CN1006399B - Method for improving flow properties of liquid hydrocarbons - Google Patents

Method for improving flow properties of liquid hydrocarbons

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Publication number
CN1006399B
CN1006399B CN85108892A CN85108892A CN1006399B CN 1006399 B CN1006399 B CN 1006399B CN 85108892 A CN85108892 A CN 85108892A CN 85108892 A CN85108892 A CN 85108892A CN 1006399 B CN1006399 B CN 1006399B
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ester
additive
multipolymer
fuel
poly suboxygen
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CN85108892A
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CN85108892A (en
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罗伯特·德里登·塔克
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or 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
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or 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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A polymer or copolymer of weight average molecular weight from 1000 to 200,000 prepared from an ethylenically unsaturated ester and containing from 0.1 to 50% by weight of polyoxyalkylene groups of molecular weight from 100 to 5000 is used to improve the cold flow properties of liquid hydrocarbon especially distillate fuels and has improved interaction with other additives.

Description

Method for improving flow properties of liquid hydrocarbons
The mineral oil of the content of wax has the characteristic that its flowability reduces with the temperature of oil.The reduction of this flowability is normally owing to the raising and/or the wax crystallization slabbing crystal of viscosity, and this crystal is last to form spongy, and oil is held back wherein.
Well-known already, there are various compositions when they and wax shape mineral oil, can play the effect of the crystal modifier and the pour point reducer of wax.The granularity of these composition for improved wax crystallss and shape, and the bounding force between reduction wax and the oil are so that make oil still keep mobile under lower temperature.
The existing in the literature narration of various pour point reducers, and some has obtained industrial application.For example, United States Patent (USP) 3,048,479 have introduced the pour point reducer of making fuel (especially oil fuel, diesel oil and jet fuel) with the multipolymer of ethene and C-C vinyl ester (as vinylacetate).With ethene and high alpha-olefin (as propylene) is that the hydrocarbon superpolymer pour point reducer of raw material also is well-known.United States Patent (USP) 3,961,916 introduce a kind of copolymer mixture of employing, and wherein a kind of multipolymer is made the nucleator of wax crystalls, and another kind of multipolymer is made the arrestant of crystal growth, with the size of control wax crystalls.
Equally, English Patent 1263152 proposes, and the big I of wax crystalls is controlled by adopting the lower multipolymer of a kind of side chain degree of branching.
United States Patent (USP) 1469016 also proposes, in the past can be with ethylene/vinyl acetate copolymer as additive as the multipolymer of the FUMARIC ACID TECH GRADE di n-alkanyl ester of the pour point reducer of lubricating oil and vinylacetate, to handle distillating fuel of high final boiling point, improve its low temperature flowability.According to English Patent 1469016, these polymkeric substance can be the C～C alkyl esters, particularly FUMARIC ACID TECH GRADE dodecyl ester of C～C unsaturated dicarboxylic acid. FUMARIC ACID TECH GRADE dodecyl-cetyl ester.Used material generally is the mixed ester (polymer A) of carbonatoms average out to about 12.
Our european patent application 85301047,85301048,853-1675 and 85301676 proposes, if multipolymer contains very special alkyl, as special FUMARIC ACID TECH GRADE di n-alkanyl ester/vinyl acetate copolymer, the effectiveness of this class material can improve so.For example, found that such polymkeric substance is effective especially in some fuel, in this polymkeric substance, the carbonatoms average out to 12～14 of the alkyl in the multipolymer, and its alkyl carbon atom quantity should be greater than 10 more than the shared weight percentage of 14 multipolymer, and the shared weight percentage of multipolymer that is less than 12 alkyl with carbon atom quantity is not more than 20 for good.The polymkeric substance of also finding to have long especially alkyl is effective especially to other fuel.
Our european patent application 0061895 A 2Narrated the additive that distillates fuel with poly suboxygen alkyl ester, ether, ester/ether and composition thereof work, they contain at least two C 10～C 30The polyoxyalkylene glycol base that straight chain saturated alkyl and molecular weight are 100～5000, its alkyl contains 1～4 carbon atom.
