US3131168A - Process for the manufacture of pour depressants for middle distillate fuels - Google Patents

Process for the manufacture of pour depressants for middle distillate fuels Download PDF

Info

Publication number
US3131168A
US3131168A US593A US59360A US3131168A US 3131168 A US3131168 A US 3131168A US 593 A US593 A US 593A US 59360 A US59360 A US 59360A US 3131168 A US3131168 A US 3131168A
Authority
US
United States
Prior art keywords
vinyl acetate
weight
reactor
ethylene
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US593A
Inventor
Ilncykyj Stephan
John L Tiedje
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL259743D priority Critical patent/NL259743A/xx
Priority to BE598930D priority patent/BE598930A/xx
Priority to NL130129D priority patent/NL130129C/xx
Priority to US593A priority patent/US3131168A/en
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to GB39/61A priority patent/GB915890A/en
Priority to FR848812A priority patent/FR1286696A/en
Priority claimed from US164248A external-priority patent/US3254063A/en
Priority to GB47962/62A priority patent/GB992817A/en
Application granted granted Critical
Publication of US3131168A publication Critical patent/US3131168A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • C10L1/1955—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
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2362—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing nitrile groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B47/00—Methods of operating engines involving adding non-fuel substances or anti-knock agents to combustion air, fuel, or fuel-air mixtures of engines

