Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/04—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of filter aids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1666—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing non-conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

• This invention relates to a novel wax crystal modifier composition and to the utilization of same, and more particularly to a wax crystal modifier comprising a polymer prepared from long chain aliphatic esters of unsaturated acids.
• the invention relates to the utilization of certain long chain ester polymers as blending agents for improving flow characteristics of high wax content petroleum oils, i.e., crudes, residua, and light fuel oils, and especially petroleum oils which boil above 650 F. and have flow points above desired specifications.
• pour point is critical with regard to the flow characteristics and, consequently, adversely aifects the storage, mixing, pumping, etc. of such oil.
• pour point characteristics are significant to the design and/or operation facilities for the storage, heat exchange, pumping, etc. of the oil.
• an oil having a high flow point e.g., light fuel oils having flow points above 20 F., cnides having flow points above 55 F. and residual fuels having tiow points above about 60 F. would provide a serious problem relative to the design of the facilities mentioned above.
• the inspections shown in the foregoing Table II illustrate that the Zelten residuum is a premium product per se, as well as a valuable product for blending and for improving other heavy fuel oils due to its low sulfur content, low viscosity, low MNI (Modified Naphtha Insolubles), and low Conradson Carbon number. Furthermore, it is low in ash and vanadium content. These qualities also make Zelten crude an excellent source of cracking stock for obtaining various valuable products, such as straight chain olefins, and the like.
• the column headed by the notation Target indicates the parameters of blends which are desirable using said Zelten residuum as a blending stock, i.e., providing the flow point can be suitably lowered.
• the flow point cannot be satisfactorily reduced without using the polymeric additives of this invention to lower the flow point below the 75 F.
• high pour point petroleum oils or mixtures containing such petroleum oils may have a relatively low viscosity as measured by conventional methods as compared to heavy oils of low wax content
• the handling of the high wax content oils creates special difliculties which are due to the manner in which the oil undergoes changes in flow characteristics on being subjected to changes in temperature.
• the standard ASTM pour point is reasonably indicative of how low the temperature of an oil can be decreased and at what point it can be satisfactorily made to flow.
• high wax content oils such as the above-described Zelten residual oil
• the flow point determined by standardized procedure is variable and is further, a func-v tion of prior thermal treatment.
• This phenomena may be referred to as a pour gap and is determined when highly waxy residua in the presence of natural pour depressants or certain synthetic pour depressants exhibit pour reversion. This is determined by subjecting a mixture of residuum and pour depressant through a series of heating and reheating cycles so as to determine a series of pour points at various reheat temperatures.
• Table III illustrates the effects of various known additives on the pour points at various reheat temperatures, and, consequently, the flow point of Zelten residuum.
• an object of the present invention to provide an additive which substantially improves the flow characteristics of wax-containing petroleum oils.
• the present invention is directed to a petroleum oil composition
• a petroleum oil composition comprising a high wax content petroleum oil, e.g. an oil having a flow point or pour point above 20 F. and especially a residual oil having a boiling point above about 650 F. and a flow point above about 75 F., improved with respect to its wax crystal characteristics by having incorporated therewith an amount of about 0.005 to about 5.5 wt. percent of a polymer prepared by the polymerization of certain long chain esters.
• the present invention especially contemplates the copolymerization of long chain unsaturated esters with an additional ester such as a vinyl ester of a short chain fatty acid.
• fumarate or maleate-vinyl acetate copolymers which contain one or more units such as:
• R has a total chain length of from about 18 to about 34 carbon atoms, excluding branching therein, and x and y are as defined above.
• the long chain ester monomers described above may be copolymerized with various amounts, e.g. 0-60 mole percent, of short chain esters such as methacrylates, acrylates, fumarates, maleates and the like, wherein the alcoholic residue contains from 1 to about 13 carbon atoms.
• the long chain aliphatic esters of unsaturated dibasic basic acids i.e., the acrylic acids
• esters of C to about C especially the C -C unsaturated monobasic acids examples include acrylic acid, the butenic acids, such as crotonic, isocrotonic, vinylacetic and methacrylic acid, the pentenic acids such as, teglic, angelic, and senecioic acid, the hexenic acids, etc.
• Esters of acrylic acid, methacrylic acid and the butenic acids are preferred for the purposes of this invention.