And now prove, under many circumstances, adopt the mixture of two kinds of additives can make the low temperature flowability of distillate fuel obtain particularly effectively improving.Yet mixing can cause the interactional problem of additive, and this reduces their effectiveness sometimes, thereby brings serious problem to refinery, because fuel a large amount of different sourcess, that have different additive usually will mix in order to lay in refinery.One of purpose of the present invention is exactly to address this problem.
We find now, the polyoxyalkylene glycol base can be attached in the unsaturated ester multipolymer, for hydrocarbon especially for distillate fuel provides a kind of effective cold flow improver, although they also can be used for heavy fuel, residual fuel, crude oil, and as the pour point reducer of lubricating oil.The unsaturated ester multipolymer of having introduced poly suboxygen alkyl can be the mobile improving agent of the sort of diesel oil fuel that proposes previously.We find that also when these multipolymers were used for distillate fuel, with other additive (as ethylene vinyl acetate copolymer) deleterious interactional problem taking place can alleviate.
Therefore, the present invention provides the method with the flowing property of additive improved liquid hydrocarbon fuel oil, this additive contains the polymkeric substance or the multipolymer of ethylenic unsaturated ester, the weight-average molecular weight of polymkeric substance or multipolymer is 1000～200,000, contain 0.1～50 weight percentage molecular weight and be 100～5000 poly suboxygen alkyl.
Polymkeric substance of the present invention should be used as the additive of distillate fuel, consumption preferably the distilled petroleum fuel oil weight 0.0001～5%.The present invention also comprises the distillate fuel that contains this additive.
The weight-average molecular weight that is used for polymkeric substance of the present invention is preferably 1000～100, and 000, be preferably 20,000～70,000, for example use gel permeation chromatography, and proofread and correct with the polystyrene molecular weight standard.
Unsaturated ester of the present invention can be derived and got by olefinic unsaturated monocarboxylic acid, di-carboxylic acid or polycarboxylic acid or its mixture, also can and get by unsaturated ester or its mixture and other ethylenically unsaturated monomer (as ethene, propylene or butylene) effect.The example that is applicable to the dicarboxylic ester of preparation polymkeric substance can be represented with following general formula:
Figure 85108892_IMG1
R in the formula 1And R 2Be hydrogen or C 1～C 4Alkyl (as methyl), R 3Carbonatoms average out to 8～18, this depends on the purposes of polymkeric substance.R 3Can be the mixture or our european patent application 85301047 of very large-scale alkyl (as those alkyl of the pour point reducer that is used as lubricating oil in the English Patent 1469016), 85301048, be used as the mixture of the particular monomers scope of distilled additive in 85301675 and 85301676, they can not only improve the low temperature flowability and the filterability of fuel, and can reduce its cloud point.R 4Be COOR 3, hydrogen or C 1～C 4Alkyl.When the unsaturated ester of these types when making the raw material of polymkeric substance of the present invention, can be when carboxylic esterification poly suboxygen alkyl be attached to and goes in the molecule to produce above-mentioned ester.For example, polyoxyethylene glycol can be in the proper ratio and R 3OH alcohol mixes and is used for esterification mutually, as makes the FUMARIC ACID TECH GRADE esterification.Ester in the following formula can with the ethylenically unsaturated monomer generation homopolymerization or the copolymerization of other short chain unsaturated ester and so on, vinyl ester (as vinylacetate, vinyl propionic ester, vinyl butyrate) for example, alkyl acrylate and alkyl methacrylate.
The typical multipolymer of the above-mentioned type can be made with other unsaturated ester or the olefin-copolymerization of different amounts (for example 5～70 molecular fractions) by the monoesters monomer or the dibasic acid esters monomer (for example FUMARIC ACID TECH GRADE dialkyl) of dicarboxylic acid.This other ester that comprises the short-chain alkyl ester has following general formula:
Figure 85108892_IMG2
R ' is hydrogen or C in the formula 1～C 4Alkyl, R " ' be-COOR " " or-OOCR " ", wherein R " " is the C of branching or non-branching 1～C 5Alkyl, R " ' be R " or hydrogen.The example of these short-chain esters has: methacrylic ester, acrylate, fumarate, maleate, the preferably vinyl ester of vinylacetate, vinyl propionic ester and so on.Example has more specifically: methyl methacrylate, methylvinyl acetate and isobutyl acrylate.
Preferably this analog copolymer contains the fumarate of polyoxyalkylene of 40～60 molecular fractions and the vinylacetate of 60～40 molecular fractions.
