CN1022045C

CN1022045C - Middle distillate composition with improved low temperature properties

Info

Publication number: CN1022045C
Application number: CN 85104294
Authority: CN
Inventors: 卢塔斯·肯尼思
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1984-03-22
Filing date: 1985-06-06
Publication date: 1993-09-08
Anticipated expiration: 2000-06-06
Also published as: CN85104294A

Abstract

Petroleum fuel distillate with the boiling range of 120 DEG C to 500 DEG C has low-temperature properties; a polymer or a copolymer of n-alkyl vinyl ester or fumaric acid ester is added, which causes the cloud point to be reduced and improved, wherein the ester comprises at least 25 wt% of n-alkyl ester with 14 to 18 carbon atoms on the average with the content of no more than 10 wt%, and no more than 10 wt% of alkyl ester with more than 18 carbon atoms on the average.

Description

Middle distillate composition with improved low temperature properties

The mineral oil that contains paraffin when oily temperature drop is low, becomes and is difficult to flowing fluid.It is because wax crystallization becomes tabular crystal that mobile funeral is decreased, and finally forms spongy material and is trapped in the oil.If they can flow, when using pump delivery, these crystal can stop up oil pipe and strainer.

People know already, when various additives contain the mineral oil fusion of wax together, can play the effect of wax crystalls improving agent.These compositions can improve the size and the shape of wax crystalls, and can reduce the bounding force between oil and the wax, can make oil keep mobile at a lower temperature with a kind of like this method.

Various pour point depressants disclosed in the literature, and wherein some has entered commercial applications.For example, United States Patent (USP) the 3rd, 048 is pointed out available ethene and C No. 479 ₃-C ₅Vinyl acetate such as the multipolymer of vinyl-acetic ester, the particularly oil fuel that acts as a fuel, the pour point depressant of diesel oil and jet fuel.Hydro carbons aggretion type pour point depressant based on ethene and alpha-olefin and propylene is also known by people.United States Patent (USP) the 3rd, 961 is pointed out for No. 916, adopts the compound of multipolymer, and one of them be the nucleator of wax crystallization, and another is the inhibitor of crystal growing, so as to controlling the size of wax crystalls.

Similarly No. 1263152 suggestion of English Patent, the size of wax crystalls can be controlled with the multipolymer of low side chain branching.English Patent was also once proposed for No. 1469016, the multipolymer of FUMARIC ACID TECH GRADE di n-alkanyl ester and vinyl-acetic ester (once making the pour point depressant of lubricating oil in the past) with it, when the processing high boiling point distillates fuel, the supplementary additive that can be used as ethylene is to improve their low-temperature fluidity.According to No. the 1469016th, English Patent, these polymkeric substance can be undersaturated C ₄To C ₈The C of dicarboxylic acid ₆To C ₁₆Alkyl ester, especially FUMARIC ACID TECH GRADE dodecyl ester; FUMARIC ACID TECH GRADE dodecyl～cetyl ester.Used typical material is the polymkeric substance by following method preparation:

The fumarate of the alcohol mixture of (I) vinyl-acetic ester and carbonatoms average out to 12.5 (being the polymer A in No. the 1469016th, the English Patent),

(II) vinyl-acetic ester and average carbon atom number are the mixing-fumarate (the polymkeric substance E in the English Patent the 1469016th) of 13.5 alcohol mixtures, and

(III) FUMARIC ACID TECH GRADE two dodecyl esters and methacrylic acid cetyl ester or FUMARIC ACID TECH GRADE two n-hexadecyl esters are with the multipolymer of lauryl methacrylate, and all these multipolymers all are invalid as the additive that distillates fuel.

In the table II of No. the 1542295th, English Patent, point out, polymer B (being the homopolymer of vinylformic acid n-tetradecane base ester) and polymkeric substance C(are the multipolymer of vinylformic acid cetyl ester and methyl methacrylate) itself is as a kind of additive, is invalid to the related fuel type of that part patent.

Along with distillating fuel multifarious increase and need obtain the maximum yield of this gasoline fraction fuel, the multipolymer that resembles ethene and vinyl-acetic ester with traditional additive is handled inapplicable.A kind of approach that improves the yield distillate fuel be to adopt more heavy gas and oil cut (HGO) with distillate cut fusion or the final boiling point (FBP) by raising fuel for example to 370 ℃ with on profoundly cut.Have only in this case, it is useful especially adopting the present invention.

Once find,, do not find as yet that in order to handle above-mentioned these oil fuel it is an effective additives improving the mobile extensively multipolymer of the vinyl-acetic ester of employing of previous those general distillate fuels.In addition, use those cited mixtures in No. the 1469016th, the English Patent, yet do not find its validity as additive of the present invention.

