WO2007065872A1 - High temperature gellant for viscosity modification of low and high density brines - Google Patents
High temperature gellant for viscosity modification of low and high density brines Download PDFInfo
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- WO2007065872A1 WO2007065872A1 PCT/EP2006/069256 EP2006069256W WO2007065872A1 WO 2007065872 A1 WO2007065872 A1 WO 2007065872A1 EP 2006069256 W EP2006069256 W EP 2006069256W WO 2007065872 A1 WO2007065872 A1 WO 2007065872A1
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- linear
- coadditive
- alkyl
- viscoelastic composition
- sulfonate
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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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
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/30—Viscoelastic surfactants [VES]
Definitions
- the present invention relates to viscoelastic compositions and to methods and agents for modifying the rheological behavior of aqueous fluids such as used in well drilling, stimulation and similar subterranean operations.
- Fluids are used in well drilling operations, for example, to cool and lubricate the drilling bit, to carry away drilled solids and other debris, to suspend drilled cuttings and other debris when the fluid column is static, to control subsurface pressure, to prevent squeezing or caving of formations, to suspend propping agents, and to minimize damage to any potential production zone.
- stimulation hydroaulic operations fluids are used to transfer pressure from one location to another.
- Drilling fluids and stimulation fluids can be water based or oil based.
- water based drilling and stimulation fluids can include one or more aqueous fluid thickening agents, lubricants, and corrosion inhibitors.
- the aqueous fluid can be fresh water or brine, and can include aqueous solutions of acids, alkali, lower alkanols (methanol, ethanol, and propanol), glycols, and the like, provided that the water miscible liquid does not adversely affect the viscoelastic properties of the aqueous fluid.
- emulsions of immiscible liquids in water and aqueous slurries of solid particulates such as clay.
- Viscoelasticity is a desirable rheological feature in drilling fluids, workover or completion fluids, and stimulation fluids which can be provided by fluid modifying agents such as polymeric agents and surfactant gelling agents.
- Viscoelastic fluids are those which exhibit both elastic behavior and viscous behavior. Elasticity is defined as an instant strain (deformation) response of a material to an applied stress. Once the stress is removed, the material returns to its undeformed equilibrium state. This type of behavior is associated with solids. On the other hand, the viscous behaviour is defined as a continuous deformation resulting from an applied stress. After a while, the deformation rate (shear rate or strain rate in general) becomes steady. Once the stress is removed, the material does not return to its initial undeformed state.
- Viscoelastic fluids may behave as a viscous fluid or an elastic solid, or a combination of both depending upon the applied stress on the system and the time scale of the observation. Viscoelastic fluids exhibit an elastic response immediately after the stress is applied. After the initial elastic response, the strain relaxes and the fluid starts to flow in a viscous manner. The elastic behaviour of fluids is believed to aid significantly in the transport of solid particles.
- the viscosity of a viscoelastic fluid may also vary with the stress or rate of strain applied. In the case of shear deformations, it is very common that the viscosity of the fluid drops with increasing shear rate or shear stress. This behavior is usually referred to as "shear thinning".
- Viscoelasticity in fluids that is caused by surfactants can manifest itself shear thinning behavior. For example, when such a fluid is passed through a pump or is in the vicinity of a rotating drill bit, the fluid is in a high shear rate environment and the viscosity is low, resulting in low friction pressures and pumping energy savings. When the shearing stress is abated, the fluid returns to a higher viscosity condition. This is because the viscoelastic behavior is caused by surfactant aggregations in the fluid. These aggregations will adjust to the conditions of the fluid, and will form different aggregate shapes under different shear stresses.
- High low shear-rate viscosities are good for solids transport.
- the elastic component of a viscoelastic fluid may also manifest itself in a yield stress value. This allows a viscoelastic fluid to suspend an insoluble material, for example sand or drill cuttings, for a greater time period than a viscous fluid of the same apparent viscosity. Yield stresses that are too high are not a good thing in drilling, as it may make restarting the drilling bit very difficult and causes a condition called "stuck pipe".
- permeability modification Another function of fluid modifying agents in oil drilling applications is in permeability modification.
- Secondary recovery of oil from reservoirs involves supplementing by artificial means the natural energy inherent in the reservoir to recover the oil.
- a pressurized fluid such as brine
- drill holes injecting wells
- rock often has areas of high and low permeability. The brine injected can finger its way through the high permeability areas leaving unrecovered oil in the low permeability areas.
- U.S. Patent No. 5,101 ,903 discloses a method for reducing the permeability of the more permeable zone of an underground formation having non-uniform permeability.
