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
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T137/00—Fluid handling
  • Y10T137/0318—Processes
  • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

• a vacuum gas oil fuel composition suitable for pipeline transportation of substantially reduced pour point comprising a wax containing vacuum gas oil base stock having incorporated therein a minor amount of high asphaltene residuum such as an Arabian Light 1,050,F. residuum and a pour depressing amount of an interpolymeric poly( n-alkylacrylate) of a molecular weight between about 3,000 and 100,000 wherein said alkyl isof at least 18 carbons and at least 70 wt. of said alkyl is between about 20 and 24 carbons inclusively, the C to C alkyl group consisting of between about 2 and 65 wt. of C alkyl, between about 18 and 65 wt. C alkyl and between about 8 and 35 wt. C alkyl.
• This invention relates to improved vacuum gas oil compositions of significantly reduced pour point and to transportation of these compositions in pipelines. More particularly, it pertains to vacuum gas oil compositions comprising a wax containing vacuum gas oil base stock. having a pour. depressing amount of an interpolymeric poly(n-alkylacrylate) and a minor amount of high asphaltene residuum incorporated therein.
• Gas oils are generally defined in the petroleum industry as hydrocarbon fractions in a crude oil ranging between the kerosene fraction and the lubricating oil fraction. However, the boundaries of the gas oil fraction can overlap into adjacent fractions within the standard definition employed.
• the vacuum gasoils are normally the heavier, that is, higher boiling portions of the gas oil fraction being recovered asits name denotes under vacuum, e.g., 0.05'0.2 atmosphere.
• pour depressors Petroleum hydrocarbon oils employed in cold climates or exposed to low temperature frequently require the use of an additive to maintain their fluidity, e.g., in pipeline transportation, or to meet pour point specifications. Additives that are effective for this are called pour depressors. The art discloses numerous classes of pour depressors. v
• Pour depressant additives are mostly high molecular weight organic compositions prepared by alkylation of benzene, naphthalene or derivatives thereof, by polymerization of low molecular weight methacrylates, and by the condensation polymerization of various types of these compounds. Many of these additives are not entirely suitable in vacuum gas oils because of their high cost, high concentration required or becausethey are relatively ineffective in reducing the pour point ofvacuumgas oil base stocks containing higher molecular weight waxes.
• pour depressants Although a wide variety of different pour depressants mentioned above are useful for incorporating in heating oils, diesel'fuels and many other liquid hydrocarbon oils, they havebeen found, in general, to be relatively ineffective in decreasing the pour point of vacuum gas oil base stocks containing the higher molecular weight waxes. The poor performance of these additives may result from the structural and/or molecular weight difference of waxes occurring in the various oil fractions.
• a main object of the present-invention is to improve the pour point characteristics of Wax containing vacuum gas oils without utilizing elaborate and expensive solvent extraction or centrifugal dewaxing procedures.
• Another object of this invention is to provide improved vacuum gas oil compositions prepared by incorporating therein a pour depressing amount of an oil soluble .interpolymeric poly(n-alkylacrylate) and a vacuum residuum of high asphaltene contentin a wax containing vacuum gas'oil.
• Still another object'of the invention isto improve the wax containing vacuum gas oil base stocks so they may be handled, e.g., in pipeline transportation with greater easeand flexibility in climates where ambient temperatures are neartheir pour points.
