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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1658—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing conjugated dienes
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/02—Well-defined aliphatic compounds
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/02—Well-defined aliphatic compounds
  • C10M2203/022—Well-defined aliphatic compounds saturated
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/02—Well-defined aliphatic compounds
  • C10M2203/024—Well-defined aliphatic compounds unsaturated
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/04—Well-defined cycloaliphatic compounds
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes

Definitions

• the invention provides a hydro carbon liquid containing a small proportion of a hydrogenated butadiene-styrene random or block copolymer which imparts thereto an improved pour point and/ or increased resistance to thermal degradation.
• the invention provides a process for the modification of the properties of a liquid hydrocarbon by incorporating therein a small amount of a hydrogenated butadiene-styrene random or block copolymer.
• the copolymer is first incorporated into an oil whereupon the oil containing the additive is incorporated into the liquid hydrocarbon or distillate.
• hydrocarbon liquids should be pourable and/or pumpable at low temperatures.
• a number of additives have been proposed for use in these hydrocarbon liquids to achieve this flowability.
• pour point depressants which have great success in reducing the pour point of lubricating oils have frequently been ineffective in reducing pour point of distillate fuels.
• some depressants which have success with some distillate fuels fail completely when used with distillates from another source.
• the commercial pour point requirements must be met by other means, such as by blending in large amounts of petroleum fractions which may have lower pour points but which are more expensive. For example, kerosene is frequently used to reduce the pour point of furnace oils and diesel fuels.
• An object of this invention is to provide an improved hydrocarbon product. Another object of the invention is to provide an improved hydrocarbon distillate product. A further object of the invention is to provide an improved petroleum distillate product. A still further object of the invention to provide an improved hydrocarbon distillate fuel product. Yet another object of the invention is to provide an improved petroleum distillate fuel product. A further object of the invention is to provide a liquid hydrocarbon product having improved pour point. A still further object of the invention is to provide a liquid hydrocarbon product having increased resistance to thermal degradation. A still further object of the invention is to provide a product containing at least a liquid hydrocarbon and an additive yielding stability to said hydrocarbon on storage.
• an improved product containing a liquid hydrocarbon and a small amount of a hydrogenated butadiene-styrene copolymer as herein described.
• the use of the additives according to the invention can eliminate a portion or all of the pour point depressants formerly used.
• large amounts of petroleum fractions for example kerosene, can be diverted for other more important uses.
• compositions having a higher heating value and higher cetane number yields compositions having a higher heating value and higher cetane number.
• distillates or fuels treated with the additives of the invention are found more stable to degradation as on storage. Thus, on aging, such fuels develop less color and form less insoluble materials.
• the additives of the invention are usually employed in an amount in the approximate range 0.005 to 0.5 weight percent of the distillate or fuel or other hydrocarbon liquid.
• One skilled in the art in possession of this disclosure having studied the same can routinely determine the optimum proportion of copolymer for his purposes.
• the hydrogenated copolymers or additives of the present invention have a molecular weight in the approximate range of from about 2000 to about 200,000, a now preferred range being from about 5000 to about 100,000 and a now still more preferred range being from about 25,000 to about 50,000,
• the copolymers can be one containing from about 2 to about 98 parts by weight of styrene per hundred parts by weight of monomers.
• the broad range of the butadiene-styrene ratio in the copolymer can extend from about 98:2 to about 2:98, but now from about 60:40 to about 90:10 is preferred with particularly satisfying results being obtained with a copolymer having a :25 ratio.