The method for preparing these ester polymers generally be make the ester monomer at varsol (as heptane, benzene, hexanaphthene or light oil) in, under 20～150 ℃ temperature, and usually with superoxide or azo-type catalyzer (as benzoyl peroxide, Diisopropyl azodicarboxylate) do promotor, (as nitrogen or carbonic acid gas, to repel oxygen) carries out polymerization under layer of inert.
It is that to make above-mentioned ethylenic unsaturated ester and chemical formula be the ethylenic unsaturated ester copolymerization of R-COOR ' that the present invention is attached to other method in the ester copolymer with poly suboxygen alkyl.R is the ethylenically unsaturated hydrocarbons base in the formula, and R is a poly suboxygen alkyl.The example of this ester has oleic acid macrogol ester or two oleic acid macrogol esters. styracin macrogol ester or two styracin macrogol esters, polyacrylic acid glycol ester etc.For example, FUMARIC ACID TECH GRADE two-cetyl ester, vinylacetate and oleic dibasic acid esters and molecular weight are that 600 polyoxyalkylene ethylene glycol can carry out copolymerization to obtain multipolymer of the present invention.
The method of poly suboxygen alkyl being introduced ester polymer also can be to make the polymkeric substance that contains free acidic group earlier, carries out esterification with poly suboxygen alkyl alcohol or polyoxyalkylene glycol then.For example, the multipolymer of MALEIC ANHYDRIDE and other unsaturated material (as vinyl ester, FUMARIC ACID TECH GRADE dialkyl, vinylbenzene or alkene) can carry out esterification with poly suboxygen alkyl alcohol or polyoxyalkylene glycol.Used poly suboxygen alkyl alcohol itself can be monohydroxy-alcohol, and the other end of its group is by etherificate or esterification, so that introduce another kind of needed group in polymer chain.As fruit product is as the additive that distillates fuel, and poly suboxygen alkyl alcohol or polyoxyalkylene glycol can mix with other alcohol, particularly straight-chain alkyl alcohol so.
The example of adoptable poly suboxygen alkyl alcohol comprises ester, ether or the ester/ether with following general formula:
R is a hydrogen in the formula ,-alkyl ,-alkyl
Figure 85108892_IMG3
,-alkyl-O- -(CH 2) n-C-, A are the poly suboxygen alkyl segment, and wherein alkylidene group contains 1～4 carbon atom, as polyoxymethylene, and polyoxyethylene or polyoxygenated trimethylene.Preferably the molecular weight of poly suboxygen alkyl segment itself is about 100～5000.
The example of suitable pure and mild ethylene glycol especially when material during as the additive that distillates fuel, has molecular weight be about 100～5000 straight chain polyoxyethylene glycol (PEG) and the polypropylene glycol (PPG) of (preferably about 200～2000).Can adopt the monoesters of these ethylene glycol, to contain 1～30(especially 2～30) fatty acid ester of carbon atom is good, the most handy C 18～C 24Lipid acid, especially behenic acid or behenic acid and stearic mixture.These esters also can prepare by the esterification of many ethoxylated fatty acids or many ethoxylated alcohols, and the Fatty Alcohol(C12-C14 and C12-C18) of the methyl ether of available polyoxyethylene glycol or many ethoxylations for example is as obtainable on the market " Brij " material.
Be particularly suitable for distillating material, the compound of particularly making the fluidity improver of narrow boiling range overhead product is vinylacetate and the multipolymer of staring at the fumarate of molar weight, fumarate is to get by FUMARIC ACID TECH GRADE and a kind of mixture esterification, and the molecular weight that this mixture contains the C12/C14 straight chain alcohol mixture of at least 95 molecular fractions and 5 molecular fractions is 600 polyoxyethylene glycol.
The other method of making material of the present invention is ester polymer or multipolymer and oxyethane or the 1,2 epoxy prapane effect that makes free carboxy acid or hydroxyl.