- the method comprises injecting into the formation a blend of surfactant and an alcohol, the blend being introduced in an amount effective to reduce the permeability of the more permeable zone of the formation.
- the preferred surfactant is an amine oxide such as dimethyltallowamine oxide delivered in water.
- a disclosed alcohol is isopropanol.
- the method may include the further step of injecting an alcohol slug following injection of the surfactant and alcohol blend.
- 4,745,976 discloses a method for partially or completely blocking the high permeability regions of a reservoir. The technique is based upon the ability to induce phase changes in surfactant solutions by changing counterions or by adding small quantities of different surfactants.
- An aqueous solution of an ionic surfactant may have a viscosity only slightly different from brine but an increase in the salt concentration or addition of a multivalent counterion can cause the surfactant to form a solid precipitate or form a gel-like structure of high viscosity.
- a first surfactant solution is injected into the formation followed by a water-soluble spacer fluid followed by a second surfactant solution.
- compositions of the first and second surfactants solutions are chosen so that upon mixing, a precipitated or gel-like structure will form blocking the high permeability zone of the reservoir.
- the rheology of an aqueous fluid is modified by a method which comprises adding to said aqueous fluid an amount of a viscoelastic composition sufficient to form a viscoelastic fluid.
- the viscoelastic composition of the invention comprises a combination of i) at least one alkyl amido quaternary amine, and ii) at least one coadditive that comprises a C ⁇ -24 linear alkyl and/or alpha-olefin sulfate and/or sulphonate.
- the present invention generally relates to a viscoelastic composition that comprises a combination of i) at least one alkyl amido quaternary amine, and ii) at least one coadditive.
- the alkyl amido quaternary amine employable in the viscoelastic composition of the invention is of the general formula:
- Ri is a saturated or unsaturated, straight or branched chain hydrocarbon chain of from 16 to 22 carbon atoms
- R 2 is a divalent alkylene group of 2-6 carbon atoms which may be linear or branched, substituted or unsubstituted
- R 3 , R 4 and R 5 are independently selected from d-C 6 substituted or unsubstituted, straight or branched chain, saturated or unsaturated alkyl or hydroxyalkyl groups that may optionally be alkoxylated
- X- is an acceptable counterion.
- R 3 , R 4 and/or R 5 together may form a heterocyclic ring of up to six members.
- Ri is preferably derived from a fatty aliphatic derived from natural fats o thor oils having an iodine value of from about 1 to about 140, preferably from about 30 to about 90, and more preferably from 40 to about 70. Ri may be restricted to a single chain length or may be of mixed chain length such as those groups derived from natural fats and oils or petroleum stocks. Preferred are tallowalkyl, hardened tallow alkyl, rapeseed alkyl, hardened rapeseed alkyl, erucic alkyl, tall oil alkyl, hardened tall oil alkyl, coco alkyl, oleyl, or soya alkyl.
- R 2 is a straight chain or branched, substituted or unsubstituted divalent alkylene group of from 2 to about 6 carbon atoms, preferably, of 2 to 4 carbon atoms and more preferably of 3 carbon atoms.
- R 3 , R 4 and R 5 are the same or different and are selected from alkyl, aryl or hydroxyalkyl groups of from 1 to about 8 carbon atoms and are preferably hydroxyethyl or methyl.
- R 3 , R 4 and R 5 together with the nitrogen atom to which these groups are bonded form a heterocyclic ring of up to 6.
- R 5 is hydrogen or a CrC 4 alkyl or hydroxyalkyl group
- X- is an acceptable counterion, including, but not limited to halides, oxo ions of phosphorous, sulfur, or chloride, organic anions including but not limited to chlorides, bromides, iodides, oxides of phosphorous, hypochlorides, phosphates, phosphates, oxides of sulfur, sulfates, sulfites, sulfonates, phosphates, acetates, carboxylates, chlorates, perchlorates, salicylates, phthalates, lactates, maleates, glycinates, citrates, citric acid, lactic acid, salicylic acid, phthalic acid, benzoic acid, naphthoic acid, amino acids, and the like.
- alkyl amido quaternary amines employable in the claimed composition include, but are not limited to, erucyl amidopropyl trimethyl ammonium chloride, isostearylamidopropylmorpholine, dimethylalkyl- glycerolammonium chloride, and the like.
- the viscoelastic composition of the invention employs at least one coadditive and/or cosurfactant.
