CN1038298A

CN1038298A - Fuel oil composition

Info

Publication number: CN1038298A
Application number: CN89104602A
Authority: CN
Inventors: 罗伯特·德里顿·塔克; 伊恩·莫尔; 肯尼思·刘达斯
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 1988-05-25
Filing date: 1989-05-25
Publication date: 1989-12-27
Anticipated expiration: 2004-05-25
Also published as: DE68919907D1; JP2723972B2; EP0343981A1; DE68919907T2; CN1024680C; EP0343981B1; KR900018339A; GB8812380D0; EP0343981B2; JPH0224394A; KR960013611B1; DE68919907T3

Abstract

A kind of fuel composition, it contains the polymkeric substance more than an amino of comprising of the liquid hydrocarbon fuel of most of weight and small part weight, this amino is primary amine, the salt of secondary amine or tertiary amine or quaternary ammonium salt, for example amine salt of the multipolymer of fumaric acid alkyl ester, vinyl-acetic ester and maleic anhydride.

Description

Fuel oil composition

The present invention relates to contain the fuel oil composition of FLOW IMPROVERS.

Wax separates the restriction that is subjected to its low-temperature fluidity in crude oil, middle distillate stock oil, heavy fuel oil (HFO) and residual fuel oil and the lubricating oil.The common method that addresses these problems is to add the compound improve wax crystallization, wax crystallization is become less (nucleator) and/or becomes less and grows into state (growth inhibitor) more closely.

Another difficulty is that little wax crystallization can stick together and forms bigger condensation product, and these condensation products and single crystal can stop up the filter screen that single crystal can pass through, and they are than the sedimentation more promptly of single small-crystalline.

We have found that some ammonia of adding or quaternary ammonium salt can improve wax crystallization, so that improve filtration capacity, reduce pour point and also reduce the tendency that wax crystallization generates condensation product.

Fuel oil composition according to the present invention comprises the polymkeric substance more than an amino of containing of the liquid hydrocarbon fuel of most of weight and small portion weight, and this amino is a kind of primary amine, secondary amine or tertiary ammonium salt or a kind of quaternary ammonium salt.And contain the FLOW IMPROVERS that is used as liquid hydrocarbon fuels more than the polymkeric substance of an amino according to the present invention, this amino is a kind of primary amine, secondary amine or tertiary ammonium salt or a kind of quaternary ammonium salt.

Liquid hydrocarbon fuel oil can be to distillate fuel oil, for example middle fraction oil fuel: as diesel oil, aviation fuel, kerosene, oil fuel, jet fuel, oil fuel (heatingoil) etc.Usually the suitable boiling spread that distillates fuel oil is 120 ℃ to 500 ℃ (ASTMD86), preferably 150 ℃ to 400 ℃.Though it a little is 357 ℃ that some specification specifies 90% distillates, representational oil fuel specification is 10% to distillate and a little be not more than 226 ℃, and 50% distillates and a little is not more than 272 ℃ and 90% and distillates and a little be at least 282 ℃, and is not more than 338 ℃～343 ℃.Oil fuel preferably is made up of with the mixture of cracking fraction such as catalytic cracking turning oil straight run such as gas oil, petroleum naphtha etc.

Polymkeric substance more than an amino can prepare by polymkeric substance and primary amine, secondary amine or the reactive tertiary amine that has polycarboxylic acid or acid anhydride.

In order to prepare quaternary ammonium salt, polymkeric substance can react with the tetraalkyl ammonium halide.Another kind method is with the reaction of tertiary amine and halon, derive like this and required polymkeric substance should contain halide based and prepare quaternary ammonium salt with reactive tertiary amine respectively.

There are many dissimilar polymkeric substance further to react to generate the required polymkeric substance contain two or more a plurality of amine salt bases.

(I) contains the example of polymkeric substance of one or more unsaturated monomers of ester and free carboxy acid's base, and the example of the monomeric multipolymer of unsaturated ester, and wherein at least a monomer also contains free carboxy acid's base.Object lesson is the multipolymer of the dialkyl of fumaric acid, toxilic acid, citraconic acid or methylene-succinic acid, the multipolymer of vinyl-acetic ester and fumaric acid, toxilic acid, citraconic acid or methylene-succinic acid mono alkyl ester, the dialkyl of the multipolymer of the mono alkyl ester of alkyl acrylate or alkyl methacrylate and fumaric acid, toxilic acid, citraconic acid or methylene-succinic acid and fumaric acid, toxilic acid, citraconic acid or methylene-succinic acid and fumaric acid mono alkyl ester and with the multipolymer of vinyl-acetic ester.

The suitable especially example of type I polymkeric substance is vinyl-acetic ester and fumaric acid mono alkyl ester and the multipolymer of dialkyl fumarate (alkyl wherein is 1: 1 the dodecyl and the mixture of tetradecyl) and the multipolymer of vinyl-acetic ester and arbitrary single dodecyl, single tetradecyl or single hexadecyl fumarate.

(II) other example is the multipolymer of unsaturated ester and/or alkene and unsaturated carboxylic acid anhydrides.These multipolymers are with primary amine or secondary amine reaction the time, owing to can generate half amide/half amine salt with the anhydride group reaction.Object lesson is the dialkyl of (a) fumaric acid, toxilic acid, citraconic acid or methylene-succinic acid and the multipolymer of maleic anhydride; Or (b) multipolymer of vinyl acetate such as vinyl-acetic ester or stearic acid vinyl ester and maleic anhydride, or (c) dialkyl of fumaric acid, toxilic acid, citraconic acid or methylene-succinic acid and the multipolymer of maleic anhydride and vinyl-acetic ester.Other example be maleic anhydride and vinylbenzene or with the multipolymer of aliphatic olefin, aliphatic olefin is C ₁₀To C ₃₀Alkene, for example decene, dodecylene, tetradecene, cetene, eicosylene, two dodecylenes, tetracosene, two vaccenic acids, the propylene tetramer or propylene six aggressiveness.The specially suitable example of type II polymkeric substance is fumaric acid two-dodecyl ester, the multipolymer of multipolymer, fumaric acid two-cetyl ester, vinyl-acetic ester and the maleic anhydride of the multipolymer of vinyl-acetic ester and maleic anhydride, fumaric acid two-tetradecyl ester, vinyl-acetic ester and maleic anhydride, or replace the equivalent multipolymer of fumarate gained with itaconic ester.