Compound of the present invention can be used as additive to improve hydrocarbon fuel (as crude oil, residual fuel and distillate fuel) low-temperature performance, these compounds can reduce the pour point of fuel, and the size of control wax crystalls also can reduce the cloud point of fuel in some cases to improve low temperature filterability.So-called distillate fuel is meant that those fuel and the oil fuel, particularly boiling spread that are generally used for the diesel oil vehicles are the domestic fuel oil of 120～500 ℃ (especially 160～400 ℃).And when being used for some and distillating fuel, they and other distillate additive to carry out deleterious interactional tendency and is less than the similar additive that does not contain polyoxyalkylenes.This compounds can use separately, but we find when other additive that they improve the cold flow properties of distillate fuel with being intended to of proposing above uses, and is effective especially to distillate fuel.
Additive of the present invention can use with poly suboxygen alkyl ester, ether, ester/ether and composition thereof, and the latter contains at least two C 10～C 30Straight chain saturated alkyl and molecular weight are that 100～5000(is preferably 200～5000) polyoxyalkylene glycol, the alkyl in the above-mentioned polyoxyalkylene glycol contains 1～4 carbon atom.These materials have constituted European patent publication 0061895 A2 number theme.The example of the additive that adds together that this class is suitable has ethylene glycol (generally using PEG and PPG) and contains about 10～30(preferably 18～24) reaction product of the lipid acid of individual carbon atom (the especially mixture of behenic acid or hard ester acid and behenic acid), ester also can make by the esterification of many ethoxylated fatty acids or many ethoxylated alcohols.Also can adopt the ester that makes by lipid acid and many alkoxylamines or ammonia effect.
During additive that polymkeric substance of the present invention and multipolymer particularly distillate fuel as fuel, also can use with ethene unsaturated ester multipolymer FLOW IMPROVERS.Can comprise unsaturated monoesters and dibasic acid esters with the unsaturated monomer of ethylene copolymer with following general formula:
Figure 85108892_IMG5
R in the formula 3Be hydrogen or methyl; R 2For-OOCR 5Base, wherein R 5Be hydrogen or C 1～C 28(be generally C 1～C 17, be preferably C 1～C 8) straight chained alkyl or branched-chain alkyl; Perhaps R 2For-COOR 5Base, wherein R 5As mentioned above, but be not hydrogen; R 4For hydrogen or top said-COOR 5, the R in general formula 2And R 4Be hydrogen and R 2For-OOCR 5The time, this class monomer comprises C 1～C 29(be generally C 1～C 18) ethene alcohol ester and C preferably 2～C 5Monocarboxylic acid.Can vinylacetate be arranged, vinyl propionic ester and vinyl isobutyrate, preferably vinylacetate with the example that ethene carries out the vinyl ester of copolymerization.Multipolymer should contain 20～40 weight percentage vinyl ester, is preferably 25～35 weight percentage.Can as described in United States Patent (USP) 3961916, be the mixture of two kinds of multipolymers also.
With gas-phase permeation press assay method measure the number-average molecular weight of these multipolymers be preferably 1000～6000, be preferably 1000～4000.
Our polymkeric substance and multipolymer also can be used from distillate fuel with polar compound one ionic or non-ionic type, can suppress the wax crystalls growth in fuel.Have found that when nitrogenous polar compound uses with glycol ester, ether or ester/ether effectively especially, back three kinds of component mixtures also belong to scope of the present invention.These polar compounds are generally C 20～C 300(be preferably C 20～C 100) amine salt and/or acyl ammonia, the amine that is replaced by the alkyl of at least 1 molar ratio acts on and gets with the alkyl acid that contains 1～4 carboxylic acid group or its acid anhydrides of 1 molar ratio; Also can adopt ester/acyl ammonia.These nitrogen compounds are at United States Patent (USP) 4,211, describe to some extent in 534.Suitable amine is generally long-chain C 12～C 40Primary amine, secondary amine, tertiary amine or its quaternary amine mixture; But short chain amine also can use, if the nitrogen compound of gained is oil-soluble, then general contained the total number of carbon atoms is 20～300, and nitrogen compound also should have at least one straight chain C 8～C 40The alkyl segment.