In addition, usually be necessary to reduce the known cloud point that distillates fuel of people, cloud point is the temperature that wax begins to crystallize out from fuel when distillating fuel cooling, this temperature is normally measured with difference formula scanning calorimeter, adopt this measuring method not only when handling above-mentioned oil fuel, to have any problem, and difficulty also takes place at the full range (boiling range of typical oil product is 120 ℃ to 500 ℃) that processing distillates fuel.

We have found the very special multipolymer of a class, it is an effective additives to the size of the wax crystalls that control forms in the oil fuel, and it can make one to be higher than 370 ℃ oil fuel to reluctant final boiling point (FBP) and to test in (PCT) (working relevant at low temperatures with oil fuel) at cold filter plugging test (CFPPT) (relevant with the operability of diesel engine) and programming cool and have filterability.We find that also this analog copolymer is an effective additives to the cloud point that reduces pluralities of fuel oil product full range.Therefore, the present invention is 370 ℃ or surpasses 370 ℃ oil product the petroleum fuel oil that distillates, particularly final boiling point of processing boiling range at 120 ℃ to 1500 ℃, provides a kind of method, in order to improve their cryogenic flowing property.

Particularly we find, containing and containing average carbon atom number in vinyl or the ester group is 14 to 18 positive alkyl fumarate, the ester that wherein contains the alkyl that is lower than 14 carbon atoms is not higher than the 10%(weight percentage), the ester that contains greater than the alkyl of 18 carbon atoms is not higher than the 10%(weight percentage) polymkeric substance or multipolymer be effective additives very.Wherein should select the multipolymer of FUMARIC ACID TECH GRADE two positive hydrocarbyl carbonates and vinyl-acetic ester for use, we find that the fumarate that makes with single alcohol or pure binary mixture is highly effective, when adopting the mixture of alcohol, we mix various alcohol earlier before esterification step, rather than adopt the mixing fumarate that is obtained by sound one alcohol.

In general, we find for the final boiling point boiling range of finding in Europe to be most of oil fuel of 370 ℃ to 410 ℃, and the carbon atom mean number of the positive alkyl of used multipolymer should be between 14 to 17.The cloud point of this fuel is generally-5 to+10 ℃.If final boiling point improves or the heavy gas and oil composition of fuel increases, for example resemble the fuel that finds as Africa, India, South East Asia etc. under the warm climate, the average carbon atom number of so said alkyl should be increased to about 16 to 18.Its final boiling point of these fuel of the latter can surpass 400 ℃ and cloud point and be higher than 10 ℃.

Preferentially select for use as additive of the present invention and to contain the 10%(weight percentage at least) the unsaturated C of a vinyl ₄To C ₈Monobasic or the monoesters of di-carboxylic acid (or acid anhydride) or the polymkeric substance or the multipolymer of di n-alkanyl ester, the carbon atom mean number of wherein positive alkyl is 14 to 18.Calculate with total alkyl number, carbonatoms is not higher than the 10%(weight percentage less than monoesters or two positive alkyl ester of 14 alkyl), and carbonatoms is not higher than the 10%(weight percentage greater than monoesters or two positive alkyl ester of 18 alkyl).The preferably same 10%(weight percentage at least of these unsaturated ester), save those ethene unsaturated ester such as vinyl acetate copolymerizations of being mentioned at supplementary additive one.The number-average molecular weight of this polymkeric substance is 1000 to 100,000, preferably 10000 to 30,000, and the number-average molecular weight of for example using vapor infiltration platen press [as plum gram Nola (Mechrolab) vapour phase pressure permeation instrument] to record.

Be used to prepare the monobasic/dicarboxylic esters of this polymkeric substance, can be represented by the formula:

In the formula, R ₁And R ₂Be hydrogen or C ₁To C ₄Alkyl, as methyl, R ₃Be C ₁₄To C ₁₈Acyloxy of (mean number) (CO.O) or C ₁₄To C ₁₈The carbalkoxy of (mean number) (O.CO), this chain are positive alkyl, R ₄Be hydrogen, R ₂Or R ₃

The monoesters of dicarboxylic acid or dibasic acid esters carry out copolymerization with other unsaturated monomer such as the ester of different amounts (as 0 to 70 mole of %).Here said other unsaturated ester comprises the short-chain alkyl ester, and its general formula is:

R in the formula ₅Be hydrogen or C ₁To C ₄Alkyl, R ₆Be COOR ₈

Or OOCR ₈And R ₈Be C ₁To C ₅The alkyl of side chain or non-side chain, R ₇Be hydrogen or R ₆The example of these short-chain esters is methyl acrylic esters, esters of acrylic acid, fumarate (and maleate) and vinyl esters.More the example of characteristics is methyl methacrylates, vinylformic acid pseudoallyl ester and isobutyl acrylate.And preferably select vinyl-acetic ester and propionate for use for vinyl acetate.

