US3658493A - Distillate fuel oil containing nitrogen-containing salts or amides as was crystal modifiers - Google Patents
Distillate fuel oil containing nitrogen-containing salts or amides as was crystal modifiers Download PDFInfo
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- US3658493A US3658493A US858180A US3658493DA US3658493A US 3658493 A US3658493 A US 3658493A US 858180 A US858180 A US 858180A US 3658493D A US3658493D A US 3658493DA US 3658493 A US3658493 A US 3658493A
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- 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
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- 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
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- 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
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- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
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- 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
- C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
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- 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
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- 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
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- 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
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- 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
- C10L1/20—Organic compounds containing halogen
- C10L1/206—Organic compounds containing halogen macromolecular compounds
- C10L1/207—Organic compounds containing halogen macromolecular compounds containing halogen with or without hydrogen
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- 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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- 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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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- 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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
Definitions
- nitrogen materials may also be utilized to advantage with ethylene polymeric pour point depressants, particularly those polymers 'wherein a polyethylene backbone resulting from ethylene polymerization is divided by side groups or branches, into segments.
- side groups include hydrocarbons, esters, ketones, chlorine, or other groups, and usually result from copolymerizing the ethylene with a comonomer, e.g. vinyl acetate, or they can result from homopolymerization of the ethylene, or by chlorinating polyethylene, etc.
- Kerosene which acts as a solvent for n-paraffin wax, had traditionally been a component of middle distillate fuel oils. Recently, with the increased demands for kerosene for use in jet fuels, the amount of kerosene used in middle distillate fuel oils has decreased. This, in turn, has frequently required the addition of wax crystal modifiers, e.g. pour point depressant additives, to the fuel oil to make up for the lack of kerosene.
- wax crystal modifiers e.g. pour point depressant additives
- the more effective of these distillate oil pour depressants are copolymers of ethylene with various other monomers, e.g. copolymers of ethylene and vinyl esters of lower fatty acids such as vinyl acetate (U.S. Pat. No.
- the amides and salts of the invention will usually total 7 to 60, preferably 12 to 30 carbons and have at least one straight chain hydrocarbon segment of at least six carbon atoms. It is polyethylene (Belgium Patent 707,371 and US. Pat. No. I
- the present invention is based on the discovery that certain classes of amides, and ammonium and amine salts, result in small particle size crystals which are usually sufficiently small to pass through the screens and filter equipment so as not to cause plugging, and at the same time do not unduly interfere with the action of the pour point depressant in preventing the oil from freezing.
- these amides and salts of the invention are effective agents for controlling the size of the wax crystals that form during cooling of the oil. It is not known believed this segment provides sites on the amide or salt crystal for the n-paraffin wax molecules to adhere onto, thereby encouraging the wax molecules to start their crystallization onto the already formed amide or salt crystals.
- amides and salts are formed from (1') an acid component including monoor dicarboxylic acid, phenol, inorganic acid, sulfonic acid, etc., reacted with (2) a nitrogen component including ammonia, monamines, polyamines, hydroxy amines, etc.
- an acid component including monoor dicarboxylic acid, phenol, inorganic acid, sulfonic acid, etc.
- a nitrogen component including ammonia, monamines, polyamines, hydroxy amines, etc.
- molar equivalents of the acid and nitrogen components i.e. one acid group per one nitrogen group, will be reacted together, although in many cases a slight excess (e.g. up to about 1 molar equivalent excess) of acid may be used to drive the salt or amide formation to completion.
- polyacids or polyamines may be used.
- one mole of monocarboxylic acid can be reacted with one mole of tetraethylenepentamine, and this is also within the scope of the present invention although it is less preferred since the test data indicates maximum effectiveness occurs with the aforesaid one to one molar equivalent ratio.
- salts or amides from straight chain, or slightly branched, acid and/or nitrogen components are preferred as they generally perform better than highly branched materials.
- mixed acids or mixed amines appear to be less effective than unmixed acids or unmixed amines in forming the salt or amide. This, too, is believed related to crystal formation.
- the mono and dicarboxylic acids utilized in the invention can be represented by the general formula: R(COOI-I),, where n is l or 2, and R is a hydrocarbon group of one to 29, e.g. three to 18, carbon atoms.