Suitable amine comprises primary amine, secondary amine, tertiary amine or quaternary amine, but secondary amine preferably.Tertiary amine and quaternary amine can only generate amine salt.The example of amine has: tetradecylamine, cocoamine amine, hydrogenated animal ester oil amine etc.The example of secondary amine has two-octadecylamine, methyl sweet potato amine etc.The mixture of amine also is suitable for, and all is mixture by natural materials deutero-amine a lot.Preferably general formula is HNR 1R 2This secondary amine of hydrogenated tallow oleyl amine, R in the formula 1And R 2Be by hydrogenated animal fat deutero-alkyl, form and be about 4%C 14, 31%C 16, 59%C 18
The carboxylic acid (and acid anhydrides) that is suitable for preparing these nitrogen compounds comprises cyclohexane dicarboxylic acid, tetrahydrobenzene dicarboxylic acid, pentamethylene dicarboxylic acid, two-Alpha-Naphthyl acetate, naphthalene dicarboxylic acids etc.Usually the carbonatoms of these sour loop sections is about 5～13.Be applicable to that acid of the present invention has benzene dicarboxylic acid, as phthalic acid, terephthalic acid and phthalic acid.Phthalic acid or its acid anhydrides are especially suitable.
Nitrogenous compound is that 8～40(is preferably 8～24 to have a carbonatoms at least) the straight chained alkyl segment be good.Also at least a kind of ammonium salt, amine salt or amido linkage to be arranged in the molecule.Especially wish amine compound be two-hydrogenated tallow oleyl amine by 1 mole phthalate anhydride and 2 moles act in proportion and acid amides-amine salt.It also can be the diamide that this acid amides-amine salt dehydration is got.
Other sulfonamide derivatives that can be used as co-additives has oil-soluble amine carboxylate salt and/or acid amides, as trioctylamine nutmeg hydrochlorate or sweet potato hydrochlorate.Polyamines can use as many aliphatics amides as the reaction product of tetren and stearic acid or behenic acid with the reaction product of aliphatic carboxylic acid.
Multipolymer can use with one or more above-mentioned additives.
The relative proportion that is used for the additive of mixture of the presently claimed invention is that per 1 part of other additive should have 0.5～20 weight part to contain the ester polymer of poly suboxygen alkyl.The total amount of additive therefor depends on concrete fuel, but general consumption is 0.0001～5% of a weight of fuel.
For supplying conveniently, additive system of the present invention can be made into concentrate in oil to add in a large amount of fuel.Concentrate also can contain other additive as required.This concentrate should contain 3～75 weight percentage, is more preferably 3～60 weight percentage, preferably the additive of 10～50 weight percentage.This concentrate also within the scope of the invention.
The present invention can obtain explanation by following example.In these examples, the validity as the pour point reducer that distillates fuel and the additive of the filterableness improving agent additive similar with other of the present invention is stopped up experimental tests (CFPPT) with cold filtration compare.The method of CFPPT is at " oil research institute magazine ", and the 52nd volume, in June, 1966, has detailed narration on the 173rd～185 page at the 510th phase.Designing this test is to reflect the cold flow situation of diesel oil fuel in automatic diesel engine.
Briefly, the 40 milliliters of oil samples that will test are placed in the groove that remains on-34 ℃ of left and right sides temperature to produce the non-linear cooling about 1 ℃/minute.Regularly measure (from more than the cloud point at least 2 ℃, 1 ℃ of temperature measuring of every reduction once) refrigerative oil and flow through the ability of fine screen mesh at interval at specific time.Used testing apparatus is a transfer pipet, and its lower end connects a funnel that turns around, and funnel is under the pasta of the oil of being tested.Across in flare opening, being a screen cloth that 350 meshes are arranged, has diameter and is 12 millimeters garden area.Each regularly mensuration when beginning vacuumizes in the transfer pipet upper end, makes oil suck transfer pipet by screen cloth, rises to the scale place of 20 milliliters of indications.At every turn smoothly by after oil is returned immediately into CFPP manage.1 ℃ of mensuration of the every reduction of temperature once, until oil can not be full of transfer pipet in 60 seconds till.This temperature just writes report as the CFPP temperature.The CFPP of doped fuel and the difference of CFPP of the same fuel that contains additive are not the CFPP decline degree of additive.Under the identical situation of additive concentration, the effectiveness of the FLOW IMPROVERS of interpolation is big more, and its CFPP decline degree is just big more.