The polymkeric substance that we preferentially select for use is to contain 40 to the 60%(moles/mole) C ₁₄To C ₁₈(mean number) FUMARIC ACID TECH GRADE dialkyl and 60 is to the 40%(moles/mole) vinyl-acetic ester.

Ester polymer generally is at varsol such as heptane; the polymerization by esters monomer under 20 ℃ to 150 ℃ of cyclohexan or light oil solution obtains; usually getting rid of under the protection of indifferent gas such as nitrogen or carbonic acid gas under the condition of oxygen, with superoxide or azo-type catalyzer such as dibenzoyl peroxide or Diisopropyl azodicarboxylate promotion polymerization.Polymkeric substance can prepare in the band pressure of autoclave or by refluxing.

Effective especially when being used in combination with other additive that improves the cold flow properties that distillates fuel proposed above when additive of the present invention, and you will find for the fuel type that the present invention relates to, and it will be effective especially.

Supplementary additive.

Additive of the present invention can and be used with ethene unsaturated ester multipolymer FLOW IMPROVERS.Can comprise undersaturated monoesters or dibasic acid esters with the unsaturated monomer of ethylene copolymer, its general formula is:

R in the formula ₁₀Be hydrogen or methyl; R ₉For-OOCR ₁₂Base, wherein R ₁₂Be hydrogen or C ₁To C ₂₈The straight or branched alkyl, and select C usually for use ₁To C ₁₇, be preferably C ₁To C ₈The straight or branched alkyl; R ₉For-COOR ₁₂Base, wherein R ₁₂Be the alkyl of mentioning in the past but be not hydrogen, R ₁₁For hydrogen or preamble defined-COOR ₁₂Work as R ₁₀And R ₁₁Be hydrogen, R ₉For-OOCR ₁₂The time, monomer is C ₁To C ₂₉, be more generally as C ₁To C ₁₈Monocarboxylic ethene alcohol ester, and must be C well ₂To C ₅Monocarboxylic vinyl acetate.Can be vinyl-acetic ester with the example of the vinyl acetate of ethene generation copolymerization, propionate and isopropylformic acid vinyl acetate, and vinyl-acetic ester is best.In addition, containing 10 to the 40%(weight percentage) multipolymer of vinyl acetate is also relatively good, and preferably contain 25 to the 35%(weight percentage) multipolymer of vinyl acetate.The mixture of those two kinds of multipolymers of mentioning on No. the 3961916th, the United States Patent (USP) also can use.The number-average molecular weight that these multipolymers preferably select for use vapor infiltration to press assay method to record is 1000 to 6000, and preferentially selecting number-average molecular weight is 1000 to 4000 multipolymer.

Additive of the present invention also can be homo-ion or the nonionic polar compound unite use, this polar compound will have the ability of wax crystalls growth inhibitor.Found that the polarity nitrogenous compound is effective especially, these compounds are C normally ₃₀～C ₃₀₀, C preferably ₅₀～C ₁₅₀Amine salt and/or acid amides, and the amine that acid amides is replaced by at least 1 mole of alkyl forms with 1 mole 1～4 carboxylic acid group or its anhydride reaction; Ester/acid amides also can be used, and these nitrogenous compounds are at United States Patent (USP) the 4th, 211, describes on No. 534.Suitable amine is the C of long-chain ₁₂～C ₄₀Primary, secondary, uncle or quaternary amine or their mixture, but as long as the nitrogenous compound that generates is that oil is molten, also can use than the amine of short chain, therefore, they normally contain total carbon atom number is 30 to 300 to replace amine, nitrogenous compound at least also should have a C ₈～C ₄₀The straight chained alkyl segment.

The example of the amine that is fit to comprises tetradecy lamine, coconut amine (cocoamine), hydrogenated tallow amine and analogue.The example of secondary amine comprises 21 octadecylamines, methyl ten or twenty dialkylamine and analogue, and amine mixt also is suitable for, and a lot of amine that obtained by natural goods are mixtures.The amine of preferentially selecting for use is hydrogenated tallow secondary amine, and its general formula is HNR ₁R ₂, R wherein ₁And R ₂All are the alkyl that obtain from hydrogenated tallow, it forms about 4%C ₁₄, 31%C ₁₆, 59%C ₁₈

The example for preparing the suitable carboxylic acid of these nitrogenous compounds (with its acid anhydride) is comprised cyclohexane dicarboxylic acid, tetrahydrobenzene dicarboxylic acid, pentamethylene dicarboxylic acid and analogue thereof.These acid are in should the have an appointment acid or especially preferentially select Tetra hydro Phthalic anhydride for use of the part of ring in general.