- R can be unsubstituted or substituted (e.g. hydroxy substitiited), saturated, unsaturated, or aromatic, and includes aliphatic, aryl, alicyclic, alkaryl, and hydroxy alkyl groups, etc.
- acids examples include formic, acetic, hexanoic, lauric, myristic, palmitic, margaric, stearic, hydroxy stearic, behenic, naphthenic, salicyclic, acrylic, fumaric, maleic, etc.
- Mixtures of acids such as the commercial tallow acids, coconut acids, etc., may also be used.
- Preferred are the straight chain monocarboxylic acids, i.e. fatty acids.
- Phenols which may be used include phenol, and alkylated phenol wherein the phenol is substituted with one to three alkyl groups of one to 12 carbons, etc.
- inorganic acids include the mineral acids such as sulfuric acid, hydrochloric acid, sulfurous acid, the various The monoamines of the invention can be primary, secondary or tertiary and are represented by the fonnula:
- R is a C, to C hydrocarbon group while R and R are each hydrogen or a C to C preferably a C, to C,,, hydrocarbon group.
- the chain length of R and R is kept short to keep oil-solubility limited so the final product functions as a nucleation agent. Longer side chains, i.e. R and R values of C and higher would tend to increase oil solubility to an undesirable extent.
- the hydrocarbon groups are preferably aliphatic, e.g. alkyl groups, and can be unsubstituted or substituted, e.g. hydroxy substituted.
- Examples of primary amines include tridecyl amine, n-octyl amine, C Oxo amine, n-dodecyl amine, coco amine, tallow amine, behenyl amine, etc.
- Examples of secondary amines include diethyl amine, di-n-octyl amine, methyl-lauryl amine, dodecyl-octyl amine, coco-methyl amine, tallow-methyl amine, methyl-n-octyl amine, methyl-n-dodecyl amine, methyl-behenyl amine, etc.
- tertiary amines include triethylene amine, coco-diethyl amine, cyclohexyldiethyl amine, coco-dimethyl amine, tri-n-octyl amine, dimethyl-dodecyl amine, methyl-ethyl-coco amine, etc.
- hydroxy substituted amines include monoethanol amine, diethanol amine, triethanol amine, diisopropanol amine, etc.
- polyamines can also be used.
- the most common commercial ones are the ethylene amines having two to ten nitrogens such as ethylenediamine, diethylenetriamine, tetra-ethylenepentamine, etc.
- Amine mixtures may also be used and many amines derived from natural materials are mixtures.
- coco amine derived from coconut oil is a mixture of primary amines with straight chain alkyl groups ranging from C to C
- tallow amine derived from hydrogenated tallow, which is a primary amine with a mixture of C, to C,, straight chain alkyl groups.
- the amides can be formed in a conventional manner by heating the amine and acid with the removal of the water of reaction.
- the salts are also conventionally prepared by simply mixing the amine and the acid together with stirring at room temperature, e.g. 77 F., or by blowing ammonia through the acid.
- the nitrogen materials, or nucleation agents, of the invention can be utilized with pour depressants, and in many cases will reduce the amount of pour depressant that is required to give the fuel oil the desired degree of fluidity at low temperatures.
- these polymeric pour depressants have a polymethylene backbone which is divided into segments by hydrocarbon or oxyhydrocarbon side chains. Generally, they will comprise about three to 40, preferably four to 20, molar proportions of ethylene per molar proportion of a second ethylenically unsaturated monomer, which latter monomer can be a single monomer or a mixture of such monomers in any proportion.
- oil-soluble polymers will generally have a number average molecular weight in the range of about 1,000 to 50,000, preferably about 1,000 to about 5,000, as measured for example, by Vapor Phase Osmometry, such as using a Mechrolab Vapor Phase Osmometer Model 310A.
- the unsaturated monomers, copolymerizable with ethylene, include unsaturated mono and diesters of the general fonnula:
- R is hydrogen or methyl
- R is a OOCR, or COOR, group wherein R, is hydrogen or a C, to C preferably a C, to C,, straight or branched chain alkyl group
- R is hydrogen or COOR,
- esters include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, palmityl alcohol ester of alpha-methyl-acrylic acid, C Oxo alcohol esters of methacrylic acid, etc.