- the coadditive functions to enhance the viscosity of the viscoelastic gel of abovementioned alkyl amido quaternary amine, especially at elevated temperatures. They also reduce the incubation time of the viscoelastic gel to shorten the preparation stage of such gel in the field.
- Preferred coadditives include, but are not limited to sulfonates, sulfates, inorganic and organic acids.
- Particularly effective coadditives are linear alkyl sulfates/sulfonates, linear alpha olefin sulfates/sulfonates, linear fatty acid sulfonates, and/or linear sulfosuccinates, optionally comprising one or more ester moieties.
- these sulfates and sulfonates have one or more
- C 6 to C 24 groups preferably Ci 0 -Ci 4 groups.
- Examples are products of the formulae given below.
- alpha olefin sulfonate sodium salts can be preferred.
- the aforementioned viscoelastic composition are Theologically stable at temperatures of up to about 150 0 C (300 0 F) and advantageously form viscoelastic gels in low or high density brines with a strong elasticity that is suitable for carrying solid materials in subterranean operations.
- the present invention also relates to a method of stimulating and/or modifying the permeability of an underground formation with the viscoelastic composition of the invention, and to drilling fluids, completion fluids, workover fluids, acidizing compositions and the like comprising the viscoelastic composition of the present invention.
- the viscoelastic compositions of the present invention can also be employed to gel most other aqueous systems, such as those utilized in cleaning formulations, water-based coatings, detergent formulations, personal care formulations, water based asphalt formulations and the like.
- the ratio of alkyl amido quaternary amines to coadditive(s) in the viscoelastic composition of the invention, on a weight basis, varies from about 1000 to 1 ; in another embodiment 100 to 2; and in still another embodiment 20 to 5. Generally, the range is from about 10:1 to about 3:1 , in another embodiment 6:1 to about 4:1.
- An aqueous viscoelastic composition especially useful in underground applications can be obtained by adding one or more cationic gelling agents such as described below.
- the concentration of gelling agent in the aqueous viscoelastic composition is generally in the range of from about 0.5% to about 10% by weight, preferably from about 2% to about 8% by weight, and more preferably from about 3% to about 5% by weight based on the total weight of the composition.
- the concentration of coadditive in the aqueous viscoelastic composition is generally in the range of from about 0.001 % to about 10% by weight, preferably from about 0.01 % to about 1 % by weight, and more preferably from about 0.1 % to about 0.5% by weight based on the total weight of the composition.
- the aqueous composition of the invention can include inorganic salts and various additives as described herein below.
- Such a composition is advantageously injected into, for example, an underground system for use in drilling, stimulation (such as hydraulic fracturing), for permeability modification of underground formations, and for uses such as gravel packing, and cementing.
- a preferred viscoelastic composition according to the invention comprises from about erucyl amidopropyl trimethyl ammonium chloride, and a C12 alpha olefin sulfonate, i.e., for example, sodium lauryl sulfate.
- a pourable, concentrated gelling agent composition in accordance with the present invention is prepared by first preparing the alkyl amido quaternary amine component by reacting the corresponding fatty acid with dimethylaminopropylamine (DMAPA) and then quaternized with methyl chloride. The alkyl amido quaternary amine component is then combined with the coadditive at a preferred ratio of 10:1.
- the concentration of viscoelastic composition preferably ranges from about 1 % to about 10% depending on the desired viscosity, more preferably about 2% to 8%, and most preferably about 3% to about 5%.
- Brines gelled with such agents are advantageously used as water diversion agents, pusher fluids, fracturing fluids, drilling muds, gravel-packing fluids, drill- in fluids, work-over fluids, completion fluids, and the like.
- the viscoelastic compositions of the present invention can also be utilized to gel most other aqueous systems, including but not limited to those utilized in cleaning and sanitizing formulations, water-based coatings (e.g. paints), detergent formulations, personal care formulations, water-based asphalt systems, concrete, building products, (e.g., motars, plasters, joint compounds, and the like), agricultural drift control agents and the like.
- the viscoelastic fluid can optionally include lubricants, corrosion inhibitors and various other additives.
- Lubricants can include metal or amine salts of an organo sulfur, phosphorus, boron or carboxylic acid.
- Typical of such salts are carboxylic acids of 1 to 22 carbon atoms including both aromatic and aliphatic acids; sulfur acids such as alkyl and aromatic sulfonic acids and the like; phosphorus acids such as phosphoric acid, phosphorous acid, phosphinic acid, acid phosphate esters, and analogous sulfur homologs such as the thiophosphoric and dithiophosphoric acid and related acid esters; mercaptobenzothiozole; boron acids including boric acid, acid borates and the like; and lauric acid amine salts.