• esters of unasturated dibasic acids which are employed as monomeric components in producing the additive agents employed in accordance with the invention are esters of C -C unsaturated dibasic acids.
• acids which may be esterified to produce such esters include maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, itaconic acid and the like. Esters of the butenedioic acids, fumaric acid and maleic acid and mixtures of the two, are preferred for the purposes of this invention.
• the short chain vinyl esters used as monomers in preparing the copolymers of this invention are vinyl esters of low molecular weight acids containing from about 2 to about 6 carbon atoms per molecule.
• Specific examples of such vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl pentanoate, vinyl hexanoate and vinyl benzoate, the like and mixtures thereof.
• Examples of long chain vinyl esters used in preparing the polymers of this invention include, among others, vinyl nonadecanoate, vinyl arachidate, vinyl behenate, vinyl 6 tetracosanoate, vinyl hexacosanoate, vinyl tricontanoate, the like and mixtures thereof.
• the long chain aliphatic esters described above may be prepared from aliphatic alcohols containing from about 18 to about 34 carbon atoms per molecule. Saturated aliphatic alcohols containing from about 19 to 29 carbon atoms per molecule are preferred for use in preparing the esters. Saturated straight chain alcohols of from 19 to 27 carbon atoms per molecule are particularly effective for purposes of the invention. Mixed esters derived by the reaction of the acids with a mixture of alcohols may be used.
• alcohols suitable for use in producing the esters include straight chain primary alcohols such as stearyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, noncosyl, triacontyl alcohols and the like; branched alcohols, e.g. oxo alcohols such as 2-methyl stearyl, Z-methyl eicosyl, Z-methyl docosyl and the like.
• mixtures of alcohols consisting essentially of saturated alcohols of the requisite chain length may be employed in preparing the long chain esters.
• One such mixture is a hydrogenated fish oil fraction and is marketed under the trade name Behenyl.
• Behenyl This mixture of alcohols consists primarily of docosyl alcohol but contains minor amounts of other alcohols containing from 16 to 24 carbon atoms per molecule.
• the dibasic acid esters of this invention may be prepared from straight chain as well as branched chain alcohols having a chain length, excluding branching, of from 18 to 34 carbon atoms per molecule.
• Typical examples of long chain esters of unsaturated dibasic acids useful in preparing the polymer and copolymer additives include eicosyl fumarate, docosyl fumarate, eicosyl maleate, docosyl citroconate, decosyl maleate, eicosyl mesaconate, eicosyl citraconate, decosyl itaconate, tricosyl fumarate, tetracosyl maleate, pentacosyl citraconate, hexacosyl mesaconate, heptacosyl itaconate, octacosyl fumarate, noncosyl maleate, triacontyl citraconate, hentriacontyl mesaconate, dotriacontyl itaconate, tria
• the monomers described in the preceding paragraphs are polymerized in a conventional manner to produce the polymers useful in the present invention.
• the polymerization reaction may be carried out without diluent or in a solution of a hydrocarbon solvent such as heptane, benzene, cyclohexane or white oil at a temperature in the range of from about 60 F. to about 250 F. and may be promoted by gamma radiation or by means of a peroxide type catalyst such as benzoyl peroxide, a hydroperoxide or an azo catalyst such as alpha-alphaazo-bis-isobutyronitrile. It is generally preferred to carry out the polymerization reaction under a blanket of an inert gas such as nitrogen or carbon dioxide in order to exclude oxygen.
• the polymerization time may vary from about 1 to about 36 hours.
• the polymers of this invention may have a viscosity average molecular weight in the range of from about 1400 to about 100,000 or higher, i.e. the upper range is limited only by the polymer oil solubility. It is preferred, however, that the molecular weight be within the range between about 1800 to about 30,000.
• the amount of short chain vinyl ester (i.e., those esters wherein the side chain R contains from 1 to about 5 carbon atoms) present in the copolymers of this invention as compared to the amount of long chain esters (i.e., those e'sters wherein the side chain R contains from about 18 to about 34 carbon atoms) present is in the range from about 10 to about mole percent, the preferred range being from about 25 to 75 mole percent.
• the long chain monomers of this invention may be polymerized together in any portion desired (i.e., 0-100 mole percent) to secure the maximum potency in a given base stock.
