atoms.
21. The process of claim 17 wherein said surfactant copolymer is an all block copolymer.
22. The process of claim 17 wherein said surfactant copolymer is a block-heteric copolymer.
23. The process of claim 17 wherein said surfactant copolymer is a heteric-heteric copolymer.
24. The process of claim 17 wherein said surfactant copolymer is a heteric-block copolymer.
25. The process of claim 21 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3- pentanediol monoisobutyrate.
26. The process of claim 22 wherein said ester alcohol comprises 2,2,4-trimethyl-l , 3- pentanediol monoisobutyrate.
27. The process of claim 23 wherein said ester alcohol comprises 2,2,4-trimethyl-l , 3- pentanediol monoisobutyrate.
28. The process of claim 24 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3- pentanediol monoisobutyrate.
29. An antifoaming agent product for drilling fluids used in the drilling of subterranean wells produced by the process comprising combining: a polyoxyalkylene glycoi ether nonionic water-soluble in an amount from about 40%> to about 95%> by weight of said antifoaming agent; a water-soluble polyoxyalkylene glycoi ether homopolymer in an amount from about 2%> to about 35%o by weight of said antifoaming agent; carbon black in an amount from about 1%> to about 10% by weight of said antifoaming agent; and an ester alcohol in an amount from about 1 % to about 10%> by weight of said antifoaming agent.
30. The product produced by the process of claim 29 wherein said surfactant is based on alkylene acids having from about two t about four carbon atoms, said surfactant having a molecular weight from about 750 to about 4000, and an HLB of from about 0.5 to about 10 and a cloud point from about 10°C to about 40 °C.
31. The product produced by the process of claim 29 wherein said surfactant has no more than about 9 to about 10% impurities, wherein said impurities are unreacted surfactant starting materials, homopolymers and non-surfactant copolymers of said starting materials.
32. The product produced by the process of claim 29 wherein said polyoxyalkylene glycoi ether homopolymer is based on alkylene oxides having from two to about four carbon atoms, said polyoxyalkylene glycoi ether homopolymer having a molecular weight from about 600 to about 3500 and having a cloud point of from about 25°C to about 60°C.
33. The product produced by the process of claim 31 wherein said ester alcohol is based on the reaction of a polyhydric alcohol and a monocarboxylic acid, or a hydroxy-carboxylic acid and an alcohol where either alcohol is a straight or branched chain aliphatic alcohol having up to about 12 carbon atoms, or a cycloaliphatic alcohol or a straight chain or branched chain alkyl substituted cycloaliphatic alcohol having from about 5 to about 14 carbon atoms, and where either acid comprises a straight chain or branched chain aliphatic acid having up to about 12 carbon atoms or a cycloaliphatic acid or straight or branched chain alkyl substituted cycloaliphatic acid having from about 5 to about 14 carbon atoms.
34. The product produced by the process of claim 31 wherein said surfactant has no more than about 2% to about 3%> by weight of said impurities, said surfactant copolymer comprises a copolymer of ethylene oxide and propylene oxide having a molecular weight from about 1500 to about 3500, and HLB of from about 1 ro about 5, a pH of from about 4.5 to about 7.2, a hydroxyl number of from about 40 to about 70, a cloud point of from about 20°C to about 30°C and a clear point of from about 10 °C to about 25 °C, and said polyoxyalkylene glycoi comprises polypropylene glycoi said polypropylene glycoi having a molecular weight from about 900 to about 3100 and a cloud point from about 30°C to about 60°C, and wherein said alcohol used to produce said ester alcohol comprises a straight or branched chain aliphatic alcohol having from about three to about 10 carbon atoms and up to about three hydroxyl groups and said acid used to produce said ester alcohol comprises a straight or branched chain aliphatic acid having up to about 6 carbon atoms.
35. The product produced by the process of claim 31 wherein said surfactant copolymer is an all block copolymer.
36. The product produced by the process of claim 31 wherein said surfactant copolymer is a block-heteric copolymer.
37. The product produced by the process of claim 31 wherein said surfactant copolymer is a heteric-heteric copolymer.
38. The product produced by the process of claim 31 wherein said surfactant copolymer is a heteric-block copolymer.
39. The product produced by the process of claim 35 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3-pentanediol monoisobutyrate.
40. The product produced by the process of claim 36 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3-pentanediol monoisobutyrate.