Definitions

  • the pour depressant of the present invention comprises copolymers of ethylene with up to about 50% by weight of an olefinically unsaturated aliphatic monomer containing from about 3 to 5 carbon atoms per molecule.
  • the copolymers of a particular average molecular weight are obtained by controlling the conditions of reaction.
  • the preferred copolymer of the present invention is a particular copolymer of ethylene and vinyl acetate and is particularly directed toward the method of manufacture wherein reagents are continuously added.
  • Aviation turbo-jet fuels in which the polymers may be used normally boil between about 250 and about 550 F. and are used in both military and civilian aircraft. Such fuels are more fully defined by US. Military Specifications MIL-F-5 624C, MlL-F255 54A, MlI.-F-25558A, and amendments thereto.
  • Kerosines and heating oils will normally have boiling ranges between about 300 and about 750 F. and are more fully described in ASTM Specification D-396 4ST and supplements thereto, where they are referred to as No. 1 and No. 2 fuel oils.
  • Diesel fuels in which the polymersmay be employed are described in detail in ASTM Specification D-975-53T and later versions of the same specification.
  • the process of the present invention produces copoly- 3,131,168 Patented Apr. 28, 1964 ice mers of ethylene and up to about 50% by weight of an olefinically unsaturated aliphatic monomer containing from about 3 to 5 carbonatoms per molecule.
  • these compounds may comprise vinyl acetate, vinyl propionate, methyl methacrylate, allyl ethyl ether, divinyl ether, acrylontrile, vinylacetonitrile and the like.
  • the preferred copolymers comprise ethylene-vinyl acetate copolymer. It is preferred that the parts by weight of ethylene in the copolymer be in the range from about 60 to 99% as compared to parts by weight of vinyl acetate in the range from about 40 to about 1%.
  • a very desirable polyethylene vinyl acetate copolymer contains about 15 to 28% by weight of vinyl acetate, as for example, about 20 parts by weight of vinyl acetate.
  • the molecular weights of the ethylene-vinyl acetate copolymer are critical and should be in the range from about 1,000 to 3,000, preferably, in the range from about 1,500 to 2,200.
  • the molecular weights are determined by K. Rasts method (Ber. 55, 1051, 3727 (1922)).
  • the ethylene-vinyl acetate copolymer as described above is used in a concentration in the range from about .001 to 0.2% by weight, preferably, in a concentration in the range from about .005 to .l% by weight.
  • the polymerization process is conducted in a solvent as, for example, toluene or hexane. It is preferred, however, to use a benzene solvent.
  • the initiator comprises any peroxy compound, preferably, di-tertiary-butyl-perordde.
  • the temperature of the polymerization reaction is in the range from about 280 to 340 F. A very desirable temperature is about 300 F.
  • the pressure is in the range from about 700 to 2,000 pounds, preferably, 800 or 900 pounds.
  • the autoclave or similar equipment containing the solvent, initiator and vinyl acetate is purged with nitrogen, then with ethylene before charging with a sulficient amount of ethylene to yield the desired pressure when heated to the reaction temperature.
  • the reagents are continuously added. A number of operations were carried out in order to establish the optimum conditions for the manufacture of the pour depressant of the present invention.
  • the manufacture of the copolymer of the present invention is carried out at a temperature in the range from about 280 to 340 F., prefenably at about 300 F.
  • the pressure is in the range from about 700 to Pilot Copolymerization of Ethylene and Vinyl Acetate [One gallon reactor, continuous addition of vinyl acetate and peroxide, 900 p.s.i.g., 300 F.]
  • Reactor 20 is then purged ethylene which is introduced by means of line 12 and pumplfl. Gases are removed from reactor 20 by means of line 11 The reactor is maintained at a positive pressure in the range from about 50 to pounds absolute.
  • Approximately 220 parts by Weight of benzene is introduced into reactor :20 from benzene storage 1 by means of dine 6 and pump 5. .Reactor 20 is then raised to a temperature of 300 F. by means of heating element 14 wherein a heating fluid or equivalent is introduced by means of line '15 [and withdrawn by means of line 16. Reactor 20 is held at 300 F. during the course of the reaction by the removal of heat or by the addition of heat thereto. Ethylene is introduced by means of line 12 so as to raise the pressure of the reactor to about 900 pounds.
  • the addition of vinyl acetate and of di-tertiary-butylperoxide is started concurrently.
  • the vinyl acetate is withdrawn from storage zone 3 and introduced into the reactor by means of line and pump 9.
  • Approximately 55 parts by weight of vinyl acetate is added over a two hour period.
  • the peroxide is introduced by passing benzene into storage zone 2 by means of line 4 and then introducing the solution into the reactor '20 by means of line 8 and pump 7.
  • Approximately 5.5 parts by weight of peroxide are combined with 16.5 parts by Weight of benzene.
  • the resulting 22 parts by weight of 25% peroxide solution in benzene is added to reactor 20 over a three hour period.
  • the reactor is held for an additional one-half hour at a temperature of about 300
  • the ethylene is added continuousiy so as to maintain the pressure at about 900 pounds. in operation, approximately 934 parts by weight or vinyl acetate are used in conjunction with from about 2,800 to 3,800 parts by weight of ethylene.
  • the reactor is allowed to cool to about 160 F. and the reaction product is then withdrawn by means of line 17 and passed into separation zone 18. Excess ethylene is removed overhead from separation zone 13 by means of line 19.
  • the polymer product comprising the copolymer in a benzene solution may be withdrawn by means of line 22 and further handled as desired. Under certain instances, it may be desirable to separate at least a portion of the benzene from the copolymer. Under these conditions, the henzene copolymer product is passed to separation zone 30 by means of line 21. Benzene is removed overhead by means of line 24, while a copolymer product is with drawn by means of line 23.
  • the quantity mentioned above may be somewhat varied.
  • the amount of benzene utilized may vary from about 180 to 300 parts by weight, and the amount of ditertiary-butyl-peroxide may vary from about 3 to 8 parts by weight.
  • the amount of ethylene utilized varies from about 2,800 to 3,800 parts by weight, or approximately 938 parts by weight of vinyl acetate.
  • T 13 time of reaction also may be varied from about 2 to 4 hours, depending upon other operating variables.
  • a pour depressant consisting essentially of a copolymer of ethylene and vinyl acetate, which copolymer has a molecular weight in the range from about 1500 to 2200 as determined by Rasts method, and is characterized by containing from about 15 to 28% by weight of vinyl acetate which comprises purging a reaction zone with nitrogen and thereafter introducing about 220 parts by weight of benzene into a reaction zone, heating the benzene to a temperature of about 300 F., thereafter pressuring said reaction Zone with ethylene to about 900 pounds, thereafter continuously adding about parts by Weight of vinyl acetate over a reaction time period of about two hours and also continuously adding over a reaction time period of about three hours about 22 parts by weight of a benzene solution containing about 25% by weight of di-tertiary-butylperoxide while maintaining said reaction zone at the conditions specified to produce said copolymer, whereby about 310 parts by weight to 142 parts by weight of ethylene will react with said 55 parts by weight of vinyl