- monomers where R, is hydrogen and R and R, are -COOR groups include mono and diesters of unsaturated dicarboxylic acids such as: mono C Oxo fumarate, di-C Oxo fumarate, di-isopropyl maleate; di-lauryl fumarate; ethyl methyl fumarate; etc.
- the Oxo alcohols mentioned above are isomeric mixtures of branched chain aliphatic primary alcohols prepared from olefins, such as polymers and copolymers of C to C, monoolefins, reacted with CO and hydrogen in the presence of a cobalt-containing catalyst such as cobalt carbonyl, at temperatures of about 300 to 400 F., under pressures of about 1,000 to 3,000 psi., to form aldehydes. The resulting aldehyde product is then hydrogenated to form the Oxo alcohol which is then recovered by distillation.
- olefins such as polymers and copolymers of C to C, monoolefins
- the aforementioned second monomers also include ketones containing a total of four to 24 carbons which can be represented by the general formula:
- R is a C, to C hydrocarbon group such as aryl, alkaryl, cycloalkane, straight or branched chain alkyl group, etc.
- R is hydrogen or a C, to C alkyl group.
- R is a C, to C alkyl group and R is hydrogen.
- ketones examples include vinyl methyl ketone (i.e., R is hydrogen and R is methyl), vinyl isobutyl ketone, vinyl n-octyl ketone, vinylisooctyl ketone, vinyl dodecyl ketone, vinyl-phenyl ketone, vinyl-naphthyl ketone, vinyl-cyclo-hexyl ketone, 3-pentein-2- one, i.e. R is methyl and R is methyl, etc.
- Another class of monomers that can be copolymerized with ethylene include C, to C alpha monoolefins, which can be either branched or unbranched, such as propylene, isobutene, n-octene-l isooctene-l, n-decene-l, dodecene-l, etc.
- Still other monomers include vinyl chloride, although essentially the same result can be obtained by chlorinating polyethylene. Or as previously mentioned, branched polyethylene can be used per se as the pour depressant.
- copolymer pour depressants are generally formed using a free radical promoter, or in some cases they can be formed by thermal polymerization, or they can be formed by Ziegler catalysis in the case of ethylene with other olefins.
- promoter usually dissolved in solvent so that it can be pumped, and additional amounts of the second monomer, e.g. unsaturated ester, are added to the vessel continuously, or at least periodically, during the reaction time, which continuous addition gives a more homogeneous copolymer product as compared to adding all the unsaturated ester at the beginning of the reaction.
- additional ethylene is supplied through a pressure controlling regulator so as to maintain the desired reaztion pressure fairly constant at all times.
- the liquid phase of the pressure vessel is distilled to remove the solvent and other volatile constituents of the reacted mixture, leaving the polymer as residue.
- the polymer is dissolved in a light mineral oil to form a concentrate usually containing 25 to 60 wt. polymer.
- the solvent can be any non-reactive organic solvent for furnishing a liquid phase reaction which will not poison the catalyst or otherwise interfere with the reaction, and preferably is a hydrocarbon solvent such as benzene, cyclohexane, and hexane.
- the promoter can be any of the conventional free radical promoters, such as peroxide or azotype promoters, including the acyl peroxides of C, to C branched or unbranched carboxylic acids, as well as other common promoters.
- promoters include dibenzoyl peroxide, di-tertiary butyl peroxide, di-tertiary butyl perbenzoate, tertiary butyl hydroperoxide, di-acetyl peroxide, di-ethyl peroxycarbonate, cumene hydroperoxide, alpha, alpha, azo-diisobutyronitrile, di-lauroyl peroxide, etc.
- the temperature used during the reaction will usually depend upon the choice of the free radical promoter and its rate of decomposition, and will usually range from 70 to 250 C.
- reaction pressures employed will usually be in the range of 800 to 10,000 psig., for example 900 to-6,000 psig. This pressure can be attained by maintaining a fairly continuous and constant pressure on the reaction chamber through controlling the inlet feed of ethylene.
- the time of reaction will depend upon, and is interrelated to, the temperature of the reaction, the choice of promoter, and the pressure employed. In general, however, one-half to 10, usually I to 5, hours will complete the reaction.