(III) required polymkeric substance also can obtain the slow Xi chaff of the thick ticket good fortune of carboxylic acid Sou people baboon    by the polymkeric substance that partial hydrolysis contains ester group and process  badger wood Feng and hold in the mouth cadmium tritium dealer to unload the dirty buffalo gnat  of a  mist expense position  from ι  coral  be that  wooden fork Feng holds in the mouth an ancient spear U shelf  Buddhist nunnery location green pepper ㄊ and sends chaff and process this lofty hazel  サ wood Feng of the lofty hazel  of the earnest   of the rampant  ┧ of  marmoset ァ ⒓ ┧ marmoset ァ ⒏ official Mang ァ ⒙ weight and hold in the mouth nobelium cricket  moat tomb book and scoop up the timid arsine ┨ of nobelium cricket   tomb book with a dustpan and scoop up an ancient spear with a dustpan

The specially suitable example of type III polymkeric substance is partial hydrolysis alkyl acrylate or methacrylate polymer, for example dodecylacrylate, vinylformic acid tetradecyl ester or vinylformic acid hexadecyl ester polymer.

(IV) suitable polymers also can be unsaturated carboxylic acid polymer, for example, and polyacrylic acid or polymethyl acrylic acid, the multipolymer of vinylformic acid and alkene such as ethene or fumaric acid alkyl ester, the multipolymer of methacrylic acid and alkene such as ethene or fumaric acid alkyl ester.

In the suitable polymkeric substance (I, II, III and IV) of all the above-mentioned types, polymkeric substance by containing carboxylic acid or acid anhydride and uncle one, secondary one, or reactive tertiary amine obtains corresponding amine salt, and (also can generate ester-amine salt with the alcohol reaction) obtains required amine salt.For example, when the polymkeric substance of reaction contained the acid anhydride, the amino that generates was amine salt and amides usually.Therefore can use and contain two mixtures that the amine salt base is so at least.

In order to prepare quaternary ammonium salt, can be with any above-mentioned polymkeric substance (I, II, III or IV) and the reaction of tetraalkyl ammonium halide, or these polymer transitions are become to contain halide group rather than hydroxy-acid group, perhaps by forming, and then with reactive tertiary amine with the reaction of unsaturated halogenide such as vinylchlorid so that generate quaternary amine.

(V) other suitable polymers can be passed through the hydrolysis of unsaturated ester polymer moieties, then and the carboxylic acid anhydride reaction, then carboxylic acid anhydride and primary-, secondary-or the reactive tertiary amine required amine salt of generation and making.Suitable unsaturated ester polymkeric substance is the homopolymer of acrylate, methacrylic ester, fumaric acid alkyl ester, or they and the multipolymer of alkene (for example ethene) or the multipolymer of vinyl-acetic ester and alkene.Object lesson is a vinyl-vinyl acetate copolymer.After the partial hydrolysis, polymkeric substance and acid anhydrides (for example succinyl oxide or maleic anhydride) reaction, resultant again with primary-, secondary-or reactive tertiary amine obtain corresponding amine salt, perhaps obtain corresponding quaternary ammonium salt with the reaction of tetraalkyl ammonium halide.

Though this point is unimportant, but the polymkeric substance that it is desirable to very much to contain at least two amine salt bases or quaternary ammonium salt base should contain the group that at least one comprises hydrogen and carbon, the total number of carbon atoms is at least 10 in the described group, and even more preferably at least one group has 12 to 18 carbon atoms.These groups are the straight or branched alkyl preferably, and they can directly or by carboxylic acid ester groups be connected on the main polymer chain, perhaps are connected on the nitrogen-atoms of amine salt or quaternary ammonium salt base.Polymkeric substance also can contain such group, and this group can be connected on nitrogen-atoms and the main chain simultaneously or be connected on the carboxylic acid ester groups.Therefore in I, II, III and IV polymer type, by the single and dialkyl of fumaric acid of its derived polymer, the alkyl in alkyl acrylate and the alkyl methacrylate comprises at least 10 carbon atoms.So specially suitable monomer is fumaric acid two-dodecyl ester, fumaric acid two-tetradecyl ester, fumaric acid two-stearyl and corresponding fumaric acid mono alkyl ester and their mixture thereof, vinylformic acid and methacrylic acid dodecyl, tetradecyl, hexadecyl and stearyl also are specially suitable monomers.In type III polymkeric substance, can use as toxilic acid two-decyl, two-dodecyl, two-tetradecyl ester.

As the another kind of compound or the additive that long chain alkyl group can be incorporated in the polymkeric substance, in the salifiable process of shape, use long-chain primary-, secondary-or tertiary amine or tetraalkyl ammonium halide or their mixture.

These amine can be represented by the formula:

R ¹NH ₂, R ¹R ²NH and R ¹R ²R ³N

With the tetraalkyl ammonium halide, its general formula is:

R ¹R ²R ³R ⁴NX

Wherein, R ¹, R ², R ³And R ⁴Be alkyl, alkyl preferably, and R wherein ¹, R ², R ³And R ⁴In preferably have at least one to contain at least 10 carbon atoms, 12～18 carbon atoms for example, for example dodecyl, tetradecyl, hexadecyl and octadecyl, wherein X is halogen, preferably chlorine.

Suitable polyamines useful molecules formula H ₂N (RHN) _XH and R ¹NH (RNR ¹) _XH represents, R in the formula ¹Be alkyl, R is a bivalent hydrocarbon radical, the alkylidene group that replaces of alkylidene group or alkyl preferably, and X is an integer.