• the final additive polymers of this invention may be blended directly with the high wax content petroleum oils. Polymer concentrations within the range of from 0.0025 to 5.0 wt. percent based on weight of wax-containing oil will be operable and will give the desired improvement in flow characteristics. Based on economic as well as flow modifying reasons, from about 0.003 to 0.45 wt. percent of the additive is preferably employed.
• the additives of this invention are found compatible with other additive materials and may, if desired, be blended with petroleum oils containing minor amounts of viscosity index improvers, rust inhibitors, oiliness agents, oxidation inhibitors and the like.
• the additives of this invention also exhibit utility as a dewaxing aid.
• admixtures of the polymers of this invention with a wax-containing oil may be processed by chilling the admixture in any suitable manner to a wax precipitation temperature, e.g., from about 30 to about -+20 F.
• the precipitated wax may then be removed by centrifugation or filtration, preferably the latter.
• Particularly desirable results are obtained in the conventional solvent dewaxing process wherein the oil, dewaxing aid and dewaxing solvent are admixed at elevated temperatures to form a solution which may then be d'ewaxed in the manner set forth above.
• solvent dewaxing feeds comprising the hereinbefore specified amount of polymer, from about 50 to about 90 wt. percent of the dewaxing solvent and from about 10 to about 50 Wt. percent of the wax-containing oil can be easily and efficiently filtered in conventional dewaxing filtration equipment.
• suitable solvents include benzene, toluene, acetone, methylethyl ketone, propane, hexane, ethylene dichloride, aliphatic alcohols, naphtha and mixtures thereof.
• EXAMPLE 1 Preparation of behenyl fumarate Two hundred grams of behenyl alcohol, 38 grams fumaric acid, 500 ml. n-heptane and 5 grams p-toluenesulfonic acid were heated to reflux and the water evolved was collected in a Dean-Stark trap. At the end of a 6 hour period, 11 mls. of water were collected and the reaction completed. The solution was cooled to 50 C. and washed with 2-100 ml. portions of sodium carbonate and then with 150 ml. portions of water until a pH of 7 was reached. The heptane solution was then dried over magnesium sulfate, filtered and the solvent removed under reduced pressure. The yield was 95%.
• EXAMPLE 4 The following example illustrates the use of a docosanoyl fumarate-vinyl acetate copolymer which has been dialyzed.
• the polymerization reaction products may, if desired, be subsequently subjected to dialysis.
• dialysis relates to the preferential diffusion of one or more lower molecular weight components of a solution of polymers in a specific solvent through a semipermeable membrane in the direction of a liquid-phase consisting predominantly of solvent.
• higher molecular weight components are found to diffuse very slowly or not at all while lower molecular weight components in true solution diffuse rapidly.
• the active pour depressant components of suitable molecular weight will not diffuse through a thin rubber membrane while the importent, e.g., diluent oil, etc., diffuse quite rapidly through said membrane.
• such dialysis can be effected at temperatures ranging from about 20 to about 150 C. and preferably about 30 to C.
• Copolymer is a dialysis fraction residue and amounts to about 90% of the crude polymer:
• Base blend no additive 75 0.075 behenyl fumarate-vinyl acetate copolymer 35 0.075 C fumarate-vinyl acetate copolymer 20 0.075 C -C polymethacrylate 45 Crude oil consisting of 50/50 vol. mixture of Redwash crude from Utah and Rungely crude from Western Colorado.
• Crude oil consisting of 50/50 vol. mixture of Redwash crude from Utah and Rangely crude from western Colorado.
• EXAMPLE 9 This example serves to illustrate the dewaxing aid characteristics of the polymers of the present invention.
• a wax-containing oil having the properties shown below 75 in Table X was dewaxed in the following manner: the
• test oil was diluted at 140 -F. with a solvent consisting of 57 wt. percent methylethyl ketone and 43 wt. percent toluene at a solvent/oil ratio of 3.5/1 and then chilled at the rate of 3 F. per minute from a feed temperature of 140 F. to a filter temperature of -10 F.
• the chilled mixture was then continuously filtered through a refrigerated circular leaf filter at a pressure diiferential of 25 inches of mercury.
• the filtration cycle consisted of a filtration time of 33 seconds, a drying time of 10 seconds, a wash time of 22 seconds, and a second drying time of 17 seconds.