• a vacuum gas oil fuel composition of reduced pour point comprising a vacuum gas oilhaving a wax content of between about 0.5 and 20 wt. and containing the pour reducing combination of between about 1 and 20 wt. of a high asphaltene containing petroleum residuum and between about 0.002 and 3 wt. of a pour depressing quantity of an oil soluble poly(nalkylacrylate) of a molecular weight between about 3,000 and 100,000 wherein said alkyl is of at least 18 carbons and at least wt. of said alkyl is about 20 to 24 carbons, the C to C n-alkyl group consisting of between about 2 and 65 wt. C alkyl, between about 18 and 65 wt. C alkyl and between about 8 and 35 wt. C alkyl.
• this invention relates to a process for the pipeline transporation of the above mentioned fuel oil compositions.
• the waxy type vacuum gas oil base stocks contemplated herein have a wax content between about 0.5 and 20 wt. a pour point betweenabout 60 and lO0F.-, an atmospheric boiling point between about 450 and l,050F., an API gravity between about 20 and 35 and are normally derived from the distillation of crude oils such as Arabian Light crude oils at vacuum pressures ranging between about 0.05 to 0.2 atmospheres.
• Typical vacuum gas oils which may be employed are Desulfurized Arabian Light Vacuum Gas Oil (DS Arabian Lt.
• the pour point depressant additives useful in the practice of this invention are the gas oil soluble interpolymeric po1y(n-a1ky1acry1ate)s of a molecular weight between about 3.000 and 100.000.
• Lago interpolymers are derived from standard polymeriza- Medio (650F. or greater), a thermally cracked tion techniques such as polymerizing the alkylacrylate heavy fraction of Amna Crude (650F. or greater), 35 monomers in the presence of acrylate polymerization West Texas Sour Residuum (650F. or greater) and catalyst, e.g., azo catalyst such as azobisisobutronitrile thermal cycle fuel oil from various crude sources.
• catalyst e.g., azo catalyst such as azobisisobutronitrile thermal cycle fuel oil from various crude sources.
• the residuous stocks employed will have an asperoxide catalysts such as benzoyl peroxide and lauroyl phaltene content of about 4 to about '15 wt. and a peroxide, utili'zingcatalyst quantities of between about carbon residue of about 5 to 25 wt. Gravity of the 0.1 and 5 wt.
• asperoxide catalysts such as benzoyl peroxide and lauroyl phaltene content of about 4 to about '15 wt. and a peroxide, utili'zingcatalyst quantities of between about carbon residue of about 5 to 25 wt. Gravity of the 0.1 and 5 wt.
• Polymerization is normally conducted residuous stocks will range from about 5 to about 20 at a temperature between about and 150C., prefer- APl (F Although the amount of residuum 1n the ably at -l00C.,' utilizing a nitrogen blanket to prefuel oilcompositions of this invention can be varied vent oxidation-of the catalyst.
• the maximum amount which can be normally a periodic sample is taken for refractive index utilized is about 20 wt. and preferably will be from 45 (R1) determination.
• the polymerization reaction is continued until the refractive index remains steady.
• the reaction time is normally between about 1 and 10 hours.
• n-alkylacrylate monomers from which the interpolymeric poly(n-alkylacrylate) products are prepared are made by standard esterification techniques through the reaction of acrylic acid with n-alkanol mixtures wherein the reactive n-alkanols in said mixture have at Tests on Residue Stocks nsoluble. wt.
• Alfols are impure mixtures of n-alkanols of various chain lengths, the remainder consisting of hydrocarbons, ketones and hindered unreactive alcohols. Typical analysis of two suitable examples of the Alfol alcohols are as follows:
• a standard means of acrylate monomer precursor preparation is reacting (esterifying) the alcohol mixture with acrylic acid in the presence of an esteritication catalyst such as p-toluenesulfonic acid and a polymerization inhibitor, e.g., hydroquinone desirably in the presence of an azeotroping agentfor water byproduct removal such as benzene.
• the esterification is conducted, for example. at a temperature between about 190 and 200F. and is continued until the amount of water by-product is removed as overhead indicating that the esterification is essentially complete.
• the residuum component can be mixed with the base vacuum gas oil or gas oils and the polyacrylate can be admixed as a solution in toluene, xylene, light lube oil or in the vacuum gas oil itself.