Nitrogenous compound preferably has ammonium salt, ammonium salt or an amide group at least.The amine compound of especially preferentially selecting for use is, by the acid amides-amine salt of 1 mole of Tetra hydro Phthalic anhydride with 2 moles of two-hydrogenated tallow amine reaction generations.Another kind of best implementation method is the diamide that this acid amides-amine salt dehydration is generated.

The long-chain ester multipolymer is as additive according to the present invention, can and use with one or both auxiliary type additives mentioned above, also can be with 20/1 to the 1/20(w/w) ratio, be 10/1 to the 1/10(w/w preferably) ratio, be preferably 4/1 to 1/4 ratio and mix.Tertiary mixture also can be used with the ratio of X/Y/Z long-chain ester and supplementary additive 1 with supplementary additive 2, X wherein, and Y and Z are respectively 1 to 20, but are 1 to 10 preferably, and best ratio ranges is 1 to 4.

Additive system of the present invention can provide easily with the enriched material form in oil, mixes during main body distillates fuel.These enriched materials also can contain desired other additive.These enriched materials are preferentially selected for use and are contained 3 to 80%(weight), be to use 5 better to 70%(weight), be preferably 10 to 60%(weight) oil solution of additive.This enriched material also belongs to scope of the present invention.

Additive of the present invention is useful especially to the fuel of handling final boiling point and being higher than 370 ℃, is 0.0001 to 5%(weight in the consumption of the general additive of fuel), and be preferably 0.001 to 2%(weight).

The present invention can illustrate by following example, and the validity of additive of the present invention in these examples can be by pour point depressant and filterability improving agent, illustrates by contrasting with other additive in the following test.

Test

By a kind of method, oil stops up experimental tests (CFPPT) to the response of additive by cold filtration and measures, the implementation method of this test is at 521 volumes such as " institute of Petroleum's magazine " (Journal of the Institute of Petroleum), 510 phases, in June, 1966, describe its operation steps in detail on the 173rd～No. 185.It is relevant with the cold flow properties of middle runnings in the automotive diesel oil that this test design becomes.

Briefly, get 40 milliliters of oil samples to be tested, in the bath of a pact-34 ℃, with about 1 ℃/minute non-linear rate of cooling cooling.Allow the oil that is cooled in specific time, pass through a dusting cover, thereby (at least 2 ℃ of beginnings on cloud point off and on, speed reduction temperature with 1 ℃/minute) tests this oily flow capacity, used testing apparatus is a transfer pipet, the lower end is connected on the anti-phase funnel, oppositely funnel is fixed under the pasta that will test, and the 350 purpose sieve plates that diameter is 12 millimeters definite areas cover in the flare opening.Each with the upper end vacuum system that is connected on transfer pipet, cause and do test off and on, oil is inhaled into by sieve plate thus, up enters transfer pipet, on oil refers to scale at 20ml.After oil successfully passes through at every turn, turn back to cold filtration again two quarters and stop up in the pipe of point (CFPP).

The every reduction of temperature repetitive operation once should be tested, till oil no longer is full of transfer pipet in 50 seconds.At this moment temperature is called as the CFPP temperature.The not additivated CFPP of fuel and contain the CFPP reduction value that difference between the fuel of the same race of additive is known as additive.Under the identical situation of additive concentration, the mobile improving agent of additive is effective more, and then the reduction value of CFPP is just big more.

The another kind of method of measuring FLOW IMPROVERS efficient is under the condition of programming cool test the cut of modification to be made fluidity test (PCT test), and this is a kind of slow cool down test, and this test design becomes the relevant form of oil fuel of storing with pump delivery.The cold flow properties that contains additive fuel is measured by following PCT method.Get 300 milliliters of fuel and be cooled to probe temperature, temperature is remained unchanged with 1 ℃/hour linear velocity.After two hours, siphon away about 20 milliliters of upper layer oil under the mensuration temperature, this is to form very large wax crystalls in the process of cooling on oil/air interface in order to prevent, thus the carrying out of influence test.Wax bottom being deposited on makes it to disperse by the stirring of gentleness, inserts the filter for installation of a CFPPT then.The top connects the vacuum of 500 mmhg, when 200 milliliters fuel enter graduated receiver by strainer, closes vacuum.If in 10 seconds, can collect 200 milliliters of oil fuel of sieve meshes by regulation, then remember one " by "; If flow velocity is too slow, show strainer with blocked, then remember one " not passing through ".

Filter device therefor is that sieve plate is 20,30,40,60, and the CFPPT filter for installation of 80,100,120,150,200,250 and 350 order numbers is in order to measure the thinnest filter screen (maximum order number) that fuel can pass through.The order number that waxy fuel can pass through is big more, and wax crystalls is just more little, and the efficient of the mobile improving agent of additive is just high more.Should be noted that for same FLOW IMPROVERS additive, two kinds of fuel can not provide identical test result on same processing horizontal.

