CN1024014C

CN1024014C - Liquid fuel compositions

Info

Publication number: CN1024014C
Application number: CN87102962A
Authority: CN
Inventors: 布朗·杰拉尔德·爱恩; 科斯特洛·琼·凯瑟林
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 1986-03-18
Filing date: 1987-03-17
Publication date: 1994-03-16
Anticipated expiration: 2002-03-17
Also published as: KR870008998A; AU7014187A; JP2514199B2; GB8609293D0; DE3788585D1; EP0239320B1; EP0239320A2; AU590827B2; JPS62270687A; KR950009004B1; DE3788585T2; EP0239320A3; ES2048157T3; CN87102962A

Abstract

The response to low temperature flow improvers to a distillate fuel containing between 4 and l0 wt % wax at l0 DEG C below cloud point and containing substantially no paraffins longer than n-triacontane, is enhanced by the addition of n-alkanes to provide C24 and higher alkanes in an amount greater than 0.35 wt.% of the fuel.

Description

Liquid fuel compositions

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

Contain heating oil and other cut oil fuel of straight-chain paraffin wax, as diesel oil, certainly will be settled out bulky crystal when low temperature, the gel structure of setting up like this causes oil fuel to lose its flowability.Oil fuel still can the mobile minimum temperature be commonly referred to pour point.

When the oil fuel temperature reaches or is lower than its pour point, when oil fuel can not freely flow again, will cause difficulty with pipeline and pump delivery oil fuel, for example when attempt to utilize gravity or pump pressure with oil fuel from a storage vessel be transported to another defeated will difficulty when depositing container or attempting that oil fuel added burner.

More than pour point temperature, the crystal that produces in the solution also often stops up oil fuel pipeline, screen cloth and strainer.These problem past are well-known, and have the people to advise using various additives with pour point that reduces oil fuel and the size that reduces wax crystalls.One of function of these additives is to change sedimentary crystalline character from oil fuel, thereby reduces the possibility that wax crystalls forms gel.Tiny crystal is an ideal, and the wax that is settled out like this will can not be blocked in the pore screen cloth that uses in transportation, storage and the blending equipment of oil fuel.Optimal oil fuel not only should have lower pour point (flow point), and should form tiny wax crystalline substance, and the obstruction of strainer will can not weaken flowing of oil fuel under low service temperature like this.

To below the cloud point 10 ℃ contain that to add mainly be that the FLOW IMPROVERS of ethylene-ethyl acetate copolymer (EVA) base can effectively be improved wax crystalline substance (with CFPP and the test of other processing property, and with simulation and field performance mensuration) in the distillate of 4Wt% normal paraffin (measuring with gravimetry or dsc (DSC)).Usually the oil refining worker adjusts the ASTMD-86 distillation characteristics of distillate so that afterbody 90% cut to the temperature difference between the final boiling point is increased to 20～25 ℃ of susceptibility that promote additive in these cuts.

United States Patent (USP) 3020696 propose U.S. nineteen sixty-eight general low wax content intermediate distillate fuel oil to being improved by mixing a spot of paraffin according to the ethene of French Patent 1461008 preparations and the susceptibility of vinyl acetate copolymer, the consumption of paraffin is 0.03～2wt%, and the molecular-weight average of paraffin is 300～650.Similarly, the intermediate oil that United States Patent (USP) 3040691 proposes same types can be improved by adding aliphatic fraction oil to the susceptibility of identical additive, and said aliphatic fraction oil contains than the higher and high alkane to positive tetracontane of n-hexacosane so that C to be provided ₂₄The amount of higher grade normal paraffin is 0.1～2wt%.In these patents, add C ₂₄More high-grade wax is minimum is 0.1wt%, and maximum is 0.3wt%, all shows and has improved susceptibility.

Yet, when handling high wax content narrow-boiling range fraction, during as those cuts that run into Australia in the Far East, although these cuts have similar distillation characteristics, but have higher wax content (with DSC method or gravimetry measure below cloud point 10 ℃ the time wax content be 5～10wt%), and different carbon number distribution is arranged, particularly at C ₂₂～C ₂₈Scope in the time, above-mentioned those ways are invalid.Difficulty is to handle the oil fuel that those have high wax content and low final boiling point is arranged especially, and promptly final boiling point is no more than 370 ℃, also will be lower than 360 ℃ oil fuel sometimes, and these oil fuel have high wax content in narrow carbon number distribution scope.The most difficult is to handle those from high-wax oil, and as the oil fuel that obtains from the crude oil of Australia and the Far East Area, the normal paraffin total content that these oil fuel are measured cut with the solution-air chromatography can all contain C greater than 20% ₁₂High-grade normal paraffin more.

Recently, total wax content that Japanese Patent prospectus 615811586 proposes to pass through fuel metering oil is preferably improved the susceptibility of middle runnings to fluidity improver by the method for concocting high and low wax content fuel at 5.5～12wt%.Wax content is the wax that is settled out from a gram oil fuel with butanone in the time of-20 ℃.This technology is not gratifying to the wax content of the oil fuel by additive treating, because it is in the cloud point of oil fuel and is added the wax that is settled out between the processing property point that agent handles, and processing property point is important to the cold property of oil fuel.We find experience the total wax content that performance do not depend on oil fuel of these oil fuel to FLOW IMPROVERS.