41. The product produced by the process of claim 37 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3-pentanediol monoisobutyrate.
42. The product produced by the process of claim 38 wherein said ester alcohol comprises 2,2,4-thrimethyl-l, 3-pentanediol monoisobutyrate.
43. A method of controlling foam produced in a drilling fluid for the drilling of subterranean wells comprising adding to said drilling fluid and antifoaming agent produced by the process comprising combining: a polyoxyalkylene glycoi ether nonionic water-soluble surfactant in an amount from about 40%) to about 95%) by weight of said antifoaming agent; a water-soluble polyoxyalkylene glycoi ether homopolymer in an amount from about 2% to about 35%o by weight of said antifoaming agent; carbon black in an amount from about 1%> to about 10%) by weight of said antifoaming agent; and an ester alcohol in an amount from about 1%> to about 10% by weight of said antifoaming agent.
44. The method of claim 40 wherein said surfactant is based on alkylene oxides having from two to about four carbon atoms, said surfactant having a molecular weight from about 750 to about 4000, and an HLB of from about 0.5 to about 10 and a cloud point from about 10°C to about 40°C.
45. The method of claim 40 wherein said surfactant has no more than about 9 to about 10% impurities, wherein said impurities are unreacted surfactant starting materials, homopolymers and non-surfactant copolymers of said starting materials.
46. The method of claim 40 wherein said polyoxyalkylene glycoi ether homopolymer is based on alkylene oxides having from two to about four carbon atoms, said polyoxyalkylene glycoi ether homopolymer having a molecular weight from about 600 to about 3500 and having a cloud point of from about 25 °C to about 60 °C.
47. The method of claim 1 wherein said ester alcohol is based on the reaction os a polyhydric alcohol and a monocarboxylic acid, or a hydroxy-carboxylic acid and an alcohol where either alcohol is a straight or branched chain aliphatic alcohol having up to about 12 carbon atoms, or a cycloaliphatic alcohol or a straight chain or branched chain alkyl substituted cycloaliphatic alcohol having from about 5 to about 14 carbon atoms, and where either acid comprises a straight chain or branched chain aliphatic acid having up to about 12 carbon atoms or a cycloaliphatic acid or straight or branched chain alkyl substituted cycloaliphatic acid having from about 5 to about 14 carbon atoms.
48. The method of claim 45 wherein said surfactant has no more than about 2%> to about 3% by weight of said impurities, said surfactant copolymer comprises a copolymer of ethylene oxide and propylene oxide having a molecular weight from about 1500 to about 3500, an HLB of from about 1 to about 5, a pH of from about 4.5 to about 7.2, a hydroxyl number of from about 40 to about 70, a cloud point of from about 20 ° C to about 30 ° C and a clear point of from about 10 ° C to about 25 °C , and said polyoxyalkylene glycoi comprises polypropylene glycoi said polypropylene glycoi having a molecular weight from about 900 to about 3100 and a cloud point from about 30°C to about 60°C, and wherein said alcohol used to produce said ester alcohol comprises a straight or branched chain aliphatic alcohol having from about three to about 10 carbon atoms and up to about three hydroxyl groups and said acid used to produce said ester alcohol comprises a straight or branched chain aliphatic acid having up to about 6 carbon atoms.