The example of suitable primary amine is that hexylamine, octylame and those contain the amine of 10 carbon atoms at least, for example decyl amine, tetradecylamine, octadecane amine, eicosane amine, mixed amine RNH ₂(ArmeenC), wherein R is 0.5 weight %C ₆Alkyl, 8 weight %C ₈Alkyl, 7 weight %C ₁₀Alkyl, 50 weight %C ₁₂Alkyl, 18 weight %C ₁₄Alkyl, 8 weight %C ₁₆Alkyl, 1.5 weight %C ₁₈Alkyl and 7.0 weight %C ₁₈/ C ₁₉Unsaturated group.

The example of suitable secondary amine is dioctylamine and contains the diamines of the alkyl of at least 10 carbon atoms, didecylamine for example, 21 n-Laurylamines, two coconut amines (i.e. two mixed C ₁₂～C ₁₄Alkylamine), two-octadecane amine, cetostearyl amine, animal fat amine of dihydridization (Armeen 2HT) (the positive C of about 4 weight % ₁₄Alkyl, the positive C of 30 weight % ₁₆Alkyl, 60 weight %C ₁₈Alkyl, all the other are unsaturated group), positive coconut-propyl diamine (C ₁₂/ C ₁₄The alkyl propyl diamine-DuomeenC), n-Tallow, beef base-propyl diamine (C ₁₆/ C ₁₈The alkyl propyl diamine-DuomeenT).

The example of suitable tertiary amine is three hexyl amines, trioctylphosphine amine and the tertiary amine that contains the alkyl with at least 10 carbon atoms, for example, and hexyl two-decyl amine, three-decyl amine and three-hexadecylamine.

The example of suitable quaternary ammonium halide is that trioctylphosphine-ammonio methacrylate contains the amine of the alkyl of at least 10 carbon atoms with those, for example three-dodecyl-ammonio methacrylate, three-tetradecyl dodecyl chlorination ammonium and hexadecyldimethyl benzyl ammonium aniline.

The example of suitable polyamines is a N-octadecyl propanediamine, N ' N '-two-octadecyl propanediamine, N-tetradecyl butane diamines and N, N '-two-hexadecyl hexane diamines.

The number-average molecular weight of polymkeric substance salt of the present invention is generally 1000 to 500,000, and for example 10,000 to 100,000.

Being used for the specially suitable examples of polymers that contains amino of the present invention is:

(1) multipolymer of fumaric acid two-tetradecyl ester, vinyl-acetic ester and maleic anhydride (acetic ester: fumarate: the mol ratio of acid anhydrides is about 50: 45: 5) and two-C ₁₆/ C ₁₈N-alkylamine (C ₁₆Alkyl/C ₁₈Alkyl is about 1: 2) reaction generation half amide, main half amine salt by the maleic anhydride unit deutero-carboxylic acid group in the multipolymer.

(2) 50.0 moles of % vinyl-acetic esters, 45.0 moles of % fumaric acid two-C ₁₂/ C ₁₄The multipolymer of alkyl (1: 1) ester and 5 moles of % maleic anhydrides and 5 moles of % three-octyl amine reactions generate half amide, by half amine salt of the maleic anhydride unit deutero-carboxylic acid group in the multipolymer.

(3) as above-mentioned (2) multipolymer, but by 10 moles of % two-coconut (C ₁₂To C ₁₄Alkyl) amine replaces the reaction of trioctylphosphine amine to make.

(4), but replace the reaction of trioctylphosphine amine to make by 5 moles of % trioctylphosphine-ammonio methacrylates and 5 moles of % sodium hydroxide (in less water) as above-mentioned (2) multipolymer.The result forms the quaternary amine of polymkeric substance.

(5), but replace dialkylamine to make by the mixture of n-Laurylamine and tetradecylamine as above-mentioned (1) multipolymer.

(6) as above-mentioned (1) multipolymer, but by just-coconut (C ₁₂To C ₁₄Alkyl) propyl diamine replaces dialkylamine to make.

(7) as above-mentioned (1) to the multipolymer of (6), wherein multipolymer based on etc. the fumaric acid alkyl ester and the vinyl-acetic ester of mol ratio, but the amount of maleic anhydride is 10 moles of % of fumarate and vinyl-acetic ester total amount.

In order to improve the cold flow properties that distillates fuel oil, when fuel oil composition of the present invention mixes other additives known, can reach usually and improve effect.The example of these additives is polyoxyalkylene esters class, ethers, ester/ethers, acid amides/ester class and their mixture, and particularly those contain at least one preferably at least two C ₁₀To C ₃₀The polyoxyalkylene glycol of straight chain saturated alkyl, molecular weight is 100 to 5000, is preferably 200 to 5000, the alkyl in the described polyoxyalkylene glycol contains 1-4 carbon atom.European Patent Publication No 0061895A ₂In these additives some have been described.

Preferred ester class, ethers or ester/ethers can structurally be described with following formula:

R ⁵-O-（A）-O-R ⁶

R in the formula ⁵And R ⁶Be identical or different, can be:

(ⅰ) positive alkyl;

Alkyl is the saturated of straight chain and contains 10 to 30 carbon atoms, A represents the polyoxyalkylene segment in the glycol, wherein alkylidene group is 1 to 4 carbon atom, for example be essentially linear polyoxymethylene, polyoxyalkylene or polyoxygenated trimethylene part, some has than low alkyl group side chain (for example in the polyoxypropylene glycol) degree of branching is tolerable, but preferably is essentially linear glycol.

In general, suitable glycol is polyoxyethylene glycol of substantial linear (PEG) and polypropylene glycol (PPG), and molecular weight is about 100 to 5000, preferably about 200 to 2000.It is useful that the lipid acid of preferred ester class and 10-30 carbon atom and glycol reaction generate ester additive, and preferably uses C ₁₈～C ₂₄Lipid acid, particularly docosoic.The esterification of the lipid acid that these esters also can be by polyethoxylated or the alcohols of polyethoxylated makes.Particularly preferred this class additive is a polyoxyethylene glycol Er docosoic ester, and the molecular weight of ethylene glycol part is about 600, usually is abbreviated as PEG600 Er docosoic ester.Similarly the molecular weight of ethylene glycol part is that about 200 and 400 polyoxyethylene glycol Er docosoic ester usually is abbreviated as PEG200 and PEG400 respectively.