Landscapes

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

Description

Aprll 28, 1964 s. ILNCYKYJ ETAL 3,131,158
PROCESS FOR THE MANUFACTURE OF FOUR DEPRESSANTS FOR MIDDLE DISTILLATE FUELS Filed Jan. 5, 1960 Stephan \lnycxyj Joh Inventors y [L0 Patent Attorney United States latent O f 3,131,168 PROCESS FOR TE MANUFACTURE OF FOUR DEPRESSANTS FOR MID DLE DISTILLATE FUELS Stephan Ilneykyj and Eehn L. Tiedie, Sarnia, Ontario, Canada, assignors to Esso Research and Engineering Company, a corporation of Delaware Filed Jan. 5, 1960, Ser. No. 593 1 Claim. (Cl. 260-873) The present invention is concerned with the manufacture of improved pour depressants, particularly, for use with middle distillates. The pour depressant of the present invention comprises copolymers of ethylene with up to about 50% by weight of an olefinically unsaturated aliphatic monomer containing from about 3 to 5 carbon atoms per molecule. The copolymers of a particular average molecular weight are obtained by controlling the conditions of reaction. The preferred copolymer of the present invention is a particular copolymer of ethylene and vinyl acetate and is particularly directed toward the method of manufacture wherein reagents are continuously added.
With the increase in the use of hydrocarbon fuels of all kinds, a serious problem has arisen in areas frequently subjected to low temperatures in the cold test characteristics of fuels. Particularly, serious problems have been encountered with heating oils and diesel and jet fuels that have too high a pour point, resulting either in distributional or operating difficulties or both. For example, the distribution of heating oils by pumping or syphoning is rendered diificult or impossible at temperatures around or below the pour point of the oil. Furthermore, the flow of the oil at such temperatures through the filters cannot be maintained, leading to the failure of the equipment to operate.
Also the low temperature properties of petroleum distillate fuels boiling in the range between about 250 and about 750 F. have attracted increasing attention in recent years because of the growth of market for such fuels in subarctic areas and because of the development of turbojet aircraft capable of operating at altitudes where temperatures of -50 F. or lower may be encountered.
It is, therefore, an object of the present invention to set forth an improved process for the manufacture of very effective pour depressants for middle distillates and lighter oils. In general, these oils boil in the range from about 250 to 750 F.
It is a still further object of the present invention to provide heating oils, diesel fuel oils, kerosines and jet fuels having low pour points. Aviation turbo-jet fuels in which the polymers may be used normally boil between about 250 and about 550 F. and are used in both military and civilian aircraft. Such fuels are more fully defined by US. Military Specifications MIL-F-5 624C, MlL-F255 54A, MlI.-F-25558A, and amendments thereto. Kerosines and heating oils will normally have boiling ranges between about 300 and about 750 F. and are more fully described in ASTM Specification D-396 4ST and supplements thereto, where they are referred to as No. 1 and No. 2 fuel oils. Diesel fuels in which the polymersmay be employed are described in detail in ASTM Specification D-975-53T and later versions of the same specification.
The process of the present invention produces copoly- 3,131,168 Patented Apr. 28, 1964 ice mers of ethylene and up to about 50% by weight of an olefinically unsaturated aliphatic monomer containing from about 3 to 5 carbonatoms per molecule. In general, these compounds may comprise vinyl acetate, vinyl propionate, methyl methacrylate, allyl ethyl ether, divinyl ether, acrylontrile, vinylacetonitrile and the like.