- the final composition of the invention will generally comprise a major amount of the distillate containing fuel oil and about 0.001 to 1 wt. preferably 0.005 to 0.15 wt. of the aforementioned described amide or salt nucleation agent.
- the composition can also contain about 0.001 to 2 wt. preferably 0.005 to 0.15 wt. of the aforedescribed methylene backbone pour point depressant. Said weight percents are based on the weight of the total composition.
- the hydrocarbon oils which are treated for pour depression with the nucleation agents of this invention, include cracked and/or virgin distillate heating oils boiling from about 300 up to about 750 F., e.g., No. l and 2 Fuel Oils.
- these distillate heating oils may also be blended with 0 to 70 wt. preferably 0 to 30 wt. based on the total weight of oil, of residua-fuel.
- a number of other nucleating agents of the invention were tried in lube oil, 100 percent residua fuel, and also crude oil, and had no effect on improving flow.
- the nucleation agents of the invention may be used alone as the sole oil additive, or in combination with other oil additives such as pour depressants or other flow improvers; corrosion inhibitors; antioxidants; sludge inhibitors; sludge dispersants; etc.
- Heating Oil This was a mixture of 20 volume percent straight run stock and 80 volume percent of crack stock. This heating oil had a cloud point of 24 F., a pour point of +20 F., an aniline point of 135 F an initial boiling point of 370 F and a final boiling point of 644 F.
- pour Depressant A This was a concentrate of 48 wt. light mineral oil and about 52 wt. ethylene-vinyl acetate copolymer having a number average molecular weight of about 2,605 by Vapor Phase Osmometry, having about l0-l2 methylene terminated branches per hundred carbon atoms in the backbone, and a relative molar ratio of about 6.8 moles of ethylene per mole of vinyl acetate in the copolymer.
- This copolymer was prepared by copolymerizing ethylene and vinyl acetate using ditertiary butyl peroxide at a temperature of about 150 C. under 950 psig ethylene pressure.
- a three liter stirred autoclave was charged with l 150 ml. of benzene as solvent. The autoclave was then purged with nitrogen and then with ethylene. An initial charge of 40 ml. vinyl acetate was added. The autoclave was then heated to a temperature of about 150 C. 2 C., while ethylene was pressured into the autoclave to a pressure of 950 psig. Then, while maintaining the temperature at about 150 C., a solution consisting of 23 wt. di-tertiary butyl peroxide dissolved in 77 wt. benzene in order to facilitate pumping was continuously injected into the autoclave at a rate of 30 cc. per hour for 150 minutes.
- pour Depressant B This was a concentrate of 48 wt. terpolymer in mineral oil, the terpolymer having a number average molecular weight (VPO) of about 2,900, and comprising about 68.0 wt. ethylene, 25.5 wt. vinyl acetate, and 6.5 wt. of-di-C -Oxo fumarate.
- VPO number average molecular weight
- a typical preparation of this terpolymer is carried out in the same manner as the typi cal laboratory preparation of Pour Depressant A described above, except that the initial charge to the reactor consists of a mixture of about 80 wt. vinyl acetate and about 20 wt. of the di-C -Oxo fumarate.
- pour depressant C This pour depressant was a random copolymer of ethylene and propylene, having a molecular weight of about 1,495, and a relative mole ratio of 12.3 molar proportions of ethylene per molar proportion of propylene. This was used in a concentrate of about 52 wt. copolymer in mineral oil.
- pour Depressant D This was a concentrate of 51 wt. oil and 49 wt. of a random copolymer of ethylene and isobutyl acrylate having a molecular weight of about 3,370, and a relative mole ratio of about 7.2 moles ethylene per mole of isobutyl acrylate, which copolymer was formed by free radical polymerization.
- Flow Test B This test is carried out using the same test device and procedure as in A above, except the oil is cooled in a cold box from room temperature to 15 F., which had been 'determined as a critical temperature for the aforedescribed maintained at 15 R, where the small sample rapidly cools from room temperature (about 70-75 F.) to 15 F. in about two hours and is then tested. Due to the sudden cooling, this test is less severe than Flow Test A where the cooling is much slower.