Embodiment 1
The fuel that is used for present embodiment is:
ASTM-D-86 distillation ℃
The untreated CFPP initial boiling point of fuel 20% 90% final boiling point
℃
A????-5????182????220????354????385
B????-5????196????253????340????363
C????-3????222????275????336????360
Used additive is:
Additive 1 is a kind of blended C 12/ C 14Fumarate and vinylacetate carry out solution copolymerization with Diisopropyl azodicarboxylate as catalyzer by 1: 1 mol ratio and the multipolymer that obtains under 60 ℃.Blended C 12/ C 14Fumarate system is by common C 12And C 1450: 50 molar mixtures of alcohol and FUMARIC ACID TECH GRADE effect and get.
Additive 2 is two behenic acid macrogol esters (molecular weight of polyoxyethylene glycol is 600)
Additive 3 is two behenic acid macrogol esters (molecular weight of polyoxyethylene glycol is 400)
Additive 4 is identical with additive 1, different just be that 600 polyoxyethylene glycol is included in so that the C of fumarateization with the molecular-weight average of 2.5 molecular fractions 12/ C 14In the alcohol mixture, and polymerization is carried out under 80 ℃.
Additive 5 is identical with additive 4, different be 600 polyoxyethylene glycol just with polyoxyethylene glycol monomethyl ether (molecular weight of polyoxyethylene glycol is 750) the substituted molecule amount of 2.5 molecular fractions.
The CFPP decline degree of handling back fuel with these additives and composition thereof is as follows:
Fuel dope consumption ppm CFPP decline degree
A????1????120????0℃
4????120????8℃
B????1∶3????200∶60????2℃
4∶3????200∶60????7℃
C????1∶3????400∶100????2℃
4∶3????400∶100????8℃
In each case, the CFPP temperature just descends morely when having the polyoxyalkylene segment to exist in the molecule.
Embodiment 2
Additive with embodiment 1 is tested in following fuel:
ASTM-D-96 distillation ℃
The untreated CFPP initial boiling point of fuel 20% 90% final boiling point
℃
D????-4????256????287????326????343
E????-3????222????275????336????360
F????-5????238????281????331????352
G????-5????182????220????354????385
H????0????196????236????344????366
I????-3????201????249????318????340
And measured to reaching the required additive amount of CFPP target (additive is the compound of additive 1 or additive 5 and additive 3, and weight ratio is 2: 1), the result is as follows:
Additive agent mixture
Fuel C FPP target 1 and 35 and 3
℃ reach CFPP target institute expense
D????-9????1100????800
F????-9????900????500
E????-9????700????300
I????-6????＞1500????800
Embodiment 3
With additive 1,4 or 5 and the CFPP decline degree that 2: 1 mixtures reached of additive 3 as follows:
CFPP decline degree
Additive agent mixture
Fuel dope consumption ppm 1 and 35 and 34 and 3
G????100????8????12????-
H????400????6????12????-
E????400????4????8????8
F????600????3????6????5
D????800????2????5????4
I????1500????2????6????6
Embodiment 4
Additive of the present invention adds fuel G with ethylene vinyl acetate (EVA) multipolymer, and the EVA multipolymer contains 36 weight percentage vinylacetates according to English Patent 1263152, and the number-average molecular weight of pressing assay method to record with gas-phase permeation is 2000.
Other used additive is:
The additive 1 of embodiment 1.
Additive 6 is identical with additive 1, different just with so that the C of fumarate 12/ C 14The molecular weight that has added 5 molecular fractions in the alcohol mixture is the dioleate of 600 polyoxyethylene glycol.
Additive 7 is identical with additive 1, and just the FUMARIC ACID TECH GRADE dialkyl is obtained by following alcohol mixture:
45 moles just-C 12Alcohol
45 moles just-C 14Alcohol
45 moles just-C 12(CH 2-CH 2O) 220-OH
Additive 8 is identical with additive 6, and the molecular weight that has just adopted 2 molecular fractions is 600 polyoxyethylene glycol.
The CFPP value that is reached is as follows:
Other addition of C of EVA multipolymer FPP
Ppm ℃ of ppm numbering
Do not have---6
100????-????-????-6
200????-????-????-8
0????1????200????-7
0????6????200????-5
0????7????200????-9
0????8????200????-10
100????1????100????-7
100????6????100????-16
100????7????100????-16
100????8????100????-14
Embodiment 5
Measured the influence of additive amount with following additive agent mixture to the CFPP value of fuel E, F, G and I:
The code name mixture
X additive 1 and additive 3,2: 1 mol ratio
Y additive 5 and additive 3,2: 1 mol ratio
The result is shown in Fig. 1～4, and Fig. 3 and Fig. 4 have also comprised the result when EVA multipolymer that embodiment 4 is adopted uses separately with same processing rate.