Other the suitable additive that is used for fuel oil composition of the present invention is an ethene unsaturated ester multipolymer FLOW IMPROVERS.The unsaturated monoesters and the dibasic acid esters that can comprise following general formula with the unsaturated monomer of ethylene copolymerization:

R in the formula ₈Be hydrogen or methyl, R ₇Be-OOCR ₁₀Group, wherein R ₁₀Be hydrogen or C ₁To C ₂₈, that more commonly used is C ₁To C ₁₇, C preferably ₁To C ₈The straight or branched alkyl; Perhaps R ₇For-COOR ₁₀, R wherein ₁₀As previous defined but be not hydrogen, R ₉Be hydrogen or-COOR ₁₀(as preceding defined).R wherein ₇And R ₉Be hydrogen and R ₈For-OOCR ₁₀Monomer comprise C ₁To C ₂₉, C more usually ₁To C ₁₈The ethene alcohol ester of monocarboxylic acid is preferably C ₂To C ₂₉, C more usually ₁To C ₁₈The ethene alcohol ester of monocarboxylic acid, preferably C ₂To C ₅Monocarboxylic acid ethene alcohol ester.Can comprise vinyl-acetic ester, propionate and vinyl butyrate or isopropylformic acid vinyl acetate, preferably vinyl-acetic ester with the example of the vinyl acetate of ethylene copolymerization.Multipolymer contains 20 to 40 weight % vinyl acetate preferably, better contains 25 to 35 weight % vinyl acetate.They also can be the mixtures of two kinds of multipolymers, as United States Patent (USP) 3,961, described in 916.The number-average molecular weight that is preferably these multipolymers is 1000 to 6000, preferably 1000 to 3000(uses the gas-phase permeation platen press to measure).

Other the suitable additive that is used for fuel oil composition of the present invention is a polar compound, ionic or non-ionic compound, and they play the wax crystalls growth inhibitor in oil fuel.Have found that when nitrogenous polar compound is used in combination with glycol ester, ether or ester/ether it is effective especially.The amine salt and/or the acid amides of the generation that carboxylic acid that the amine that these polar compounds are normally replaced by at least 1 molar part alkyl and the alkyl that 1 molar part contains 1 to 4 carboxylic acid group replace or their carboxylic acid anhydride react; Also can use and contain 30 to 300, preferably ester/the amides of 50 to 150 total carbon atom numbers.These nitride have been described in United States Patent (USP) 4211534.Suitable amine is the C of long-chain normally ₁₂-C ₄₀Primary amine, secondary amine, tertiary amine or quaternary amine or their mixture, as long as but the nitrogen compound that obtains is oil-soluble, also can use the short amine of chain, therefore contain 30 to 300 total carbon atom numbers of having an appointment usually.Nitrogen compound preferably contains at least one straight chain C ₈To C ₄₀, C preferably ₁₄-C ₂₄The alkyl chain link.

Suitable amine comprises primary amine, secondary amine, tertiary amine and quaternary amine, but secondary amine preferably.Tertiary amine and quaternary amine can only form amine salt.The example of amine comprises tetradecylamine, coconut amine, hydrogenated tallow amine or the like.The example of secondary amine comprises two-octadecane amine, methyl-docosyl amine or the like.The mixture of amine also is suitable for, and is mixture from many amine of natural matter derivative.Amine is that molecular formula is HNR preferably ₁R ₂The secondary amine of hydrogenated tallow, R in the formula ₁And R ₂Be by about 4%C ₁₄, 31%C ₁₆, 59%C ₁₈The hydrogenated tallow deutero-alkyl of forming.

The example that is used to prepare the suitable carboxylic acid (with their carboxylic acid anhydride) of these nitrogen compounds comprises hexanaphthene 1, the 2-dicarboxylic acid, cyclohexane dicarboxylic acid, pentamethylene 1,2-dicarboxylic acid, naphthalene dicarboxylic acids or the like, generally these acid are at circular part 5-13 the carbon atom of having an appointment.Acid preferably is benzene dicarboxylic acid, for example phthalic acid, terephthalic acid and m-phthalic acid.Phthalic acid or its acid anhydrides are particularly preferred.Particularly preferred compound is the acid amides-amine salt that is generated by 1 molar part Tetra hydro Phthalic anhydride and the reaction of 2 molar part animal fat amine of dihydridization.Another kind of compound preferably is the diamide that this acid amides-the amine salt dehydration generates.

The relative proportion that is used for the various additives of this mixture is preferably from 0.05-20 part weight, preferably from the polymkeric substance that contains amine salt or quaternary ammonium salt of 0.1-5 part weight other additive than 1 part of weight, as polyoxyalkylene esters, ether, ester/ether or amide ether.

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Polymkeric substance can be dissolved in the suitable solvent easily, and forming the concentration of polymkeric substance in solvent is 20-90, for example 30-80 weight %.Suitable solvent comprises kerosene, aromatic hydrocarbons petroleum naphtha, mineral lubricating oils etc.

Embodiment 1

In this example, join two kinds of F that distillate fuel oil as copolymer A A, BB, CC and DD with following properties ₁And F ₂The time, vinyl-acetic ester-dialkyl fumarate copolymer A A and multipolymer BB that contains two amine salt and CC are compared with the multipolymer DD that contains quaternary amine:

F ₁F ₂

D-86 distillates: 222 ℃ 238 ℃ of initial boiling points

20% 275℃ 281℃

90% 336℃ 331℃

360 ℃ 352 ℃ of final boiling point

Wax appearance point-3 ℃-3.5 ℃

Basis CFPPT ^*-3 ℃-3 ℃

^*Cold filter stoppage experimental tests

Polymkeric substance is described in detail as follows:

AA: etc. mol ratio vinyl-acetic ester and C ₁₂Alkyl/C ₁₄The multipolymer of the dialkyl fumarate of alkyl (1: 1).

BB:50.0 mole % vinyl-acetic ester, 45.0 moles of %C ₁₂Alkyl/C ₁₄The product of the dialkyl fumarate of alkyl (1: 1) and the terpolymer of 5 moles of % maleic anhydrides and 5 moles of % trioctylphosphine amine reactions.