- EXAMPLE ll Ammonium Salts Of Fatty Acids a series of ammonium salts were prepared by saturating a fatty acid solution in kerosene with ammonia until no more ammonia was absorbed. This reaction was carried out in the solvent at room temperature and a typical preparation is as follows:
- compositions were made up using Heating Oil and Pour Depressant A, with and without an ammonium salt. These compositions were tested according to Flow Tests A and B.
- the Coconate of Table 11 was obtained from coconut acid which on a weightpercent basis is a mixture of 4% C 4% C 45% C 15% C 14% C and 18% C,, saturated straight chain carboxylic acids.
- Trldecyl Lauri0 391 0.05 0.02 70 These amine salts were prepared by simple mixing of the Tallow Stearic 553 8-32 8-8; 3% amine and the acid at 77 F. r 0:03 0:02 100 I1 Octyl 1 413 0 06 0 02 1
- the tridecyl amine that was used is a mixture of C to C 83 mono amines with branched tertiary alkyl groups and primary "'Dodecyl 470 0106 0: 02 1 0 amine groups, with an average molecular weight of 191.
- the naphthenic acid that was used is a mixture of saturated 2O Coco .410 494 0:03 0.' 02 100 straight chain, branched and cyclic carboxylic acids, including Cyclohexyl d0 383 ggg 3' 8g igg some keto and hydroxy acids.
- the minor components are. 3 100 Tallow ..do 553 o 06 0 02 100 phenolic materials and sulfur-containing acids.
- the average 70 molecular weight was 225. 596 i 02 60 -do 377 0. 05 0. 100
- the results obtained when using these salts in Heating Oil Tridecylfl Behenic 521 0 05 0 02 100 are summarized in the following Table IV: 0. 03 0. 02 100 g "3 g 0. 00 0.02 too TABLE IV.--'IRIDEOYL' AMINE NAPH'IHENATE AND a 3; @3555? $2 3; 3; 38
- the cold room is lowered at 4 F. per hour from +35 to 40 F.
- the fuel blend (50 gallons) is contained in a typical 275-gallon tank connected through the usual fittings and a three-eighths inch copper line to a regular oil filter and oil burner pump in an adjoining room at about 60 to 70 F.
- the fuel blend is recycled from the tank through the filter and burner pump, and back to the tank until flow stops due to plugging.
- This test is useful in predicting the lowest temperature at which the fuel is operable as related to the coldest weather to be expected. It has been demonstrated that fuels which pass this test (pumping to -20 F. or lower) will perform well under actual winter field conditions where the temperature frequently drops as low as -30 F.
- Table Vlll shows that the 0.05 wt. triethanolamine stearate was about as effective in improving the cold flow as 0.10 wt. of the Pour Depressant. Use of the combination of Pour Depressant and amine salt gave better results than either alone.
- pour point depressants such as homopolymers of polyethylene having 3 to 12 methylene terminating branches per carbon atoms, polyethylene chlorinated with 5 to 35 wt. chlorine, etc.
- an inert carrier such as a major amount of mineral oil, and about 1 to 20 wt. of the aforesaid nitrogen-containing material and about 2 to 29 wt. of the methylene backbone pour point depressant can be made for ease of shipping and handling.
- substantially oil insoluble the amides and salts of the invention, in a finely divided form, can be readily dispersed in the carrier by agitating thus making such concentrates practical.
- a fuel oil composition comprising middle distillate fuel containing n-paraffin wax, about .001 to 2 wt. of an oil-soluble polymethylene backbone pour point depressant having a molecular weight in the range of about 1,000 to 50,000 selected from the group consisting of:
- R is selected from the group consisting of hydrogen and methyl
- R is selected from the group consisting of OOCR and COOR.
- R is a C, to C alkyl group
- R: is selected from the group consisting of hydrogen and COOR
- n is one to two and R is a C, to C hydrocarbon group which may be unsubstituted or hydroxy substituted,
- B a nitrogen component selected from the group consisting of: 1. ammonia, 2. monoamine of the formula:
- R is a C, to C hydrocarbon group, and R and R are each selected 3. inorganic acid
- R is a C to C, hydrocarbon group, R, and R are each selected from the group consisting of hydrogen and C to C hydrocarbon groups, said hydrocarbon groups being unsubstituted or hydroxy substituted and 3.