• the hydrogenated copolymer molecular weight referred to throughout this application refers to number-average molecular weight.
• the number-average molecular weight of a specific butadiene-styrene copolymer is determined by methods which are conventional in the art. For example, a particularly convenient method for determining the molecular weight of copolymers in the 15,000 to 200,000 range is by the membrane osmometer. Such a procedure is described in a paper by R. E. Steele et al. at the Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy in March 1963. For copolymers in the 5,000 to 15,000 range, ebullioscopic methods are appropriate, such as the technique described by R. L. Arnett et al.
• the hydrogenated copolymers of the present invention can be prepared by any of the conventional techniques known in the art.
• the hutadiene-styrene mixture of monomers can be polymerized using butyl lithium as the catalyst.
• the hydrogenation can be carried out over a nickel octoate-triethylaluminum catalyst system.
• the hydrogenated butadiene-styrene copolymers of the present invention are polymers which have been sufiiciently hydrogenated to remove substantially all of the olefinic unsaturation leaving only the aromatic unsaturation.
• the above-described copolymers can be dispersed in a carrier such as a low viscosity lubricating oil stock, a hydrocarbon solvent such as cyclohexane, or any inert diluent in which the additive is sufiiciently soluble.
• a carrier such as a low viscosity lubricating oil stock, a hydrocarbon solvent such as cyclohexane, or any inert diluent in which the additive is sufiiciently soluble.
• the pour point depressant additive of the present invention is generally added to the petroleum distillate fuels in amounts which range from about .005 to about 0.5 weight percent (exclusive of carrier) based on the weight of the fuel. Conventional techniques for dispersing the additives in the distillate fuels can be used.
• the distillate fuels to which the present invention is applicable include such petroleum fractions or catalytically modified fractions or mixtures thereof which boil at temperatures in the range of from about 70 to about 750 F.
• These fuels include gasolines, such as aviation, marine, and automotive gasolines, jet fuels, diesel fuels, heating oils, and the like.
• the treated petroleum distillate fuels can also contain other commonly used ingredients such as anti-oxidants, colorants, combustion improvers, anti-knock compounds, and the like.
• butadiene Styrene Hydrogenated Random Copolymer having indicated molecular weight.
• Example ll Another series of tests were carried out to demonstrate still another advantage of the additives of the present invention. The ability of the additives to improve the heat stability of a number of fuel blends was shown. The same two hydrogenated random copolymers, described in Example I, were also used in these tests in concentrations of 0.18 weight percent of active ingredient based on the weight of the fuel.
• the fuels were heated to 300 F. for a period of 90 minutes. After the heating period the fuels were subjected to a color determination, the higher numbered color rating indicating the greater amount of color present.
• Example I The data in the table above show that, without exception, the polymeric additives of the present invention stabilized both the color and the insolubles formation of all the fuel blends.
• Example III The distillate fuel blends described in Example 11 were tested for response in regard to pour point depression using various levels of the invention additive.
• the additive was a hydrogenated, 25,000 molecular weight random butadiene: styrene copolymer in which the ratio f the butadiene to styrene was 75:25. The results of this series of tests are shown in the table below.
• Example V A number of other tests were carried out to demonstrate the variations possible in the invention additive. Hydrogenated random copolymers of butadiene and styrene having different molecular weights and different proportions of butadiene and styrene were tested. The tests for pour point depression were similar to those in preceding examples using the previously described distillate fuel blends.
• Example VII Several tests were carried out to show that, to be effec tive, the additives of the present invention must be copolymers and that they must be hydrogenated.
• distillate fuel stock B was treated with 0.1.8 weight percent, based on the weight of the fuel stock, of a 35,000 molecular weight hydrogenated polybutadiene homopolymer.
• the pour point of the fuel stock treated in this manner was found to be 0 F.,.com-