The preferred copolymers comprise ethylene-vinyl acetate copolymer. It is preferred that the parts by weight of ethylene in the copolymer be in the range from about 60 to 99% as compared to parts by weight of vinyl acetate in the range from about 40 to about 1%. A very desirable polyethylene vinyl acetate copolymer contains about 15 to 28% by weight of vinyl acetate, as for example, about 20 parts by weight of vinyl acetate.
The molecular weights of the ethylene-vinyl acetate copolymer are critical and should be in the range from about 1,000 to 3,000, preferably, in the range from about 1,500 to 2,200. The molecular weights are determined by K. Rasts method (Ber. 55, 1051, 3727 (1922)).
The ethylene-vinyl acetate copolymer as described above is used in a concentration in the range from about .001 to 0.2% by weight, preferably, in a concentration in the range from about .005 to .l% by weight.
In accordance with the present invention, the polymerization process is conducted in a solvent as, for example, toluene or hexane. It is preferred, however, to use a benzene solvent. The initiator comprises any peroxy compound, preferably, di-tertiary-butyl-perordde. The temperature of the polymerization reaction is in the range from about 280 to 340 F. A very desirable temperature is about 300 F. The pressure is in the range from about 700 to 2,000 pounds, preferably, 800 or 900 pounds. The autoclave or similar equipment containing the solvent, initiator and vinyl acetate is purged with nitrogen, then with ethylene before charging with a sulficient amount of ethylene to yield the desired pressure when heated to the reaction temperature. During the polymerization, additional ethylene is added to maintain the pressure at the desired level. Polymerization is considered complete when the pressure drops less than 50 p.s.i.g. per hour. The product is stripped free of solvent and unreacted vinyl acetate under vacuum.
In accordance with the present invention, the reagents are continuously added. A number of operations were carried out in order to establish the optimum conditions for the manufacture of the pour depressant of the present invention.
In other operations, reactants were continuously fed to the reactor. In the first phase of this operation, vinyl acetate was charged into the reactor at the start of each run and di-tertiary-butyl-peroxide in 25% concentration in benzene was fed continuously as the copolymerization proceeded. Table I compares products obtained with the best copolymer, A, produced when all reactants were charged to the reactor at the beginning of the reaction.
The effect of reaction variables on yield and potency of pour depressant was studied in some detail. Generally it was found that the yield of copolymer increased with polymerization time, slower rate of addition of initiator, and increases in pressure. In the range studied, the highest potency pourdepressant was obtained when operating at 650 p.s.i.g. and using short polymerization times with fast addition of peroxide. When considering both yield and quality of pour depressant, the best product was obtained at 900 p.s.i.g., 300 F., 3 hours total polymerization time and 1 hour addition time of peroxide.
TABLE I Operation A B O D E F G H I Reactor 1 2 Conditions:
Vinyl acetate, ml 30 150 150 150 150 120 120 120 90 Peroxide, ml 15 15 15 15 15 15 15 Peroxide addition, hrs 0 4 1 1 1 1 1 1 1 Polymerization, hrs. 6 6 6 3 3 3 6 6 6 Pressure, p.s.i.g.. 850 900 900 3 1, 200 900 650 650 650 550 Temperature, F 300 300 300 300 300 300 300 280 300 Product:
Yield, g 100 731 615 585 530 414 434 396 352 Initiator elficiency 61. 4 51. 7 49. 2 44. 5 34. 8 36. 5 33. 3 29. 5 Vinyl acetate, wt. percent 20. 4 15. 8 20.6 18. 8 21.9 22. 8 21.0 21.9 20.9 Pour depressant, F.:
05 wt. percent 60 25 40 50 15 0.1 wt. percent 90 40 65 80 100 90 90 80 Vinyl Acetate Balance:
Polymen'zed, wt. percent 72. 9 87. 5 90.6 78. 7 83.0 84.4 81.3 77. 5 87. 4 Recovered monomer,
wt. percent 4. 9 8.2 7. 9 13.3 11.3 4. 7 7.6 Unaccounted for, wt.
percent 27. 1 7. 6 1.2 13.4 3. 7 4. 2 14.0 5.0