- ethylene polyamine having two to ten nitrogen atoms, said nitrogen-containing material having at least one straight chain hydrocarbon group of at least six carbon atoms and having a total number of carbon atoms in the range of about seven to 60, and wherein said methylene backbone pour point depressant has a number average molecular weight of about 1,000 to 5,000, and is a eopolymer of 3 to 40 moles of ethylene per molar proportion of an ester of the formula:
- composition according to claim 1 wherein said material is a salt.
- composition according to claim 1 wherein said acid component is a monocarboxylic acid and said nitrogen component is a primary monoamine.
- composition according to claim 4 wherein said acid is hydroxy substituted.
- composition according to claim 5 wherein said amine is an ethanol amine.
- composition according .to claim 1 wherein said material is an amide of a monocarboxylic acid and an ethanol amine.
- composition according to claim 1 wherein said material is a salt of monocarboxylic acid and ammonia.
- composition according to claim 1 wherein said material is the salt of a monocarboxylic acid and said monoamine.
- composition according to claim 1 wherein said material is a salt of a monocarboxylic acid and of an ethanol amine.
- a composition according to claim 11 wherein in said ester, R is hydrogen and R, is selected from the group consisting of OOCR and COOR, wherein R is a C to C alkyl group, and wherein R is selected from the group consisting of hydrogen and COOR 13.
- a fuel oil composition for heating comprising a major amount of fuel oil consisting essentially of middle distillate fuel and 0 to 70 wt. of residua fuel, 0.005 to 0.15 wt. of an oil-soluble polymethylene backbone pour depressant, having a molecular weight of about L000 to 5,000, which is a copolymer of 4 to 20 molar proportions of ethylene per molar proportion of an ester of the formula:
- B a nitrogen component selected from the group consisting of: 1. ammonia, 2. monoamine of the formula:
- R is a C, to C hydrocarbon group
- R and R are each selected from the group consisting of hydrogen and C, to C hydrocarbon groups, said hydrocarbon groups being unsubstituted or hydroxy substituted
- said nitrogen-containing materials having at least one straight chain hydrocarbon group of at least six carbon atoms and having a total number of carbon atoms in the range of about 12 to 30.
- An additive concentrate for treating fuel oil compositions containing distillate fuel oil to improve its cold flow properties comprising a major amount of a hydrocarbon carrier and about one to 20 wt. of finely divided limited, solubilityin-oil nitrogen-containing wax crystal modifier suspended in said oil, and about two to 29 wt. of a methylene backbone oil-soluble pour point depressant dissolved in said hydrocarbon carrier, said nitrogen-containing material being selected from the group consisting of amides and salts of:
- n is one to two and R is a C to C hydrocarbon group which is unsubstituted or hydroxy substituted,
- alkylene polyamine having two to ten nitrogen atoms
- said nitrogen-containing material having at least one straight chain hydrocarbon group of at least six carbon atoms and having a total number of carbon atoms in the range of about seven to 60.
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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)
- Liquid Carbonaceous Fuels (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US85818069A | 1969-09-15 | 1969-09-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3658493A true US3658493A (en) | 1972-04-25 |
Family
ID=25327678
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US858180A Expired - Lifetime US3658493A (en) | 1969-09-15 | 1969-09-15 | Distillate fuel oil containing nitrogen-containing salts or amides as was crystal modifiers |
Country Status (9)
Country | Link |
---|---|
US (1) | US3658493A (ru) |
JP (1) | JPS5036246B1 (ru) |
CA (1) | CA920365A (ru) |
DE (1) | DE2042683C3 (ru) |