The cloud point that mensuration distillates fuel is measured with standard cloudy test (IP-219 or ASTM-D2500), use Mei Teer (Mettler) TA2000B difference formula scanning calorimeter, by the time of scanning the thermal hysteresis of calorimeter without gauged poor formula, just can estimate the temperature (Wax Appearance Temperature) that wax occurs by measurement to reference sample kerosene.In this calorimeter, get 25 microlitre fuel sample, on the cloud point of estimating at least 10 ℃, with the rate of cooling of 2 ℃ of per minutes sample is cooled off, the cloud point of fuel is temperature to occur and add 6 ℃ and estimate to differ from the indicated wax of formula scanning calorimeter.

Example

Fuel

The fuel used at these examples is:

Fuel I II III IV V

Cloud point *+4+9+8+14+3

Wax appearance point *+3+3+7+13+1

Wax occurs 0-0.3+2.6+8.2-3.9

Temperature ℃

ASTM D-86 distills *

Initial boiling point 196 182 176 180 188

10%

20% 223 234 228 231 236

50% 272 275 276 289 278

90% 370 352 360 385 348

Final boiling point 395 383 392 419 376

In the fuel just

Structure alkane scope * * 10～35 10～36 9～36 9～38 11～30

* degree centigrade value

* kapillary solution-air phase chromatographic determination

Additive therefor

The multipolymer of long-chain ester

The same vinyl-acetic ester of FUMARIC ACID TECH GRADE di n-alkanyl ester (with the 1/1 mol ratio) copolymerization of following straight chain and making.

The polymkeric substance n-alkyl chain is long

A1 10

A2 12

A3 14

A4 16

A5 18

A6 20

Following dibasic ester (weight ratio is 1: 1) be FUMARIC ACID TECH GRADE before esterification, two kinds of alcohol that following chain length is not waited mixed must, carry out copolymerization with vinyl-acetic ester (mol ratio is 1: 1) then and finish.

The polymkeric substance n-alkyl chain is long

B1 10/12

B2 12/14

B3 14/16

B4 16/18

B5 18/20

The multipolymer of two kinds of fumarate-vinyl-acetic esters is that fumarate makes with the mixture generation esterification of the alcohol of certain chain length scope.Various alcohol at first mix then with the FUMARIC ACID TECH GRADE esterification, and last and vinyl-acetic ester (mol ratio is 1: 1) copolymerization obtains being similar to the product of No. 1469016 described polymer A of English Patent.

The polymkeric substance n-alkyl chain is long

8 10 12 14 16 18

C1 9 11 36 30 10 4

C2 10 7 47 17 8 10

The value of the various alcohol of contained n-alkyl chain is that percentage ratio calculates by weight in the mixture, and average carbon atom number is respectively 12.8 and 12.6.

At first make a series of fumarates, synthetic subsequently fumarate-vinyl acetate copolymer.Fumarate series is mixed by 5/2 weight ratio with vinyl-acetic ester, make the method for polymkeric substance E for No. 1469016, obtain following polymkeric substance D with being similar to English Patent.

The n-alkyl chain of polymkeric substance fumarate is long

6 8 10 （12，14）（16，18）

D 4.2 6.2 7.3 38.6 43.7

* coconut oleyl alcohol C ₁₂/ C ₁₄Ratio be approximately the 3/3(w/w)

* FUMARIC ACID TECH GRADE tallow C ₁₆/ C ₁₈Ratio be approximately the 1/2(w/w), its value is in (w/w) %.

The average carbon atom number of polymkeric substance D is 13.9.

The multipolymer of short-chain ester

Vinyl-vinyl acetate copolymer as supplementary additive has following characteristic.

Polymkeric substance VA ^*Mn ^*

E1 17.6 2210

E2 24.6 3900

E3 36 2500

E4 16 2500

E5 the mixture of E3/E4 is the 3/3(w/w)

* VA means vinyl acetate content % meter by weight.

The * number-average molecular weight is to measure with vapour phase osmometer.

The polarity nitrogenous compound

Compound F 17-hydroxy-corticosterone is mixed in 60 ℃ with 1 mole of Tetra hydro Phthalic anhydride, two-hydrogenated tallow amine of 2 moles together and makes.Generate 2-N, the dialkyl ammonium salt of N dialkyl amide benzoic ether.

Test fuel

Take passages fusion additive and cold flow test result in following table, additive concentration is to calculate with per hundred umbers (PPM) in very much in the fuel.