1 Litres. 2 One gallon. 3 Av.
Further improvements in the process were obtained when the vinyl acetate was continuously added to the reactor as the polymerization reaction proceeded. These runs are shown in 'Table II.
TABLE 11 In general, the manufacture of the copolymer of the present invention is carried out at a temperature in the range from about 280 to 340 F., prefenably at about 300 F. The pressure is in the range from about 700 to Pilot Copolymerization of Ethylene and Vinyl Acetate [One gallon reactor, continuous addition of vinyl acetate and peroxide, 900 p.s.i.g., 300 F.]
Operation A B O 1 D B E 2 F 2 G H 3 Conditions:
Benzene, ml 1,395 315 330 1, 395 345 405 1, 290 7, 740 Vinyl acetate, total 1111-. 150 150 150 150 150 150 300 1, 800 Vinyl acetate, at start, m1--- 150 30 16 150 0 0 0 0 Vinyl acetate, balance ml min 0 2.0 1. 1 0 2. 5 2. 5 5 15 Di-t-butylperoxide, tot 15 15 15 15 15 30 180 Di-t-butylperoxide, mllm' 0.25 0.25 0.25 0.25 0.25 0.125 0. 25 1.0 Polymerization time, hrs 3 3 6 3 3 3 3 3- 5 Product:
Yield, g 530 343 344 477 314 345 810 6, 700 Yield, g./g. peroxide 44. 5 28.9 28. 9 40. 0 26. 3 29. 0 v34. 0 46. 9 Vinyl acetate, Wt. percent.-- 21. 9 34. 0 33. 5 22. 7 27.6 31. 1 29. 8 23. 5 Pour depressant, F.: 4
0.05 wt. percent 60 55 45 50 35 75 80 90 0.1 wt. percent 80 70 90 90 80 90 Vinyl acetate balance:
Polymerized, wt. percent--- 83. 6 83.4 82. 4 77.4 77. 4 77. 1 86. 2 93. 9 Recovered monomer, Wt.
percent 13. 3 6. 0 8. 2 11.4 12. 4 11. 3 10. 5 Un accounted for, wt. percent 3. 7 10. 6 9. 4 11. 2 10.2 11. 6 3. 8 6. 1
1 800 p.s.i.g.
1 Inhibitor removed from vinyl acetate.
3 5 U.S. gallons reactor.
4 50/50 blend of virgin and cat. cracked gas oils, pour +20 F.
The advantages of these operations were improved quality of pour depressant and substantially reduced solvent requirement. This latter factor resulted not only in a reduction of solvent required, but also in much higher utilization of reactor volume. See Table III.
TABLE III Synthesis of Pour Depressants 50/50 blend of virgin gas oil and cat. cracked gas oil, ASTM pour +20 F.
,is first purged with nitrogen, introduced by means of line, 7'
12 and pump 13. Reactor 20 is then purged ethylene which is introduced by means of line 12 and pumplfl. Gases are removed from reactor 20 by means of line 11 The reactor is maintained at a positive pressure in the range from about 50 to pounds absolute.
Approximately 220 parts by Weight of benzene is introduced into reactor :20 from benzene storage 1 by means of dine 6 and pump 5. .Reactor 20 is then raised to a temperature of 300 F. by means of heating element 14 wherein a heating fluid or equivalent is introduced by means of line '15 [and withdrawn by means of line 16. Reactor 20 is held at 300 F. during the course of the reaction by the removal of heat or by the addition of heat thereto. Ethylene is introduced by means of line 12 so as to raise the pressure of the reactor to about 900 pounds.
The addition of vinyl acetate and of di-tertiary-butylperoxide is started concurrently. The vinyl acetate is withdrawn from storage zone 3 and introduced into the reactor by means of line and pump 9. Approximately 55 parts by weight of vinyl acetate is added over a two hour period. The peroxide is introduced by passing benzene into storage zone 2 by means of line 4 and then introducing the solution into the reactor '20 by means of line 8 and pump 7. Approximately 5.5 parts by weight of peroxide are combined with 16.5 parts by Weight of benzene. The resulting 22 parts by weight of 25% peroxide solution in benzene is added to reactor 20 over a three hour period.
After the addition of the peroxide has been completed, the reactor is held for an additional one-half hour at a temperature of about 300 The ethylene is added continuousiy so as to maintain the pressure at about 900 pounds. in operation, approximately 934 parts by weight or vinyl acetate are used in conjunction with from about 2,800 to 3,800 parts by weight of ethylene.