DK (1) | DK127790B (ru) |
FR (1) | FR2061372A5 (ru) |
GB (1) | GB1318241A (ru) |
NO (1) | NO127198B (ru) |
SE (1) | SE372557B (ru) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3946053A (en) * | 1970-09-30 | 1976-03-23 | Cities Service Oil Company | Hydrocarbyl hydrogen phosphate salts of amino-amides |
DE2604396A1 (de) * | 1975-02-13 | 1976-08-26 | Exxon Research Engineering Co | Brennstoffoel |
FR2426730A1 (fr) * | 1978-05-25 | 1979-12-21 | Exxon Research Engineering Co | Compositions d'additifs pour ameliorer l'ecoulement et la filtrabilite des fuel-oils distilles |
US4211534A (en) * | 1978-05-25 | 1980-07-08 | Exxon Research & Engineering Co. | Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils |
US4261703A (en) * | 1978-05-25 | 1981-04-14 | Exxon Research & Engineering Co. | Additive combinations and fuels containing them |
EP0030099A1 (en) * | 1979-11-23 | 1981-06-10 | Exxon Research And Engineering Company | Additive combinations and fuels containing them |
DE3137233A1 (de) * | 1980-09-19 | 1982-06-09 | Elf France, 75007 Paris | Zusammensetzungen zur verbesserung der kaltfiltirerbarkeit von mittleren erdoelschnitten |
US4402708A (en) * | 1980-11-18 | 1983-09-06 | Exxon Research & Engineering Co. | Dialkyl amine derivatives of phthalic acid |
US4464182A (en) * | 1981-03-31 | 1984-08-07 | Exxon Research & Engineering Co. | Glycol ester flow improver additive for distillate fuels |
US4491455A (en) * | 1982-02-10 | 1985-01-01 | Nippon Oil And Fats Co., Ltd. | Method for improving cold flow of fuel oils |
US4537602A (en) * | 1982-09-16 | 1985-08-27 | Exxon Research & Engineering Co. | Additive concentrates for distillate fuels |
US4556499A (en) * | 1981-03-28 | 1985-12-03 | Hoechst Aktiengesellschaft | Process for improving the flow properties of mineral oils |
US4564460A (en) * | 1982-08-09 | 1986-01-14 | The Lubrizol Corporation | Hydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
US4575526A (en) * | 1982-08-09 | 1986-03-11 | The Lubrizol Corporation | Hydrocarbyl substituted carboxylic acylaging agent derivative containing combinations, and fuels containing same |
US4613342A (en) * | 1982-08-09 | 1986-09-23 | The Lubrizol Corporation | Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
US4623684A (en) | 1982-08-09 | 1986-11-18 | The Lubrizol Corporation | Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
US5009670A (en) * | 1988-05-19 | 1991-04-23 | Basf Aktiengesellschaft | Fuels for gasoline engines |
US6017370A (en) * | 1998-09-25 | 2000-01-25 | The Lubrizol Corporation | Fumarate copolymers and acylated alkanolamines as low temperature flow improvers |
US6086645A (en) * | 1996-05-17 | 2000-07-11 | Ethyl Petroleum Additives, Ltd | Fuel additives and compositions |
US6554876B1 (en) * | 1997-04-11 | 2003-04-29 | Infineum International Ltd. | Oil compositions |
WO2012076896A1 (en) * | 2010-12-09 | 2012-06-14 | Innospec Limited | Improvements in or relating to additives for fuels and lubricants |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3049553A1 (de) * | 1980-12-31 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | Erdoeldestillate mit verbessertem kaelteverhalten |
JPS59149988A (ja) * | 1983-02-16 | 1984-08-28 | Nippon Oil & Fats Co Ltd | 燃料油用流動性向上剤 |
GB2214517A (en) * | 1988-01-27 | 1989-09-06 | Exxon Chemical Patents Inc | Carrier for additives for liquid hydrocarbons |
CA2042855A1 (en) * | 1990-06-28 | 1991-12-29 | Nicholas Feldman | Composition for improving cold flow properties of middle distillates |
GB2446801B (en) | 2007-02-23 | 2011-06-29 | Schlumberger Holdings | Wellbore treatment fluid |
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- 1969-09-15 US US858180A patent/US3658493A/en not_active Expired - Lifetime
-
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- 1970-08-19 CA CA091116A patent/CA920365A/en not_active Expired
- 1970-08-21 GB GB4041870A patent/GB1318241A/en not_active Expired
- 1970-08-28 DE DE2042683A patent/DE2042683C3/de not_active Expired