If the CFPP value of the fuel of handling in ℃ it, then the CFPP value is reduced to and is lower than untreated fuel.

The sieve number of PCT value for passing through under-9 ℃, numeral is big more, just easy more the passing through of expression.

Following table shows that the long fumarate-vinyl acetate copolymer of specific n-alkyl chain influences in fuel.

Table 1

Additive concentration CFPP CFPP PCT

(to reduce in the fuel

PPM meter)

E5 175 -6 6 200

E5 300 -12 12 200

A1 175 0 0 40

A1 300 0 0 60

A2 175 0 0 60

A2 300 0 0 60

A3 175 -8 8 250

A3 300 -10 10 250

A4 175 -1 1 60

A4 300 -3 3 60

A5 175 +1 -1 30

A5 300 +1 -1 30

A6 175 0 0 40

A6 300 +1 -1 40

The FUMARIC ACID TECH GRADE tetradecyl ester that this shows usefulness is renderd a service best.

Table 2

In the fuel I, when adding when using vinyl-vinyl acetate copolymer, the long fumarate-vinyl acetate copolymer of specific n-alkyl chain is respectively the 1/4(w/w) the influence of ratio be listed below:

Additive concentration CFPP CFPP PCT

(to reduce in the fuel

PPM meter)

E5+A1 175 -2 2 250

E5+A1 300 -10 10 250

E5+A2 175 -3 3 250

E5+A2 300 -9 9 250

E5+A3 175 -17 17 350

E5+A3 300 -21 21 350

E5+A4 175 -13 13 80

E5+A4 300 -12 12 100

E5+A5 175 -4 4 250

E5+A5 300 -6 6 250

E5+A6 175 -11 11 250

E5+A6 300 -6 6 250

Here observe once more and use C ₁₄The fumarate of alkyl is renderd a service best.

Table 3

In the fuel II, when uniting use with vinyl-vinyl acetate copolymer as ancillary additions, the influence of fumarate-vinyl acetate copolymer that specific n-alkyl chain is long is listed below:

Additive concentration CFPP CFPP PCT

(to reduce in the fuel

PPM meter)

E5+A1 175 -9 9 60

E5+A1 300 -10 10 100

E5+A2 175 -8 8 60

E5+A2 300 -10 10 100

E5+A3 175 -15 15 80

E5+A3 300 -17 17 200

E5+A4 175 0 0 80

E5+A4 300 -3 3 80

E5+A5 175 -9 9 60

E5+A5 300 -10 10 100

E5+A6 175 -9 9 80

E5+A6 300 -10 10 100

Thus, observe once more and use C ₁₄The fumarate of alkyl is renderd a service best.

Table 4

Once found in the fuel I that when with vinyl-vinyl acetate copolymer (weight ratio is respectively 1/4), the influence of the fumarate-vinyl acetate copolymer that makes from the binary blend of adjacent alcohol was listed below:

The positive total concn of additive B series is (with CFPP CFPP PCT

Reduction in the alkyl carbon crude fuel

Sub-mean number PPM meter)

E5+B1 11 175 -10 10 250

E5+B1 11 300 -14 14 250

E5+B2 13 175 -14 14 250

E5+B2 13 300 -17 17 250

E5+B3 15 175 -19 19 350

E5+B3 15 300 -21 21 350

E5+B4 17 175 -7 7 100

E5+B4 17 300 -8 8 100

Here as can be seen, use C ₁₅The fumarate of alkyl is renderd a service best.

Table 5

Once found in the fuel III that when with vinyl-vinyl acetate copolymer (weight ratio is 1/4), the influence of fumarate-vinyl acetate copolymer was listed below:

The total concn of additive A and B series is (with CFPP CFPP

Reduction in the fuel of n-alkyl chain

Carbon atom mean number PPM meter)

E5 - 300 0 3

E5 - 500 -2 5

E5+A1 10 300 +2 1

E5+A1 10 500 0 3

E5+B1 11 300 0 3

E5+B1 11 500 -1 4

E5+A2 12 300 +2 1

E5+A2 12 500 0 3

E5+B2 13 300 0 3

E5+B2 13 500 -1 4

E5+A3 14 300 -10 14

E5+A3 14 500 -14 17

E5+B3 15 300 -14 17

E5+B3 15 500 -13 16

E5+A4 16 300 0 3

E5+A4 16 500 -10 13

E5+B4 17 300 -2 5

E5+B4 17 500 -3 6

E5+A5 18 300 +3 0

E5+A5 18 500 -1 4

Can observe C ₁₄/ C ₁₅The fumarate of alkyl is renderd a service best.