CC:50.0 mole % vinyl-acetic ester, 45.0 moles of %C ₁₂Alkyl/C ₁₄The dialkyl fumarate of alkyl (1: 1) and the terpolymer of 5 moles of % maleic anhydrides and 10 moles of % two coconut (C ₁₂-C ₁₄) product of amine reaction.

DD:47.5 mole % vinyl-acetic ester, 47.5 moles of %C ₁₂Alkyl/C ₁₄The dialkyl fumarate of alkyl (1: 1) and the multipolymer of 5 moles of % maleic anhydrides and 5 moles of % tri-n-octyl methyl ammonium chlorides and 5 moles of %NaOH react in less water, therefrom isolate NaCl.

Half the mixture of PEG200 docosoic ester, PEG400 docosoic ester and PEG600 docosoic ester (mol ratio is 1: 1: 1) of each and its weight among polymer A A, BB, CC and the DD is mixed, in all cases, the mixture of polymkeric substance and PEG docosoic ester is added to oil fuel F ₁And F ₂In, wherein active material concentration is 0.1%(1000ppm), the result is as follows for CFPPT test gained:

Polymer fuel F ₁Fuel F ₂

AA -11 -10

BB -13 -12

CC -14 -12

DD -14 -13

This shows that polymer B B, CC and DD gained result are better than not containing amino polymer A A.

The CFPPT experimental details is as follows:

Cold filter stoppage experimental tests (CFPPT).

Measure the cold filtering property of mixture with cold filter stoppage experimental tests (CFPPT)." Journal of the Institute of petroleum " used in this test, 52 volumes, and 510 phases, in June, 1966,173-goes up the methods of describing in detail for 185 pages and carries out.Briefly, 40 milliliters of oil samples will testing cool off with being maintained at about in-34 ℃ the bath, regularly (since 2 ℃ of 1 ℃ of every declines of temperature on the cloud point) measure the ability that the oil that is cooled flows through fie screen at certain time intervals.With this cold flow properties of a device to test, this device by with the lower end of a suction pipe with place the subsurface inverted funnel of tested oil to be connected to form.With area is that 350 about 0.45 square inch purpose filter screens are laid on flare opening, the beginning routine test, all vacuumize in the upper end of suction pipe at every turn, make oil by 20 milliliters of oily mark in the filter screen suction suction pipe, the every decline of temperature was once being carried out revision test until oil can not be full of suction pipe in 60 seconds till.CFPPT(℃ of △ of test-results) expression, △ CFPPT(℃) be untreated fuel (CFPP ₀) and the fuel (CFPP that handles with FLOW IMPROVERS ₁) stop poor between the yield temperature, promptly

△CFPP＝CFPP ₀-CFPP ₁

Embodiment 2

In the present embodiment, the polymkeric substance that contains various amine salt based on fumaric acid alkyl ester-vinyl-acetic ester-maleic anhydride is mixed (molecular weight (MW) of ethylene glycol part is about 6,00(,PEG,600 two docosoic esters) with polyoxyethylene glycol two docosoic esters, be added to the oil mixt F that distillates fuel ₃In, F ₃Property column in table 1.

In all cases, as follows with PEG600 Er docosoic ester with the various polymkeric substance of weight ratio blended of 4 parts of polymkeric substance of every part of PEG600 Er docosoic ester:

Polymer salt describes in detail

A fumaric acid 21 tetradecyl ester-vinyl-acetic esters-10 mole % maleic anhydride altogether

The half amide of polymers, half amine salt, amine are R ₂NH, wherein R such as front provide,

Be Armeen C.

The half amide of B fumaric acid 21 tetradecyl ester-vinyl-acetic esters-10 mole % maleic anhydride copolymers, half amine salt, amine are positive Tallow, beef propyl diamine.

C fumaric acid 21 tetradecyl ester-vinyl-acetic esters-10 mole % maleic anhydride altogether

Single trioctylphosphine amine salt of polymers.

50 moles of % vinyl-acetic esters of D, 45 moles of % fumaric acid 21 tetradecyl esters

Multipolymer and R with 5 moles of % maleic anhydrides ₂R=C in the NH(formula ₁₆/

C ₁₈Alkyl) with 1: 1 molar ratio reaction.Generate half amide-half amine salt.

Being total to of E fumaric acid 21 tetradecyl ester-vinyl-acetic esters-5 mole % maleic anhydride

The half amide of polymers-half amine salt, amine are R ₂NH, R such as front provide in the formula,

Be Armeen C.

Mole % maleic anhydride copolymerization of F fumaric acid 21 tetradecyl ester-vinyl-acetic esters-5

The single trioctylphosphine amine salt of thing.

Mole % maleic anhydride copolymerization of G fumaric acid 21 tetradecyl ester-vinyl-acetic esters-5

21 trioctylphosphine amine salt of thing.

Mole % maleic anhydride copolymerization of H fumaric acid 21 tetradecyl ester-vinyl-acetic esters-5

The half amide of thing, half amine salt, amine are R ₂NH, R=C in the formula ₁₆/ C ₁₈

Alkyl.

Mole % maleic anhydride copolymerization of I fumaric acid 21 tetradecyl ester-vinyl-acetic esters-5

The half amide of thing, half amine salt, amine are R ₂NH, R such as front provide in the formula,

Be Armeen C.

Mensuration contains the CFPPT of the oil fuel mixture of polymer A, and this mixture is carried out PCT test (programming cool test) is specified in down:

Programming cool test (PCT)

This is one and is designed to the slow refrigeration test relevant with the suction of the oil fuel that stores.The cold flow properties of measuring the described fuel contain additive with the PCT method is as follows: 300 milliliters of fuel are cooled to test temperature with 1 ℃/hour linearity, make this temperature keep constant then.After this test temperature keeps 2 hours, remove about 20 milliliters of upper layers with aspirating, prevent to test the influence that is subjected to the unusual big wax crystallization that in process of cooling, on oil/air interface, forms.By slow stirring the wax at the bottom of being deposited in bottle is disperseed, insert the CFPPT filter for installation then.Open switch, vacuumize the 500mm mercury column, when 200 milliliters of fuel enter when having the scale receptor by strainer, close switch: if by given order number in 10 seconds, collect 200 milliliters of notes do PASS(by), if flow velocity represents that too slowly strainer has stopped up note and failed.