- 1970-09-11 JP JP45079429A patent/JPS5036246B1/ja active Pending
- 1970-09-14 NO NO03497/70A patent/NO127198B/no unknown
- 1970-09-14 FR FR7033214A patent/FR2061372A5/fr not_active Expired
- 1970-09-14 DK DK471770AA patent/DK127790B/da unknown
- 1970-09-14 SE SE7012469A patent/SE372557B/xx unknown
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Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3946053A (en) * | 1970-09-30 | 1976-03-23 | Cities Service Oil Company | Hydrocarbyl hydrogen phosphate salts of amino-amides |
DE2604396A1 (de) * | 1975-02-13 | 1976-08-26 | Exxon Research Engineering Co | Brennstoffoel |
US3982909A (en) * | 1975-02-13 | 1976-09-28 | Exxon Research And Engineering Company | Nitrogen-containing cold flow improvers for middle distillates |
US4211534A (en) * | 1978-05-25 | 1980-07-08 | Exxon Research & Engineering Co. | Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils |
FR2426730A1 (fr) * | 1978-05-25 | 1979-12-21 | Exxon Research Engineering Co | Compositions d'additifs pour ameliorer l'ecoulement et la filtrabilite des fuel-oils distilles |
US4261703A (en) * | 1978-05-25 | 1981-04-14 | Exxon Research & Engineering Co. | Additive combinations and fuels containing them |
EP0030099A1 (en) * | 1979-11-23 | 1981-06-10 | Exxon Research And Engineering Company | Additive combinations and fuels containing them |
US4375973A (en) * | 1979-11-23 | 1983-03-08 | Exxon Research & Engineering Co. | Additive combinations and fuels containing them |
DE3137233A1 (de) * | 1980-09-19 | 1982-06-09 | Elf France, 75007 Paris | Zusammensetzungen zur verbesserung der kaltfiltirerbarkeit von mittleren erdoelschnitten |
US4402708A (en) * | 1980-11-18 | 1983-09-06 | Exxon Research & Engineering Co. | Dialkyl amine derivatives of phthalic acid |
US4556499A (en) * | 1981-03-28 | 1985-12-03 | Hoechst Aktiengesellschaft | Process for improving the flow properties of mineral oils |
US4464182A (en) * | 1981-03-31 | 1984-08-07 | Exxon Research & Engineering Co. | Glycol ester flow improver additive for distillate fuels |
US4491455A (en) * | 1982-02-10 | 1985-01-01 | Nippon Oil And Fats Co., Ltd. | Method for improving cold flow of fuel oils |
US4623684A (en) | 1982-08-09 | 1986-11-18 | The Lubrizol Corporation | Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
US4564460A (en) * | 1982-08-09 | 1986-01-14 | The Lubrizol Corporation | Hydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
US4575526A (en) * | 1982-08-09 | 1986-03-11 | The Lubrizol Corporation | Hydrocarbyl substituted carboxylic acylaging agent derivative containing combinations, and fuels containing same |
US4613342A (en) * | 1982-08-09 | 1986-09-23 | The Lubrizol Corporation | Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
US4537602A (en) * | 1982-09-16 | 1985-08-27 | Exxon Research & Engineering Co. | Additive concentrates for distillate fuels |
US5009670A (en) * | 1988-05-19 | 1991-04-23 | Basf Aktiengesellschaft | Fuels for gasoline engines |
US6086645A (en) * | 1996-05-17 | 2000-07-11 | Ethyl Petroleum Additives, Ltd | Fuel additives and compositions |
US6554876B1 (en) * | 1997-04-11 | 2003-04-29 | Infineum International Ltd. | Oil compositions |
US6017370A (en) * | 1998-09-25 | 2000-01-25 | The Lubrizol Corporation | Fumarate copolymers and acylated alkanolamines as low temperature flow improvers |
EP0989176A1 (en) * | 1998-09-25 | 2000-03-29 | The Lubrizol Corporation | Low temperature flow improvers |
WO2012076896A1 (en) * | 2010-12-09 | 2012-06-14 | Innospec Limited | Improvements in or relating to additives for fuels and lubricants |
Also Published As
Publication number | Publication date |
---|---|
DE2042683A1 (de) | 1971-03-25 |
DE2042683C3 (de) | 1978-11-02 |
DK127790B (da) | 1974-01-07 |
CA920365A (en) | 1973-02-06 |
NO127198B (ru) | 1973-05-21 |
SE372557B (ru) | 1974-12-23 |
FR2061372A5 (ru) | 1971-06-18 |
DE2042683B2 (de) | 1978-03-02 |
JPS5036246B1 (ru) | 1975-11-22 |
GB1318241A (en) | 1973-05-23 |
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