- Corrosion inhibitors can include alkali metal nitrites, nitrates, phosphates, silicates and benzoates.
- Representative suitable organic inhibitors include hydrocarbyl amine and hydroxy-substituted hydrocarbyl amine neutralized acid compound, such as neutralized phosphates and hydrocarbyl phosphate esters, neutralized fatty acids (e.g., those having 8 to about 22 carbon atoms), neutralized aromatic carboxylic acids (e.g., 4-(t-butyl)-benzoic acid), neutralized naphthenic acids and neutralized hydrocarbyl sulfonates.
- Mixed salt esters of alkylated succinimides are also useful.
- Corrosion inhibitors can also include the alkanolamines such as ethanolamine, diethanolamine, triethanolamine and the corresponding propanolamines as well as morpholine, ethylenediamine, N,N-diethylethanolamine, alpha- and gamma-picoline, piperazine and isopropylaminoethanol.
- Stimulation fluids can also include additives for specific applications to optimize the performance of the fluid.
- Examples include colorants; dyes; deodorants such as citronella; bactericides and other antimicrobials; chelating agents such as an ethylene diamine tetraacetate sodium salt or nitrilo triacetic acid; antifreeze agents such as ethylene glycol and analogous polyoxyalkylene polyols; anti-foamants such as silicone-containing agents and shear stabilizing agents such as commercially available polyoxyalkylene polyols. Anti-wear agents, friction modifiers, anti-slip and lubricity agents may also be added. Also included are extreme pressure additives such as phosphate esters and zinc dialkyl dithiophosphate.
- the surfactants disclosed and described herein are advantageously used as gelling agents for fracturing fluids.
- Such fluids create channels or fractures in oil producing reservoir zones in order to improve oil production by providing a high permeability pathway from the reservoir rock to the well bore.
- fracturing fluids are pumped at pressures exceeding the overburden weight of the rock formation thereby causing splits and fractures in the formation rock.
- Propping agents e.g. particulate matter
- Gelling agents are added to the fluid to transport such propping agents and to reduce fluid leakoff.
- the viscoelastic compositions disclosed herein provide several advantages over the polymers (e.g., polysaccharides) currently used as gelling agents for downhole fluids.
- the compounds set forth herein when used as gelling agents for downhole fluid produce less residue on the formation which could result in formation damage during and after the downhole process.
- One can also "break” the gelled fluid by using solvents such as hydrocarbons, alcohols, or even oil from the formation.
- the gelling agents set forth below are useable over a wide range of temperature depending on chain length, and can assist in removing oil from the formation.
- a suitable downhole fluid can include fresh water or seawater or a brine containing sodium chloride (typically 1-5% by weight) and/or calcium chloride (typically 0.5-3% by weight), to which optionally about 3% to about 10%, and preferably about 4% to about 6%, of the viscoelastic composition in accordance with the present invention.
- the viscoelastic composition of the invention can first be blended with water to form a viscoelastic fluid which is then injected into the rock formation in an amount effective to reduce the permeability of the more permeable zone(s) of the formation.
- the concentration of viscoelastic composition in the fluid can be from about 0.5% to about 10%, preferably from about 2% to about 8%, and more preferably from about 3% to about 5% by weight.
- the following non-limiting examples are illustrative of the method of modifying the rheological behavior of aqueous fluids in accordance with the present invention.
- Arquad® APA-E (shown below) is made by reacting erucic acid with DMAPA and then quaternized with methyl chloride in a suitable solvent. The final product has 80% active content and 20% solvent. The structure of the active component is shown below.
- Witconate® AOS-12 is a commercial surfactant sample obtained from Akzo Nobel Surface Chemistry LLC, Chicago, Illinois, which is a 40% Ci 2 alpha olefin sulfonate sodium salt.