At the end of the reaction, the reactor is allowed to cool to about 160 F. and the reaction product is then withdrawn by means of line 17 and passed into separation zone 18. Excess ethylene is removed overhead from separation zone 13 by means of line 19. The polymer product comprising the copolymer in a benzene solution may be withdrawn by means of line 22 and further handled as desired. Under certain instances, it may be desirable to separate at least a portion of the benzene from the copolymer. Under these conditions, the henzene copolymer product is passed to separation zone 30 by means of line 21. Benzene is removed overhead by means of line 24, while a copolymer product is with drawn by means of line 23.
The quantity mentioned above may be somewhat varied. For example, based upon 55 parts by weight of vinyl acetate, the amount of benzene utilized may vary from about 180 to 300 parts by weight, and the amount of ditertiary-butyl-peroxide may vary from about 3 to 8 parts by weight. Also as mentioned, the amount of ethylene utilized varies from about 2,800 to 3,800 parts by weight, or approximately 938 parts by weight of vinyl acetate. T 13 time of reaction also may be varied from about 2 to 4 hours, depending upon other operating variables.
While the above operation has been described utilizing a single reactor, it is to be understood that a plurality of reactors may be employed in a similar manner in order to secure continuous production of the copolymer.
What is claimed is:
Process for the manufacture of a pour depressant consisting essentially of a copolymer of ethylene and vinyl acetate, which copolymer has a molecular weight in the range from about 1500 to 2200 as determined by Rasts method, and is characterized by containing from about 15 to 28% by weight of vinyl acetate which comprises purging a reaction zone with nitrogen and thereafter introducing about 220 parts by weight of benzene into a reaction zone, heating the benzene to a temperature of about 300 F., thereafter pressuring said reaction Zone with ethylene to about 900 pounds, thereafter continuously adding about parts by Weight of vinyl acetate over a reaction time period of about two hours and also continuously adding over a reaction time period of about three hours about 22 parts by weight of a benzene solution containing about 25% by weight of di-tertiary-butylperoxide while maintaining said reaction zone at the conditions specified to produce said copolymer, whereby about 310 parts by weight to 142 parts by weight of ethylene will react with said 55 parts by weight of vinyl acetate.
References Cited in the file of this patent UNITED STATES PATENTS 2,396,785 Hanford Mar. 19, 1946 2,414,311 Larson Ian. 14, 1947 2,450,451 Schmerling Oct. 5, 1948 2,551,643 Seger et a1 May 8, 1951 FOREIGN PATENTS 459,662 Canada Sept. 13, 1949
US593A 1960-01-05 1960-01-05 Process for the manufacture of pour depressants for middle distillate fuels Expired - Lifetime US3131168A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL259743D NL259743A (en) 1960-01-05
BE598930D BE598930A (en) 1960-01-05
NL130129D NL130129C (en) 1960-01-05
US593A US3131168A (en) 1960-01-05 1960-01-05 Process for the manufacture of pour depressants for middle distillate fuels
GB39/61A GB915890A (en) 1960-01-05 1961-01-02 Process for the manufacture of improved pour point depressants for middle distillates
FR848812A FR1286696A (en) 1960-01-05 1961-01-04 Process for the production of improved products lowering the freezing point of middle distillates
GB47962/62A GB992817A (en) 1960-01-05 1962-12-19 Improved process for preparation of pour depressants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US593A US3131168A (en) 1960-01-05 1960-01-05 Process for the manufacture of pour depressants for middle distillate fuels
US164248A US3254063A (en) 1962-01-04 1962-01-04 Process for preparation of pour depressants