The order number that passes through under the record test temperature.

The gained result is as follows:

△CFPP PCT（+2℃）

Polymer salt PEG600 1,500 3,000 1,500 3000

Er docosoic ester PPm PPm PPm PPm

4 parts (weight) 1 part of (weight) (active constituent) (active constituent)

A 1 4.5 40 100

^*Test temperature

Further measure with the CFPPT method and to contain polymer B and all mix with 4: 1 weight ratio respectively with PEG600 Er docosoic ester to all polymkeric substance of I() F ₃Mixture.Multipolymer X is used for than than purpose, and it is the multipolymer of vinyl-acetic ester and fumaric acid 21 tetradecyl esters.The result is as follows:

△CFPP

1500PPm 3000PPm

Polymer salt (active constituent) (active constituent)

B 1.5 2.5

C 1 2

D -2 ^＊5.5

E 0.5 3

F 0 3

G 0 2.5

H 0.5 3.5

I 0.5 3

X 1.5 3.5

^*Negative sign represents that CFPP increases.

To containing polymkeric substance D, E, F, G, the F of H and I ₃Mixture carries out PCT(+2 ℃) test, all polymkeric substance mix with 4: 1 weight ratio respectively with PEG600 Er docosoic ester.The gained result is as follows:

Polymer salt is at 2 ℃ of PCT orders that pass through

1500PPm active constituent 3000PPm active constituent

D 60 150

E 30 80

F 40 80

G 30 80

H 100 200

I 30 60

X 80 150

No polymkeric substance＜20

(independent basic fuel oil)

Can be clear that the advantage that contains mixture of polymers has surpassed independent basic fuel oil.

Table 1

Wax _(a)WAT _(b)WAP D86 distillates

Content % (℃) (℃) initial boiling point D20 D50 D90 final boiling point

F ₃4.9/9.8 ^（c）10.3 7.5 204 262 295 346 362

(a) 5 ℃ of waxes are lower than WAT/10 ℃ and are lower than WAT

(b) gauged thermal hysteresis.

(c) value of estimating from component.

Embodiment 3

Present embodiment makes polymer salt D, E, F, G, H and the I in the use-case 2 be added to F ₄During a kind of high boiling point distillates fuel oil, measure the independent F of CFPP(in all cases ₄) and △ CFPP.F ₄ASTM D86 distillate that details are as follows:

172 ℃ of initial boiling points

D20 228℃

D50 276℃

D90 362℃

389 ℃ of final boiling point

To basic fuel oil F ₄Middle 300PPm and 500PPm, i.e. 0.03 weight % and the 0.05 weight %(active constituent of adding) various polymkeric substance and untreated oil fuel compare, and the result is as follows:

Polymer concentration

Salt ppm CFPP △ CFPP

D 300 -3-3 7

D 500 -6-5 9

E 300 +3+4 0

E 500 -4-5 8

F 300 +1+5 1

F 500 -5-5 9

H 300 -5-2 7

H 500 -6-6 10

I 300 +1+2 2

I 500 -8-5 10

G 300 +3+4 0

G 500 -6-6 10

Independent basis

Oil fuel+4+3

Polymer salt D, E, F, G, H and I also with multipolymer Y respectively with 1: 4 mixed in molar ratio, be added to F then ₄In, concentration is 300ppm and 500ppm(0.03 mole % and 0.05 mole of %).Multipolymer Y is that to contain 36% weight molecular weight be the ethylene of about 2000 vinyl-acetic ester and the mixture that contains the ethylene (3: 1 weight) of 13% weight vinyl-acetic ester (molecular weight is about 3000).

As the front, measure the oil fuel that the CFPP(under the various situations handles) and △ CFPP.The result is as follows:

Concentration

Polymer salt Y(PPm) polymer salt CFPP △ CFPP

（ppm）

D 240 60 -14 -12 17

D 400 100 -17 -16 20

E 240 60 -14 -13 17

E 400 100 -15 -14 18

F 240 60 -15 -14 18

F 400 100 -15 -15 19

H 240 60 -15 -14 18

H 400 100 -14 -14 18

I 240 60 -12 -13 16

I 400 100 -16 -14 19

G 240 60 -15 -13 18

G 400 100 -14 -14 18

Independent basis

Oil fuel+4+3

Can see that in all cases yield point obviously reduces when polymer salt is added in the basic fuel oil.

Embodiment 4

Various polymer salts individually or be added to the F that distillates fuel oil after polymkeric substance bifurcation (see numeral 2) mixes ₅In, F ₅ASTM D86 to distillate characteristic as follows:

188 ℃ of initial boiling points

D20 236℃

50 278℃

D90 348℃

378 ℃ of final boiling point

CFPPT and PCT result are as follows:

Polymer salt concentration (ppm) CFPP △ CFPP PCT(is at-9 ℃)

D 375 -3 -3 3 40

D 625 -4 -4 4 80

E 375 -5 -5 5 40

E 625 -5 -4 4 60

F 375 -4 -3 3 40

F 625 -3 -3 3 60

H 375 -3 -3 3 40

H 625 -4 -4 4 60

I 375 -3 -4 3 40

I 625 -5 -5 5 60

G 375 -5 -4 4 40

G 625 -6 -6 6 60

Concentration (ppm)

Bifurcation polymkeric substance CFPP CFPP PCT(is at-9 ℃)

300 75 D -16 -18 17 150

500 125 D -16 -18 17 200

300 75 E -14 -16 15 120

500 125 E -17 -16 16 200

300 75 F -16 -14 15 150

500 125 F -17 -18 17 200

300 75 H -14 -15 14 120

500 125 H -14 -15 14 200

300 75 I -17 -14 15 150

500 125 I -16 -19 17 200

300 75 G -16 -17 16 120

500 125 G -16 -13 14 200

Embodiment 5

Present embodiment polymer salt C(as using in the example 2) and another kind of polymer salt J be added to the F that distillates fuel oil ₆In, F ₆D86 to distillate characteristic as follows:

173 ℃ of initial boiling points

D20 222℃

D50 297℃

D90 356℃

371 ℃ of final boiling point

Polymkeric substance J is half amide, half amine salt of the multipolymer of fumaric acid 21 tetradecyl ester-vinyl-acetic esters-10 mole % maleic anhydride, and amine is R ₂NH, wherein R is C ₁₆/ C ₁₆Alkyl.