• Example VIII Another series of tests was carried out to show that a hydrogenated, simple block copolymer of butadiene and styrene is also effective in depressing the pour point of a distillate fuel.
• a distillate fuel stock was treated, at an 0.18 weight percent level, with several variations of such a hydrogenated, simple block copolymer.
• the results of the pour point determination on these treated fuels are 1 A hydrogenated, simple block copolymer of butadiene-styrene having the indicated molecular weight and butadiene-styrene incorporation.
• Example 1X The following is a description of a typical preparation of a hydrogenated 25,000 molecular weight random copolymer having a butadiene:styrene ratio of 75:25.
• a dry 26-ounce bottle was charged with 400 g. cyclohexane, purged with nitrogen, capped, and then charged, by syringe, with 37.5 g. butadiene, 12.5 g. styrene, 0.75 g. tetrahydrofuran, and 2.2 millimoles of secondary butyllithium.
• the bottle was placed, for 2 hours, in a constant temperature bath maintained at 122 F.
• the polymer-containing solution was then drawn into a hydrogenation pressure vessel where it was contacted for two hours at about 350 F. with 400 p.s.i.g. hydrogen pressure in the presence of a hydrogenation catalyst comprising 12 ml. of nickel octoate solution (containing 0.0061 g. Ni/ml.) and 5 ml. of triethylaluminum.
• the cyclohexane diluent was Throughout the examples the additives were added to the fuels in a 10 stock neutral oil in about a 10 percent by weight concentration. All of the loading levels shown in the examples, however, are in weight percent of the active ingredient, that is, the polymer only.
• distillates which are applicable for use in the present invention are the following Distillate: Boiling range (initial-final) F. Gasolines 70-420 Jet fuels -500 Diesel fuels 350-625 Heating and stove oils 350-570 High boiling distillate fuels 400-750
• Reasonable variation and modification are possible in the scope of the foregoing disclosure and the appended claims to the invention, the essence of which is that a hydrogenated styrene-butadiene copolymer has been incorporated into a liquid hydrocarbon obtaining improved properties and advantages as set forth and described.
• composition suitable for use as a fuel said composition containing a liquid hydrocarbon distillate and a small amount effective to act as a pour point depressant and/or a thermal degradation inhibitor of a hydrogenated styrene-butadiene copolymer additive having a molecular weight in the approximate range 2,000 to 200,000.
• a product according to claim 1 wherein the additive is selected from random and block copolymers of butadiene and styrene and is present in an amount in the approximate range 0.005 to 0.5 weight percent of the liquid hydrocarbon distillate.
• a product according to claim 2 wherein the copolymer has a molecular weight in the approximate range 2000 to 200,000.
• a product according to claim 2 wherein the copolymer has a molecular Weight in the approximate range 5000 to 100,000.
• a product according to claim 2 wherein the copolymer has a molecular weight in the approximate range 25,000 to 50,000.
• distillate is a petroleum distillate and is at least one 'of a gasoline, a jet fuel, a diesel fuel and a heating oil.
• composition according to claim 1 wherein said liquid hydrocarbon distillate is selected from the following:
• jet fuels which boil in the range 120-500 F.;

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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)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Telephone Set Structure (AREA)

Priority Applications (13)

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Publications (1)

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Cited By (19)

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Citations (6)

• 0
  • NL NL133183D patent/NL133183C/xx active
• 1966
  • 1966-11-21 US US595614A patent/US3419365A/en not_active Expired - Lifetime
• 1967
  • 1967-10-06 GB GB45836/67A patent/GB1205594A/en not_active Expired
  • 1967-10-20 FI FI672830A patent/FI49316C/fi active
  • 1967-10-24 ES ES345724A patent/ES345724A1/es not_active Expired
  • 1967-10-25 NO NO170277A patent/NO120297B/no unknown
  • 1967-11-03 DK DK549567AA patent/DK129094B/da unknown
  • 1967-11-13 SE SE15517/67A patent/SE321598B/xx unknown
  • 1967-11-17 DE DE19671645780 patent/DE1645780A1/de not_active Withdrawn
  • 1967-11-20 BE BE706751D patent/BE706751A/xx unknown
  • 1967-11-20 AT AT1043967A patent/AT276603B/de active
  • 1967-11-20 NL NL6715720A patent/NL6715720A/xx unknown

Patent Citations (6)

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