Publications (1)

Publication Number Publication Date
US3131168A true US3131168A (en) 1964-04-28

Family

ID=26667859

Family Applications (1)

Application Number Title Priority Date Filing Date
US593A Expired - Lifetime US3131168A (en) 1960-01-05 1960-01-05 Process for the manufacture of pour depressants for middle distillate fuels

Country Status (4)

Country Link
US (1) US3131168A (en)
BE (1) BE598930A (en)
GB (2) GB915890A (en)
NL (2) NL259743A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451981A (en) * 1966-06-29 1969-06-24 Nat Distillers Chem Corp Polymerization of vinyl chloride and mixtures of vinyl acetate and ethylene using tertiary alkyl per-3-alkenoates as catalysts
US3458430A (en) * 1967-05-15 1969-07-29 Exxon Research Engineering Co Separation of hydrocarbon wax from mineral oil using dewaxing aids
DE1914756A1 (en) * 1968-04-01 1969-11-06 Exxon Research Engineering Co Process for the production of copolymers and their use in distillation units
US3627838A (en) * 1964-12-11 1971-12-14 Exxon Research Engineering Co Process for manufacturing potent pour depressants
US3693720A (en) * 1971-01-29 1972-09-26 Exxon Research Engineering Co Crude oil recovery method using a polymeric wax inhibitor
DE3308238A1 (en) * 1982-03-11 1983-10-06 Petrolite Corp., St. Louis, Mo. POLYALKYLENES CARRYING HALOGEN AND / OR ESTER GROUPS AND METHOD FOR THE PRODUCTION THEREOF
US4559155A (en) * 1982-08-09 1985-12-17 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
US4623684A (en) 1982-08-09 1986-11-18 The Lubrizol Corporation Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4020640A1 (en) * 1990-06-29 1992-01-02 Hoechst Ag TERPOLYMERISATES OF ETHYLENE, THEIR PRODUCTION AND THEIR USE AS ADDITIVES FOR MINERAL OIL DISTILLATES
DE4027140A1 (en) * 1990-08-28 1992-03-05 Basf Ag ETHYLENE / VINYL ACETATE COPOLYMERISATES WITH INCREASED RESISTANCE POINT