Embodiment 6
Compound of the present invention is tested as the pour point reducer of the neutral lubricating oil of solvent.Polymer system adopts preceding method, and (by the alcohol mixture preparation, this alcohol mixture contains C to the fumarate of usefulness equimolar amount 1220 parts of alcohol, C 1330 parts of alcohol, C 1430 parts of alcohol, C 1520 parts of alcohol) and vinylacetate prepare and get (additive 9).Also adopt another kind of similarly polymkeric substance, alcohol mixture wherein contains the polyoxyethylene glycol (additive 10) of molecular weight 750 used in the additive 5 of 2.5 molecular fractions.
Method according to ASTM D97 has been measured pour point, and the result is as follows:
Processing rate 0 0.1(accounts for the weight percentage of polymkeric substance) 0.2(accounts for the weight percentage of polymkeric substance)
Additive-9 10 9 10
Pour point ℃-6-9-15-15-21
Embodiment 7
Additive 9 is identical with additive 1, does not just adopt C 12/ C 14Alcohol mixture, and adopt the Dobanol 25 industrial alcohols mixtures of selling on the market, it consists of:
20 weight percentage C 12Alcohol
30 weight percentage C 13Alcohol
30 weight percentage C 14Alcohol
20 weight percentage C 15Alcohol
Wherein 80 weight percentage are positive alcohol, and 209 weight percentage have methyl branch on 1
Additive 10 is identical with additive 9, just adopts the mixture of 1.975 moles of Dobanol 25 and 0.025 mole of polyoxyethylene glycol (molecular weight is 750).
Each mixes these two kinds of additives with additive 3 with 4: 1 ratios, adds among fuel D and the fuel J to test.The untreated CFPP of fuel J is-5 ℃, and its ASTM D-96 distillation situation is as follows:
202 ℃ of initial boiling points
20%????272
90%????329
Final boiling point 344
Test-results is as follows:
Total processing rate 500ppm 800ppm 1200ppm
Additive 9: 3 10: 39: 3 10: 39: 3 10: 3
CFPP in fuel D-6-9
CFPP in fuel J-8-10-9-11
Embodiment 8
Additive adds among the fuel K to be tested.The cloud point of fuel K is+5 ℃, and its ASTMD-96 distillation situation is as follows:
203 ℃ of initial boiling points
20%????261
90%????322
349 ℃ of final boiling point
And writing down its outward appearance with 1 ℃/hour speed cooling back at-5 ℃.
Added 4: 1 mixed additives of 1000ppm, the result is as follows:
The additive outward appearance
Additive 1: additive 2 solids
Additive 5: additive 2 liquid
Additive 1: additive 3 solids
Additive 5: additive 3 liquid
Embodiment 9
Additive 11 is identical with additive 1, just replaces the C of 10 molecular fractions with polyoxyethylene glycol (molecular weight is 750) monomethyl ether 12/ C 14Alcohol.
Several additives add in the propellant combination of fuel D of the fuel L of 50 weight percentage and 50 weight percentage, in the propellant combination and contain 200ppm ethylene vinyl acetate copolymer (vinylacetate accounts for 32 weight percentage) so that CFPP reaches-9 ℃.(the untreated CFPP of fuel L is-2 ℃, and its ASTM-D-96 distillation situation is:
Initial boiling point～198 ℃,
20%????～256℃
90%????～343℃
Final boiling point～367 ℃
Test-results, the CFPP of mixture is reached, and-9 ℃ of required additive amount are as follows:
Used additive 1: 11: 31: 3
Ratio 1: 1: 12: 1
Desired additives consumption 600＞1200
Repeat above-mentioned test, but adopt the propellant combination of the fuel M of the fuel J of 50 weight percentage and 50 weight percentage, wherein and contain the 200ppm ethylene vinyl acetate copolymer.