These polymer salts C and J also can 1: 1 mol ratio and vinyl-vinyl acetate copolymer blended mixture (seeing example 3).

Various mixture salt and be added in the oil fuel, concentration with the mixture of 1: 1 mol ratio and bifurcation be 300 and the 600ppm(active constituent) (0.03% and 0.06 weight %), the gained mixture is carried out PCT and CFPPT test, the result is as follows:

Polymer poly compound concentration PCT CFPP

Salt ppm (8 ℃)

J 300 40 +3 +3

J 600 80 +2 +3

J Z 300 40 -5 -8

J Z 600 80 -9 -8

C 300 ＜20 +3 +3

C 600 20 +3 +2

C Z 300 40 -1 -2

C Z 600 80 -6 -6

Embodiment 6

Present embodiment, polymer salt A and B(as using in the example 2) and J(as use in the example 5) be added to the F that distillates fuel oil of example 5 ₆In, also add following polymers salt in addition in the oil fuel.Every kind of polymer salt mixes with the copolymer mixture bifurcation of use in the example 3 with 1: 1 mol ratio.

Polymer salt

K fumaric acid two-tetradecyl ester-vinyl-acetic ester-10 mole % maleic anhydride altogether

The half amide of polymers, half amine salt, wherein amine is RNH ₂, R=C ₁₆/

C ₁₈Alkyl.

L fumaric acid two-tetradecyl ester-vinyl-acetic ester-10 mole % maleic anhydride altogether

The half amide of polymers, half amine salt, wherein amine be just-coconut-propyl diamine.

The same L of M, but wherein R is that the front provides, and is Armeen C.

With every kind of polymer salt of copolymer mixture bifurcation blended with two kinds of different concns promptly 300 and 600ppm(0.03 weight % and 0.06 weight %) active ingredient is added in the oil fuel, carries out PCT and CFPPT test.The gained result is as follows:

Additive concentration PCT CFPP

+ bifurcation (1: 1) is (8 ℃) (ppm)

K 300 - 20

K 600 - 20

K 300 40 60

K 600 80 100

L 300 - 20

L 600 - 20

L 300 40 60

L 600 80 100

J 300 40 60

J 600 100 120 +2 +1

J 300 60 80

J 600 80 100 -7 -8

A 300 20 30

A 600 20 30 +2 +1

A 300 40 60

A 600 60 80 -9 -11

B 300 - 20

B 600 - 20 +2 +1

B 300 40 60

B 600 60 80 -9 -9

F 300 - 20

F 600 - 20 +2 +2

F 300 30 40 -1 -2

F 600 80 100 -5 -8

M 300 - 20

M 600 - 20 +2 +1

M 300 30 40

M 600 80 100

Independent

Basic fuel oil 20 30+3+3

Can see and add the flowing property that polymer salt can improve basic fuel oil usually.

Embodiment 7

Relatively use the vinylbenzene of tetradecanol partial esterification and the multipolymer of maleic anhydride (multipolymer XX) and the nonesterified group by hydrolysis XX and make the multipolymer that contains the carboxylic acid group and polymer salt (N) that the reaction of three-octadecane amine obtains between PCT and CFPPT.

When N and XX are added to the oil fuel F that uses in the example 4 ₅In the time of in (concentration is 500ppm), can find that CFPPN reaches 2 ℃ than XX is more effective, and PCT-14 ℃ with 6 mesh sieve branches, can be by 60 millimicrons of filter screens to 250 millimicrons.

Embodiment 8

In the present embodiment, align-multipolymer and the diamines R of octadecylene and maleic anhydride ₂(R is positive C to NH in the formula ₁₆/ positive C ₁₈The alkyl mixed base) reacting generating copolymer salt (P), (P) be added to separately distillate fuel oil, and be added in the oil fuel with multipolymer bifurcation (seeing example 3), carry out PCT(at-10 ℃ with the multipolymer that is added to the prior art in the same oil fuel again), CFPP and DSC test are relatively.

To the F that distillates fuel oil ₇In add multipolymer, concentration is 175 and 300ppm, F ₇ASTM D86 characteristic as follows:

184 ℃ of initial boiling points

D20 226℃

D50 272℃

D90 368℃

398 ℃ of final boiling point

Compare with the multipolymer BB and the CC of other prior art, multipolymer (comprising copolymer A A) is specified in down:

Copolymer A A: the multipolymer of vaccenic acid and maleic anhydride.

The ester that multipolymer BB: copolymer A A and cetyl alcohol reaction generate.

The ester that multipolymer CC: copolymer A A and Stearyl alcohol reaction generate.

Difference formula scanning calorimetry (DSC).

Use the DSC(dsc) measure WAT ℃ of △ (temperature appears in wax), when the equivalent speed meter cooled off with 2 ℃/minute, △ WAT was exactly the temperature (WAT that distillates fuel oil and wax occurs in independent basis ₀) and treated distillating fuel oil the temperature (WAT of wax appears ₁) poor.In the DSC test, be 300ppm only with a concentration, 25 μ l oil fuel sample determination test-results, i.e. △ WAT=WAT ₀-WAT ₁

The gained result is as follows, and wherein first digit is obtained by 175ppm, and second digit obtains (except the DSC) by 300ppm.