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2396785A (en) * 1941-03-15 1946-03-19 Du Pont Process for polymerizing olefins with other polymerizable organic compounds
US2414311A (en) * 1943-07-30 1947-01-14 Du Pont Preparation of polymers of ethylene
US2450451A (en) * 1946-05-31 1948-10-05 Universal Oil Prod Co Polymerization of ethylene
CA459662A (en) * 1949-09-13 Edward Hanford William Interpolymer of ethylene with vinyl ester and processes of making same
US2551643A (en) * 1949-01-25 1951-05-08 Socony Vacuum Oil Co Inc Synthetic lubricants from alphamonoolefins and unsaturated esters and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA459662A (en) * 1949-09-13 Edward Hanford William Interpolymer of ethylene with vinyl ester and processes of making same
US2396785A (en) * 1941-03-15 1946-03-19 Du Pont Process for polymerizing olefins with other polymerizable organic compounds
US2414311A (en) * 1943-07-30 1947-01-14 Du Pont Preparation of polymers of ethylene
US2450451A (en) * 1946-05-31 1948-10-05 Universal Oil Prod Co Polymerization of ethylene
US2551643A (en) * 1949-01-25 1951-05-08 Socony Vacuum Oil Co Inc Synthetic lubricants from alphamonoolefins and unsaturated esters and method for producing the same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627838A (en) * 1964-12-11 1971-12-14 Exxon Research Engineering Co Process for manufacturing potent pour depressants
US3451981A (en) * 1966-06-29 1969-06-24 Nat Distillers Chem Corp Polymerization of vinyl chloride and mixtures of vinyl acetate and ethylene using tertiary alkyl per-3-alkenoates as catalysts
US3458430A (en) * 1967-05-15 1969-07-29 Exxon Research Engineering Co Separation of hydrocarbon wax from mineral oil using dewaxing aids
DE1914756A1 (en) * 1968-04-01 1969-11-06 Exxon Research Engineering Co Process for the production of copolymers and their use in distillation units
US3981850A (en) * 1968-04-01 1976-09-21 Exxon Research And Engineering Company Process for preparing copolymers of ethylene and vinyl esters or mixtures with other ethylenically unsaturated monomers
US3693720A (en) * 1971-01-29 1972-09-26 Exxon Research Engineering Co Crude oil recovery method using a polymeric wax inhibitor
DE3308238A1 (en) * 1982-03-11 1983-10-06 Petrolite Corp., St. Louis, Mo. POLYALKYLENES CARRYING HALOGEN AND / OR ESTER GROUPS AND METHOD FOR THE PRODUCTION THEREOF
US4559155A (en) * 1982-08-09 1985-12-17 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
US4623684A (en) 1982-08-09 1986-11-18 The Lubrizol Corporation Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same

Also Published As

Publication number Publication date
NL130129C (en)
BE598930A (en)
GB992817A (en) 1965-05-19
GB915890A (en) 1963-01-16
NL259743A (en)

Similar Documents

Publication Publication Date Title
US3093623A (en) Process for the manufacture of improved pour depressants for middle distillates
US3627838A (en) Process for manufacturing potent pour depressants
US3131168A (en) Process for the manufacture of pour depressants for middle distillate fuels
US3048479A (en) Ethylene-vinyl ester pour depressant for middle distillates
US3159608A (en) Copolymerization of ethylene and vinyl acetate
US3981850A (en) Process for preparing copolymers of ethylene and vinyl esters or mixtures with other ethylenically unsaturated monomers
US3642459A (en) Copolymers of ethylene with unsaturated esters and oil compositions containing said copolymers
US5200484A (en) Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
US3341309A (en) Terpolymer pour point depressant and method of manufacture
US3126364A (en) Process for the manufacture of pour depressant
AU2010227355B2 (en) Low molecular weight (meth) acrylic polymers free of sulphur-containing, metallic and halogenated compounds and with a low degree of residual monomers, process for the preparation thereof and uses thereof
NO310826B1 (en) Terpolymerisates of ethylene, their process for preparation, mixtures as well as mineral oil or mineral oil distillates of the same
US3792983A (en) Ethylene and acrylate esters, their preparation and their use as wax crystal modifiers
KR102357888B1 (en) Additives for fuels and oils comprising functionalised diblock copolymers
CA1222348A (en) Ethylene-alkyne copolymers, their preparation and their use as additives to petroleum distillates
US3236612A (en) Middle distillate composition of improved pour characteristics
US3449251A (en) Wax crystal modifiers for hydrocarbon oils
US4419106A (en) Hydrocarbon oils with improved pour points
US5684108A (en) Ethylene-based copolymers and their use as flow improvers in mineral oil middle distillates
US3254063A (en) Process for preparation of pour depressants
US3260728A (en) Process for polymerizing ethylene with lauryl methacrylate and n-vinyl-2-pyrrolidone
US4547202A (en) Hydrocarbon oils with improved pour points
EP0184048B1 (en) Terpolymers of ethylene, vinyl acetate and isobutylene useful as pour point depressants in distillate oils
US3915668A (en) Crude oils and residual fuel oils containing a terpolymer of ethylene, vinyl ester, and dialkylvinyl carbinol
US3087894A (en) Oil composition having low pour point