Table 6

Found that in the fuel IV influence that the multipolymer of the same fumarate-vinyl-acetic ester of vinyl-vinyl acetate copolymer (weight ratio is respectively 1/4) is united when using is listed below:

Positive alkyl total concn CFPP CFPP in additive A and the B series

The carbon atom mean number of chain reduces

E5 - 300 +5 5

E5 - 500 +5 5

E5+A1 10 300 +5 5

E5+A1 10 500 +5 5

E5+B1 11 300 +6 6

E5+B1 11 500 +5 5

E5+A2 12 300 +5 5

E5+A2 12 500 +4 6

E5+B2 13 300 +5 5

E5+B2 13 500 +5 5

E5+A3 14 300 +6 6

E5+A3 14 500 +5 5

E5+B3 15 300 -9 4

E5+B3 15 500 -11 5

E5+A4 16 300 -5 15

E5+A4 16 500 -10 20

E5+B4 17 300 +5 5

E5+B4 17 500 +3 7

E5+A5 18 300 +6 4

E5+A5 18 500 +2 8

Here observe C again ₁₄/ C ₁₅Effectiveness the best of the fumarate of alkyl.

Table 7

We find that the influence of the same fumarate-vinyl acetate copolymer of vinyl-vinyl acetate copolymer (weight ratio is respectively 1/1) is listed below in the fuel III, and with itself ethylene comparison.

Additive total concn CFPP CFPP reduces

E1 300 -7 10

E2 300 +1 2

E5 300 -1 4

E1+A3 300 -11 14

E1+C1 300 0 3

E1+C2 300 +1 2

E1+D 300 -5 8

E2+A3 300 -11 14

E2+C1 300 +2 1

E2+C2 300 +1 2

E2+D 300 -5 8

E5+A3 300 -10 14

E5+C1 300 +2 1

E5+C2 300 -1 4

E5+D 300 -5 8

Table 8

We find to contain fumarate-vinyl acetate copolymer in the fuel V, and the three component additives of vinyl-vinyl acetate copolymer and polarity nitrogenous compound and the influence of usefulness are listed below:

Additive is also used total concn CFPP CFPP PCT

Reduce

E5+A3 4/1 375 -13 12 120

E5+A3 4/1 625 -15 14 200

E5+A3+F 4/1/1 375 -15 14 250

E5+A3+F 4/1/1 625 -16 15 250

Table 9

We find that the influence of various binary and ternary component additive and usefulness is listed below in the fuel I.

Additive also uses total concn CFPP to reduce PCT

E5 -175 6 200

E5 -300 12 200

E5+A3 4/1 175 17 350

E5+A3 4/1 300 21 350

E5+A3+F 4/1/1 175 19 350

E5+A3+F 4/1/1 300 22 350

Table 10

Fumarate-the vinyl acetate copolymer of specific n-alkyl chain length is listed below the influence of fuel III pour point:

The depression of pour point of additive concentration pour point

A2 500 +3 0

A3 500 -15 18

A4 500 -9 12

A5 500 -9 12

Nothing-+3-

Pour point ASTM D-97 test determination.

Additive of the present invention occurs Temperature Influence for the fuel I of using previously to V and fuel VI wax, the following character that records

180 ℃ of initial boiling points

20% o'clock heat up in a steamer a little 223 ℃

90% the time heat up in a steamer a little 336 ℃

Network heats up in a steamer a little 365 ℃

Temperature-9.4 ℃ appears in wax

Cloud point-2 ℃

And with itself invention scope other additive contrast in addition.

Fuel VI additive

The change of temperature appears in quantity (PPM) wax

FUMARIC ACID TECH GRADE ester in the last of the ten Heavenly stems/200+0.2 ℃

500-0.6 ℃ of vinyl acetate copolymers

FUMARIC ACID TECH GRADE ten diester/200+0.1 ℃

500-1.0 ℃ of vinyl acetate copolymers

FUMARIC ACID TECH GRADE 14 esters/200-1.2 ℃

500-1.0 ℃ of vinyl acetate copolymers

FUMARIC ACID TECH GRADE hexadecyl ester/200-2.6 ℃

500-2.1 ℃ of vinyl acetate copolymers

FUMARIC ACID TECH GRADE octadecyl ester/200-0.7 ℃

500 0 ℃ of vinyl acetate copolymers

FUMARIC ACID TECH GRADE 20 esters/200+0.3 ℃

500+0.9 ℃ of vinyl acetate copolymers

The change of temperature appears in fuel IV amount of additives (PPM) wax

500-0.4 ℃ of FUMARIC ACID TECH GRADE ester/vinyl acetate copolymers in the last of the ten Heavenly stems