49. The method of claim 45 wherein said surfactant copolymer is an all block copolymer.
50. The method of claim 45 wherein said surfactant is a block-heteric copolymer.
51. The method of claim 45 wherein said surfactant copolymer is a heteric-heteric copolymer.
52. The method of claim 45 wherein said surfactant copolymer is a heteric-block copolymer.
53. The method of claim 49 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3- pentanediol monoisobutyrate.
54. The method of claim 50 wherein said ester alcohol 2,2,4-trimethyl- 1, 3- pentanediol monoisobutyrate .
55. The method of claim 51 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3- pentanediol monoisobutyrate.
56. The method of claim 52 wherein said ester alcohol comprises 2,2,4-trimethyl-l, 3- pentanediol monoisobutyrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU18098/00A AU1809800A (en) | 1998-10-29 | 1999-10-29 | Antifoaming agents for drilling fluids used in the drilling of subterranean wells |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10609298P | 1998-10-29 | 1998-10-29 | |
| US60/106,092 | 1998-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2000026321A1 true WO2000026321A1 (en) | 2000-05-11 |
Family
ID=22309444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/025483 WO2000026321A1 (en) | 1998-10-29 | 1999-10-29 | Antifoaming agents for drilling fluids used in the drilling of subterranean wells |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU1809800A (en) |
| WO (1) | WO2000026321A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004043567A1 (en) | 2002-11-07 | 2004-05-27 | Bayer Materialscience Llc | A process for suppressing the foaming of an aqueous system |
| CN100348687C (en) * | 2004-11-29 | 2007-11-14 | 兰州理工大学 | Solid foaming agent |
| CN103867170A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Low-yield low-pressure gas well self-production gas foam liquid discharging method |
| CN104272081A (en) * | 2012-05-08 | 2015-01-07 | 本特利仪器有限公司 | Reagent for clarifying emulsions and method of clarification |
| US10066144B2 (en) | 2013-11-08 | 2018-09-04 | Halliburton Energy Services, Inc. | Copolymer surfactants for use in downhole fluids |
| WO2021109299A1 (en) * | 2019-12-06 | 2021-06-10 | 江苏四新科技应用研究所股份有限公司 | Defoamer used for thin-layer self-leveling mortar, and preparation method therefor |
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| US5114597A (en) * | 1990-02-22 | 1992-05-19 | Sun Drilling Products Corporation | Method of making a drilling fluid containing carbon black in a dispersed state |
| US5843872A (en) * | 1997-11-19 | 1998-12-01 | Sun Drilling Products Corp | Drilling fluid system and related methods |
| US5891832A (en) * | 1997-12-08 | 1999-04-06 | Sun Drilling Products Corp. | Drilling fluid additive containing a fish oil/glycol mixture and related methods |
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1999
- 1999-10-29 AU AU18098/00A patent/AU1809800A/en not_active Abandoned
- 1999-10-29 WO PCT/US1999/025483 patent/WO2000026321A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5114597A (en) * | 1990-02-22 | 1992-05-19 | Sun Drilling Products Corporation | Method of making a drilling fluid containing carbon black in a dispersed state |
| US5843872A (en) * | 1997-11-19 | 1998-12-01 | Sun Drilling Products Corp | Drilling fluid system and related methods |
| US5891832A (en) * | 1997-12-08 | 1999-04-06 | Sun Drilling Products Corp. | Drilling fluid additive containing a fish oil/glycol mixture and related methods |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004043567A1 (en) | 2002-11-07 | 2004-05-27 | Bayer Materialscience Llc | A process for suppressing the foaming of an aqueous system |
| US7001634B2 (en) | 2002-11-07 | 2006-02-21 | Bayer Materialscience Llc | Process for suppressing the foaming of an aqueous system |
| CN100396353C (en) * | 2002-11-07 | 2008-06-25 | 拜尔材料科学有限责任公司 | Process for suppressing the foaming of an aqueous system |
| KR101073772B1 (en) * | 2002-11-07 | 2011-10-13 | 바이엘 머티리얼싸이언스 엘엘씨 | A process for suppressing the foaming of an aqueous system |
| CN100348687C (en) * | 2004-11-29 | 2007-11-14 | 兰州理工大学 | Solid foaming agent |
| CN104272081A (en) * | 2012-05-08 | 2015-01-07 | 本特利仪器有限公司 | Reagent for clarifying emulsions and method of clarification |
| CN104272081B (en) * | 2012-05-08 | 2017-07-28 | 本特利仪器有限公司 | For the method for the reagent and clarification of clarifying emulsion |
| CN103867170A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Low-yield low-pressure gas well self-production gas foam liquid discharging method |
| CN103867170B (en) * | 2012-12-10 | 2016-05-11 | 中国石油天然气股份有限公司 | The method of a kind of low production and low pressure gas well automatic gas-producing foam discharge opeing |
| US10066144B2 (en) | 2013-11-08 | 2018-09-04 | Halliburton Energy Services, Inc. | Copolymer surfactants for use in downhole fluids |
| US10597571B2 (en) | 2013-11-08 | 2020-03-24 | Halliburton Energy Services, Inc. | Copolymer surfactants for use in downhole fluids |
| WO2021109299A1 (en) * | 2019-12-06 | 2021-06-10 | 江苏四新科技应用研究所股份有限公司 | Defoamer used for thin-layer self-leveling mortar, and preparation method therefor |
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|---|---|
| AU1809800A (en) | 2000-05-22 |
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