• Dewaxing aid used 0.06 wt. percent GaL/hr. ft. None 4.7 n-C polymethacrylate 11.7 n-C fumarate-vinyl acetate copolymer 18.8 Behenyl fumarate-vinyl acetate copolymer 17.0
• An oil composition having improved flow or pour point characteristics which comprises wax-containing oil selected from the group consisting of residua boiling above about 650 F. and crude oil, having incorporated therewith a wax modifying effective amount of oil-soluble flow improving polymer having molecular weight of at least 1400 selected from the group consisting of:
• polymers consisting essentially of long chain unsaturated ester selected from the group consisting of -(1) esters of C to C saturated aliphatic alcohol having a substantially linear C to C alkyl group and unsaturated carboxylic acid selected from the group consisting of C to C monobasic acid and C to C dibasic acid and (2) vinyl esters having a substantially linear C to C alkyl group attached to the carbonyl group of said vinyl ester, and mixtures thereof;
• copolymers consisting essentially of said long chain unsaturated ester and between 0 to about 60 mole percent of a short chain ester selected from the group consisting of methacrylates, acrylates, fumarates, and maleates, wherein the alcoholic residue of such short chain esters contains 1 to 13 carbon atoms.
• composition according to claim 1 wherein said oil is residua having a pour point above 65 F.
• composition according to claim 1 wherein said oil is crude oil having a pour point above about 40 F.
• composition according to claim 1 wherein said long chain unsaturated ester is acrylate ester.
• composition according to claim 1 wherein said long chain unsaturated ester is methacrylate ester.
• composition according to claim 1 wherein said long chain unsaturated ester is fumarate ester.
• composition according to claim 1 wherein said molecular weight is in the range of about 1400 to 100,000 and wherein the amount of said polymer in said oil is about .0025 to 5 weight percent.
• composition according to claim 1 wherein said saturated aliphatic alcohol of (a) contains about 19 to 27 carbon atoms, and said molecular weight is about 1800 to 30,000.
• composition according to claim 1 wherein said flow improving polymer is a homopolymer of C methacrylate.
• composition according to claim 1 wherein said flow improving polymer is a copolymer of C fumarate and vinylacetate.
• a composition according to claim 1, wherein said fiow improving polymer is a copolymer of C and C methacrylate.
• composition according to claim 1 wherein said flow improving polymer is a homopolymer of C polymethacrylate.
• a composition according to claim 1, wherein said flow improving polymer is a polymer of behenyl polyacrylate.
• a composition having improved flow or pour point characteristics which comprises a Wax-containing residue from the topping of crude oil and boiling above 650 F. having incorporated therewith a wax modifying effective amount of oil soluble flow improving polymer having a molecular weight of at least 1400 selected from the group consisting of (a) polymers consisting essentially of long chain unsaturated esters selected from the group consisting of 1) esters of unbranched C to C saturated aliphatic alcohols and unsaturated carboxylic acids selected from the group consisting of C and C monobasic acids and C dibasic acids and (2) vinyl esters having an unbranched C to C alkyl group attached to the carbonyl group of said vinyl ester; (b) copolymers consisting essentially of said long chain unsaturated ester and a short chain unsaturated vinyl ester; and
• copolymers consisting essentially of said long chain unsaturated ester and a short chain ester selected from the group consisting of methacrylates, acrylates, fumarates and maleates.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)

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Cited By (20)

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• 1966
  • 1966-10-14 US US00586654A patent/US3729296A/en not_active Expired - Lifetime
• 1967
  • 1967-08-31 CA CA999,174A patent/CA977549A/en not_active Expired
  • 1967-09-05 GB GB40549/67A patent/GB1197474A/en not_active Expired
  • 1967-10-02 FR FR1553794D patent/FR1553794A/fr not_active Expired
  • 1967-10-13 NL NL676713932A patent/NL154550B/xx not_active IP Right Cessation
  • 1967-10-13 DE DE19671645738 patent/DE1645738A1/de active Pending
  • 1967-10-13 DE DE1794416A patent/DE1794416B2/de not_active Ceased
• 1970
  • 1970-02-13 BE BE745920A patent/BE745920Q/xx not_active IP Right Cessation
• 1975
  • 1975-03-11 CA CA221,758A patent/CA980568A/en not_active Expired

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