• One preferred solvent to facilitate introduction of the polyacrylate pour depressor into the vacuum gas oil base stock is a solvent such as a light lubricating oil of a kinematic viscosity of between about 2 and 4 cs. at 100F. to form between about and 50 wt. polyacrylate lube oil concentrate.
• the residuum and gas oil components are heated to a temperature of about 175 to 300F., preferably at 175 to 250F. prior to the addition of the polyacrylate following which addition the resulting mixture is heated at a temperature of about 175 to 300F., preferably 175 to 250F., for about 0.2 to 1.5 hours or more to insure complete solution of the interpolymeric blend.
• the polyacrylate pour depressor be introduced at a temperature above the solution point of the wax component. 1f the polyacrylate is mixed with a vacuum gas oil at a temperature substantially below the solution point of a substantial portion of the wax component, there is little or no pour depressing effect afforded by the polyacrylate-- residuum combination.
• the improved process of this invention for the pipeline transportation of viscous fuel oils comprises introducing into the pipeline a fuel oil composition comprising a major amount of vacuum gas oil boiling between 450 and 1,050F. and a minor amount (i.e. not over 20 percent by weight and preferably about 1 to about 15 wt. based on the weight of the composition) of a high asphaltene residuum and an effective pour depressant amount of a poly(n-alkylacrylate) as heretofore described.
• EXAMPLE I This example describes two species of the po1y(nalkylacrylate), Polyacrylate A and B, contemplated herein and their method of preparation.
• Blends D, F and H are representative of the compositions of the invention and Blends A, C, E and G are comparative blends.
• Table 4 when only vacuum residuum is employed as the pour depressing ingredient even in amount of 10 wt. essentially no pour depression takes place.
• the polyacrylate is'employed as the sole pour depressor at 0.1 wt. amount the pour depression is about 15F.
• the average pour depression is about F.
• Fuel oils of the type presented in Table 4 normally carry an ASTM pour requirement of +60F. maximum.
• a vacuum gas oil fuel oil composition comprising a major amount of vacuum gas oil boiling between about 450 and 1,050F. and having a wax content between about 0.5 and 20 wt. containing 1). between about 1 and 20 wt. of an asphaltene petroleum residuum having an asphaltene content of between about 4 and 15 wt. and an API Gravity of between about and 20 and a carbon residue of between about 5 and 25 wt. and 2). between about 0.002 and 3 wt. of an interpolymeric poly(n-alkylacrylate) of amolecular weight between about 3,000 and 100,000 wherein said n-alkyl is at least 18 carbons and where at least 70 wt.
• n-alkyl is of 20 to 24 carbons consisting of between about 2 and 65 wt. C alkyl, between about 18 and 65 wt. C alkyl, and between about 8 and 35 wt. C alkyl, said p oly(n-alkylacrylate) incorporated in said base stock at a temperature above the solution point of said wax.
• the improvement which comprises introducing into the said pipeline a fuel composition comprising a major amount of vacuum gas oil boiling between about 450 and 1,050F. and having a wax content between about 0.5 and 20 wt. containing 1). between about l and 20 wt. of an asphaltene petroleum residuum having an asphaltene content of between about 4 and wt.

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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)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Priority Applications (8)

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Cited By (9)

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Citations (6)

• 1972
  • 1972-11-08 US US30467672 patent/US3853497A/en not_active Expired - Lifetime
• 1973
  • 1973-07-31 DE DE19732338727 patent/DE2338727A1/de active Pending
  • 1973-09-07 JP JP10041673A patent/JPS4978705A/ja active Pending
  • 1973-10-04 CA CA182,635A patent/CA1017144A/en not_active Expired
  • 1973-10-19 GB GB4877273A patent/GB1395264A/en not_active Expired
  • 1973-10-30 NL NL7314846A patent/NL7314846A/xx not_active Application Discontinuation
  • 1973-11-08 FR FR7339656A patent/FR2205568B2/fr not_active Expired
  • 1973-11-08 IT IT3105773A patent/IT1045919B/it active

Patent Citations (6)

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