BB CC P

PCT independent 60,/60 30,/30 40/40

+ bifurcation ^*80,/80 1,00/,100 250/250

Independent 0/ △ of CFPP 1 0/0 △ 1/ △ 1

+ bifurcation ^*△ 18/ △ 19 △ 15/ △ 16 △ 16/ △ 19

DSC△WAT 4.2 2.8 2.2

^*When bifurcation existed, the mol ratio of bifurcation and BB, CC or N was 4: 1.

Claims

1, a kind of fuel composition, it contains most of weight liquid hydrocarbon fuels and small part weight and contains polymkeric substance more than an amino, and this amino is the salt or the quaternary ammonium salt of primary amine, secondary amine or tertiary amine.

2, according to the composition of claim 1, wherein fuel is to distillate fuel oil.

3, according to any one composition of claim 1 and 2, wherein polymkeric substance is from also containing one or more unsaturated ester polymer of monomers deutero-of free acidic group, or the monomeric multipolymer deutero-of unsaturated ester from wherein having at least to contain free acidic group.

4, according to any one composition of claim 1 and 2, wherein polymkeric substance is the multipolymer deutero-by unsaturated ester and/or alkene and unsaturated carboxylic acid anhydrides.

5, according to any one composition of claim 1 and 2, wherein polymkeric substance is from containing the polymer-derived that partial hydrolysis generates carboxylic acid group's ester group.

6, according to any one composition of claim 1 and 2, wherein polymkeric substance is to be reacted with carboxylic acid anhydride subsequently by the polymer moieties hydrolysis of unsaturated ester to obtain.

7, according to the composition of the arbitrary claim in front, wherein polymkeric substance contains a group that comprises hydrogen and carbon at least, and total carbon atom number is at least 10 carbon atoms in described group.

8, according to the composition of claim 7, wherein said group directly or by carboxylic acid ester groups is connected on the main polymer chain.

9, according to the composition of claim 7, wherein said group is connected on the nitrogen-atoms of amine salt or quaternary ammonium salt.

10, according to the composition of the arbitrary requirement in front, said composition also comprises polyoxyalkylene esters, ether, ester/ether or acid amides/ester, ethene unsaturated ester multipolymer FLOW IMPROVERS, polarity nitrogenous compound or their mixture.

11, according to the composition of claim 10, wherein polyoxyalkylene esters, ether, ester/ether or acid amides/ether contain at least two C ₁₀To C ₃₀Linear saturated alkyl molecular weight is 100 to 5000 polyoxyalkylene glycol.

12, according to the composition of the arbitrary claim in front, the amount that wherein contains the polymkeric substance amine salt is 0.0001 to 5.0 a weight %(active substance of hydrocarbon fuel weight).

13, use polymkeric substance to make the purposes of the FLOW IMPROVERS of liquid hydrocarbon fuel, this polymkeric substance contains more than an amino, and this amino is the salt or the quaternary ammonium salt of primary amine, secondary amine or tertiary amine.

14, according to the purposes of claim 13, wherein fuel is to distillate fuel oil.

15, according to the purposes of any one claim of claim 13 and 14, wherein polymkeric substance is from also containing one or more unsaturated ester polymer of monomers deutero-of free acidic group, or the monomeric multipolymer deutero-of ester from wherein having at least to contain free acidic group.

16, according to the purposes of any one claim of claim 13 and 14, wherein polymkeric substance is the multipolymer deutero-from unsaturated ester and/or alkene and unsaturated acid anhydride.

17, according to the purposes of any one claim of claim 13 and 14, wherein polymkeric substance is from containing the mixture deutero-that partial hydrolysis becomes carboxylic acid group's ester group.

18, according to the purposes of any one claim of claim 13 and 14, wherein polymkeric substance be by the polymkeric substance of the unsaturated ester of partial hydrolysis subsequently with carboxylic acid anhydride reaction deutero-.

19, according to the purposes of any one claim of claim 13 and 18, wherein polymkeric substance contains the group that at least one comprises hydrogen and carbon, and the total carbon atom number of described group is at least 10 carbon atoms.

20, according to the purposes of claim 19, wherein said group directly or by carboxylic acid ester groups is connected on the main polymer chain.

21, according to the purposes of claim 19, wherein said group is connected on the nitrogen-atoms of amine salt or quaternary ammonium salt.

22, according to the purposes of arbitrary claim of claim 13 to 21, wherein liquid hydrocarbon fuels also comprises polyoxyalkylene esters, ether, ester-ether or acid amides/ester, ethene-unsaturated ester multipolymer FLOW IMPROVERS, polarity nitrogenous compound or their mixture.

23, according to the purposes of claim 22, wherein polyoxyalkylene esters, ether, ester/ether or acid amides/ether contain at least two C ₁₀To C ₃₀Straight chain saturated alkyl molecular weight is 100 to 5000 polyoxyalkylene glycol.

24, a kind of solvent and 20～90%(weight of the containing) enriched material of polymkeric substance (is benchmark with the solvent), wherein polymkeric substance comprises more than an amino, and this amino is the salt or the quaternary ammonium salt of primary amine, secondary amine or tertiary amine.

25, according to the enriched material of claim 24, wherein polymkeric substance is from also containing one or more unsaturated ester polymer of monomers deutero-of free acidic group, or from one of them contains the monomeric multipolymer deutero-of unsaturated ester of free acidic group at least.

26, according to the enriched material of claim 24, wherein polymkeric substance is the multipolymer deutero-by undersaturated carboxylic acid anhydride.

27, according to the enriched material of claim 24, wherein polymkeric substance is by containing the polymer-derived that partial hydrolysis becomes carboxylic acid group's ester group.

28, according to the enriched material of claim 24, wherein polymkeric substance is that polymkeric substance from the unsaturated ester of partial hydrolysis makes with the carboxylic acid anhydride reaction subsequently.

29, according to the enriched material of arbitrary claim of claim 24 to 28, wherein polymkeric substance contains at least one hydrogeneous and group carbon, and the total carbon atom number of described group is at least 10 carbon atoms.

30, according to the enriched material of claim 29, wherein said group directly or by carboxylic acid ester groups is connected on the mixture main chain.

31, according to the enriched material of claim 29, wherein said group is connected on the nitrogen-atoms of amine salt or quaternary ammonium salt.