500-0.5 ℃ of FUMARIC ACID TECH GRADE ten diester/vinyl acetate copolymer

500-0.4 ℃ of FUMARIC ACID TECH GRADE 14 esters/vinyl acetate copolymer

500-2.6 ℃ of FUMARIC ACID TECH GRADE hexadecyl ester/vinyl acetate copolymers

500-3.6 ℃ of FUMARIC ACID TECH GRADE octadecyl ester/vinyl acetate copolymers

500-1.4 ℃ of FUMARIC ACID TECH GRADE 20 esters/vinyl acetate copolymer

The change of temperature appears in fuel III amount of additives (PPM) wax

500-0.2 ℃ of FUMARIC ACID TECH GRADE ten diester/vinyl acetate copolymer

500-0.2 ℃ of FUMARIC ACID TECH GRADE 14 esters/vinyl acetate copolymer

500-4.1 ℃ of FUMARIC ACID TECH GRADE hexadecyl ester/vinyl acetate copolymers

500-3.3 ℃ of FUMARIC ACID TECH GRADE octadecyl ester/vinyl acetate copolymers

500-1.1 ℃ of FUMARIC ACID TECH GRADE 20 esters/vinyl acetate copolymer

The change of temperature appears in fuel V amount of additives (PPM) wax

625+0.1 ℃ of FUMARIC ACID TECH GRADE ester/vinyl acetate copolymers in the last of the ten Heavenly stems

625 0 ℃ of FUMARIC ACID TECH GRADE ten diester/vinyl acetate copolymer

625-0.9 ℃ of FUMARIC ACID TECH GRADE 14 esters/vinyl acetate copolymer

625-3.3 ℃ of FUMARIC ACID TECH GRADE hexadecyl ester/vinyl acetate copolymers

625-1.5 ℃ of FUMARIC ACID TECH GRADE octadecyl ester/vinyl acetate copolymers

625-0.1 ℃ of FUMARIC ACID TECH GRADE 20 esters/vinyl acetate copolymer

Claims

1, with polymkeric substance or multipolymer as additive to improve the boiling range scope 120 ℃ of purposes to 500 ℃ of low-temperature performancies that distillate fuel, wherein polymkeric substance or multipolymer are following general formula ester polymer of monomers or multipolymer

R in the formula ¹And R ²All represent hydrogen or C ₁-C ₄Alkyl;

R ³Represent C ₁₄-C ₁₈(on average) COO or C ₁₄-C ₁₈(on average) OCO, chain are n-alkyl chain; And

R ⁴Represent hydrogen or C ₁-C ₄Alkyl or R ³,

And containing this ester of the alkyl that is less than 14 carbon atoms and no more than 10% (w/w), this ester of no more than 10% (w/w) contains alkyl more than 18 carbon atoms,

The additive that contains 0.001% to 2% (weight) in the said fuel in weight of fuel, and contain no more than 5 carbon atoms in any other ester comonomer.

2, according to the described purposes of claim 1, wherein the final boiling point of fuel is equal to or higher than 370 ℃.

3, according to the described purposes of claim 1, wherein used multipolymer is the multipolymer of vinyl-acetic ester with the FUMARIC ACID TECH GRADE di n-alkanyl ester.

4,, wherein unite use with the cold flow improver of short-chain ester according to the described purposes of claim 1.

5, according to the described purposes of claim 4, wherein the cold flow improver of short-chain ester is ethene and C ₁To C ₄The multipolymer of the vinyl acetate of carboxylic acid.

6, according to any one described purposes in the claim 1 to 5, wherein additive and polarity nitrogenous compound use together.

7, the boiling range scope is 120 ℃ to 500 ℃ a petroleum distillate, wherein contains 0.001% to 2%(weight) polymkeric substance or multipolymer, wherein polymkeric substance or multipolymer are following general formula ester polymer of monomers or multipolymer

R in the formula ¹And R ²All represent hydrogen or C ₁-C ₄Alkyl;

R ⁴Represent hydrogen or C ₁-C ₄Alkyl or R ³,

And no more than 10%(w/w) this ester contains alkyl and the no more than 10%(w/w that is less than 14 carbon atoms) this ester contain alkyl more than 18 carbon atoms, and contain no more than 5 carbon atoms in other ester comonomer.

8, according to the described petroleum distillate of claim 7, wherein final boiling point is equal to or higher than 370 ℃.

9, according to the described petroleum distillate of claim 7, wherein used multipolymer is the multipolymer that vinyl-acetic ester and FUMARIC ACID TECH GRADE di n-alkanyl ester constitute.

10,, wherein all contain the cold flow improver of short-chain ester according to the described petroleum distillate of claim 7.

11, according to the described petroleum distillate of claim 10, wherein the cold flow improver of short-chain ester is ethene and C ₁To C ₄The multipolymer of the vinyl acetate of carboxylic acid.

12, according to any one described petroleum distillate in the claim 7 to 11, wherein also contain the polarity nitrogenous compound.