The untreated CFPP of fuel M is-4 ℃, and its ASTM D-96 distillation situation is:
186 ℃ of initial boiling points,
20%????254℃
90%????331℃
355 ℃ of final boiling point
Measurement result, for the required additive amount of CFPP that reaches-9 ℃ is:
Used additive 1: 11: 31: 3
Ratio 1: 1: 12: 1
Desired additives consumption 600 1200

Claims (15)

1, using polymer or multipolymer improvement boiling range is the method for 120-400 ℃ the low-temperature fluidity that distillates fuel, wherein polymkeric substance or multipolymer are made by olefinic insatiable hunger ester, and its weight-average molecular weight is 1,000-200,000, containing 0.15-5% (weight) molecular weight is the poly suboxygen alkyl of 100-5000.
2, method according to claim 1, wherein ethylenic unsaturated ester is a kind of fumarate.
3, method according to claim 2, wherein poly suboxygen alkyl is to introduce by FUMARIC ACID TECH GRADE and the alcohol mixture esterification that contains poly suboxygen alkyl alcohol or polyoxyalkylene glycol.
4, according to claim 2 or 3 described methods, wherein fumarate and another kind of ethylenic unsaturated ester copolymerization.
5, method according to claim 4, wherein another ethylenic unsaturated ester is a vinylacetate.
6, method according to claim 1, wherein polymkeric substance or multipolymer are that unsaturated ester and another ethylenically unsaturated monomer copolymerization of RCOOR ' makes by general formula, and in this general formula, R is the ethylenically unsaturated hydrocarbons base, and R ' is a poly suboxygen alkyl.
7, method according to claim 6, wherein another ethylenically unsaturated monomer is a kind of vinyl ester.
8, method according to claim 1, wherein polymkeric substance or multipolymer contain the polymkeric substance of free carboxy acid's base and poly suboxygen alkyl alcohol or polyoxyalkylene glycol esterification by one and make.
9, method according to claim 8, wherein use mixes with other alcohol in poly suboxygen alkyl alcohol or polyoxyalkylene glycol system.
10, according to the described method of above-mentioned any one claim, use one or more additives simultaneously, this additive system is selected from following one group of material:
(ⅰ). ethene unsaturated ester multipolymer FLOW IMPROVERS
(ⅱ). poly suboxygen alkyl ester ether, ester/ether and composition thereof
(ⅲ). ionic or non-ionic type polar compound
11, a kind of 0.0001～5%(weight that contains) (is benchmark to distillate the oil fuel gross weight) polymkeric substance or multipolymer, boiling range are 120-400 ℃ the oil fuel that distillates, the weight-average molecular weight of this polymkeric substance or multipolymer is 1000～200,000, system is made by ethylenic unsaturated ester, and it is heavy to contain 0.1～50%() molecular weight is 100～5000 poly suboxygen alkyl.
12, a kind of oil fuel that distillates according to claim 11, wherein ethylenic unsaturated ester is a kind of fumarate.
13, a kind of oil fuel that distillates according to claim 12, wherein poly suboxygen alkyl is to introduce by the alcohol mixture esterification of FUMARIC ACID TECH GRADE and poly suboxygen alkyl alcohol or polyoxyalkylene glycol.
14, a kind of according to claim 12 or the 13 described oil fuels that distillate, wherein fumarate and another ethylenic unsaturated ester copolymerization.
15, a kind of oil fuel that distillates according to claim 14, wherein another ethylenic unsaturated ester is a vinylacetate.
CN85108892A 1984-11-15 1985-11-14 Method for improving flow properties of liquid hydrocarbons Expired CN1006399B (en)

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DE59207320D1 (en) * 1991-07-18 1996-11-14 Hoechst Ag Copolymers of ethylenically unsaturated carboxylic acid esters with polyoxyalkylene ethers of lower, unsaturated alcohols as flow improvers for oils containing paraffin
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GB798457A (en) * 1956-05-23 1958-07-23 California Research Corp Copolymer composition
US3347645A (en) * 1963-12-20 1967-10-17 Exxon Research Engineering Co Multipurpose gasoline additive
US4160459A (en) * 1977-11-23 1979-07-10 Texaco Inc. Low pour crude oil compositions
RU2014347C1 (en) * 1981-03-31 1994-06-15 Эксон Рисерч энд Энджиниринг Компани Fuel composition
US4464182A (en) * 1981-03-31 1984-08-07 Exxon Research & Engineering Co. Glycol ester flow improver additive for distillate fuels
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