- Example 1 heat up curves of 3.4% Arquad APA-E+0.6% Witcolate LCP (Gel 1 ) and 3.0% Arquad APA-E+ 2% Witconate SXS (Gel 2) in 4% KCI at 100 s "1 Q- ⁇
- Example 2 Shear sweep of the gel of 3.4% Arquad APA-E + 0.6% Witconate AOS-12 in 4% KCI at room temperature
- Example 3 Heat up curve of the gel of 2.6% Arquad APA-E + 0.4% Witconate AOS-12 in 14.2ppg * CaBr 2 at 100 s "1
- ppg means density in pounds (0.453 g) per gallon (3.785 I) at 20 0 C, meaning that CaBr 2 is added to the water phase in such an amount that this density is achieved.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002632656A CA2632656A1 (en) | 2005-12-07 | 2006-12-04 | High temperature gellant for viscosity modification of low and high density brines |
GB0812307A GB2447587B (en) | 2005-12-07 | 2006-12-04 | High temperature gellant for viscosity modification of low and high density brines |
BRPI0619530-0A BRPI0619530A2 (en) | 2005-12-07 | 2006-12-04 | high temperature gel forming agent for low and high density brine viscosity modifications |
NO20082963A NO20082963L (en) | 2005-12-07 | 2008-07-04 | High temperature gel for low viscosity modification and high density salt solutions |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/296,145 | 2005-12-07 | ||
US11/296,145 US20070125542A1 (en) | 2005-12-07 | 2005-12-07 | High temperature gellant in low and high density brines |
EP06101407A EP1795571A1 (en) | 2005-12-07 | 2006-02-08 | High temperature gellant for viscosity modification of low and high density brines |
EP06101407.2 | 2006-02-08 |
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WO2007065872A1 true WO2007065872A1 (en) | 2007-06-14 |
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PCT/EP2006/069256 WO2007065872A1 (en) | 2005-12-07 | 2006-12-04 | High temperature gellant for viscosity modification of low and high density brines |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009158392A1 (en) * | 2008-06-26 | 2009-12-30 | The Procter & Gamble Company | Liquid laundry treatment composition comprising a mono-hydrocarbyl amido quaternary ammonium compound |
WO2010071784A1 (en) * | 2008-12-16 | 2010-06-24 | Pq Corporation | Friction modifier for drilling fluids |
US8097580B2 (en) | 2008-06-26 | 2012-01-17 | The Procter & Gamble Company | Liquid laundry treatment composition comprising an asymmetric di-hydrocarbyl quaternary ammonium compound |
CN101560380B (en) * | 2008-12-12 | 2012-06-27 | 中国石油化工股份有限公司胜利油田分公司采油工艺研究院 | Preparation method of depolymerized and dispersed viscosity reducer of heavy oil |
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WO1999035120A1 (en) * | 1998-01-09 | 1999-07-15 | Witco Corporation | Novel quaternary ammonium compounds, compositions containing them, and uses thereof |
WO2001018147A1 (en) * | 1999-09-07 | 2001-03-15 | Crompton Corporation | Quaternary ammonium salts as thickening agents for aqueous systems |
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2006
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Patent Citations (3)
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US20030019627A1 (en) * | 1996-10-09 | 2003-01-30 | Qi Qu | Compositions containing aqueous viscosifying surfactants and methods for applying such compositions in subterranean formations |
WO1999035120A1 (en) * | 1998-01-09 | 1999-07-15 | Witco Corporation | Novel quaternary ammonium compounds, compositions containing them, and uses thereof |
WO2001018147A1 (en) * | 1999-09-07 | 2001-03-15 | Crompton Corporation | Quaternary ammonium salts as thickening agents for aqueous systems |
Non-Patent Citations (1)
Title |
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KALUR GOKUL C ET AL: "Viscosity increase with temperature in cationic surfactant solutions due to the growth of wormlike micelles", LANGMUIR; LANGMUIR NOV 22 2005, vol. 21, no. 24, 22 November 2005 (2005-11-22), pages 10998 - 11004, XP002372339 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009158392A1 (en) * | 2008-06-26 | 2009-12-30 | The Procter & Gamble Company | Liquid laundry treatment composition comprising a mono-hydrocarbyl amido quaternary ammonium compound |
US8097580B2 (en) | 2008-06-26 | 2012-01-17 | The Procter & Gamble Company | Liquid laundry treatment composition comprising an asymmetric di-hydrocarbyl quaternary ammonium compound |
US8163690B2 (en) | 2008-06-26 | 2012-04-24 | The Procter & Gamble Company | Liquid laundry treatment composition comprising a mono-hydrocarbyl amido quaternary ammonium compound |
CN101560380B (en) * | 2008-12-12 | 2012-06-27 | 中国石油化工股份有限公司胜利油田分公司采油工艺研究院 | Preparation method of depolymerized and dispersed viscosity reducer of heavy oil |
WO2010071784A1 (en) * | 2008-12-16 | 2010-06-24 | Pq Corporation | Friction modifier for drilling fluids |
US8003576B2 (en) | 2008-12-16 | 2011-08-23 | The Lubrizol Corporation | Friction modifier for drilling fluids |
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