The more unmanageable distillate fuel oil of a kind of typical case, it contains the wax of 5～10wt% 10 ℃ the time and/or contains normal paraffin C more than the 20wt% under its cloud point ₁₂₊, it has following ASTM D-86 characteristic:

212 ℃ of initial boiling points

5% 234℃

10% 243℃

20% 255℃

30% 263℃

40% 279℃

50% 288℃

60% 298℃

70% 303℃

80% 321℃

90% 334℃

95% 343℃

361 ℃ of final boiling point

We find, contrast with the Japanese patent application of introducing previously 615811586, such distillate fuel oil can improve the material of adding is widened the carbonatoms of wax content in the scope that limits wax content distribution by add some material in oil fuel to the susceptibility of FLOW IMPROVERS.

Mainly contain (by weight) distillate fuel oil according to liquid fuel oil compositions of the present invention, this distillate fuel oil contains the wax of 4～10wt% and narrower distribution of normal alkanes is arranged 10 ℃ the time under cloud point, promptly is substantially free of than positive triacontane (C ₃₀) high-grade alkane more, the fuel composition of this liquid also contains the cold flow improver of (by distillate fuel oil) 0.001～2.0wt% and the normal paraffin of the interpolation of 0.001～2.0wt%, C in the normal paraffin that is added ₂₄More the amount of high-grade alkane is greater than the 0.35wt% of oil fuel weight.

In addition according to the present invention, cold flow improver is applied to distillate fuel oil, this distillate fuel oil content of wax 4～10wt% and narrower carbon number distribution is arranged 10 ℃ time the under cloud point promptly is substantially free of the positive triacontane (C than the mixture of the normal paraffin of distillate fuel oil FLOW IMPROVERS and interpolation ₃₀) high-grade alkane more, the normal paraffin C that is added ₂₄More the amount of higher alkane is greater than the 0.35wt% of oil fuel weight.

Used FLOW IMPROVERS can be any FLOW IMPROVERS commonly used among the present invention, yet we recommend to use the FLOW IMPROVERS that contains ethene and at least a second kind of unsaturated monomer copolymer type.This second kind of unsaturated monomer can be another kind of monoolefine, for example C ₃～C ₁₈α-monoolefine maybe can be a kind of unsaturated ester, as vinyl-acetic ester, vinyl butyrate, propionate, isopropylformic acid lauryl, ethyl propenoate or other analogue.This second kind of monomer also can be the mixture of unsaturated monoesters or dibasic acid esters and side chain or straight chain alpha-monoolefine.Also can use the mixture of multipolymer, for example the multipolymer of ethene and vinyl-acetic ester and alkylating polystyrene or with the mixture of the polystyrene of acidylate.Adoptable other material has maleic anhydride copolymers, poly-alpha olefins of aminosuccinic acid derivative, ester class such as polyacrylic ester and esterification or the like.

The preferable distillate fuel oil FLOW IMPROVERS of using among the present invention is to contain 1～40 by every mole of unsaturated hydrocarbon monomer, better be 1～20, the ethene that is more preferably 3～20 moles is formed, wherein the ethylenic unsaturation monomer can be single monomer or the such monomer mixture with arbitrary proportion, said polymkeric substance is that molten and its molecular-weight average of oil is about 1000～50000, preferably about 1000～5000.Molecular weight can use cryoscopy or vapor infiltration platen press to measure, and for example uses Mei Keluobei (Mechrolab) vapour phase osmometer 310A type determining molecular weight.

Unsaturated monomer can homopolymerization or with ethene or its mutual copolymerization, it comprises unsaturated acid, acid anhydrides, monoesters and diester, general formula is as follows:

R in the formula ₁Be hydrogen or methyl; R ₃Be-OOCR ₄Or-COOR ₄Base, wherein R ₄Be hydrogen or C ₁～C ₁₆, C preferably ₁～C ₄The straight or branched alkyl, and R ₃Be hydrogen or-COOR ₄Work as R ₁With R ₃Be hydrogen and R ₂Be-OOCR ₄The time, monomer comprises C ₂～C ₇Monocarboxylic ethene alcohol ester.The example of these esters comprises ethyl acetate, ethyl isobutyrate, Laurate ethyl, ethyl myristate, ethyl palmitate or the like.Work as R ₂Be-COOR ₄The time these esters comprise C ₈The palm alcohol ester of the acrylate of oxo alcohol, methyl acrylate, methyl methacrylate, lauryl acrylate, methylacrylic acid isobutyl ester, α-methylacrylic acid, the C of methylacrylic acid ₁₃Oxo process alcohol ester or the like.Work as R ₁Be hydrogen and R ₂And R ₃All be-OOCR ₄The time monomeric example comprise single C ₁₂The fumarate of oxo alcohol, toxilic acid diisopropyl ester, FUMARIC ACID TECH GRADE dilauryl ester, FUMARIC ACID TECH GRADE ethyl-methyl ester; Fumaric acid, toxilic acid or the like.Work as R ₂Be hydrogen, R ₁Be COOR ₄And R ₃Be CH ₂COOR ₄The time, monomer is an itaconic ester.

What in the present invention, be used to prepare pour point reducer or FLOW IMPROVERS can comprise C with other unsaturated monomer of ethylene copolymerization ₃～C ₁₆Side chain or straight chain alpha-monoolefine, for example propylene, positive octene-1,2-ethyl decylene-1, positive decylene-1 or the like.

The third monomer that in multipolymer, also can comprise a small amount of (0～20 molecular fraction according to appointment), even the 4th kind of monomer, for example C ₂～C ₁₆Side chain or straight chain alpha-monoolefine, as propylene, positive octene-1, positive decylene-1 or the like.Therefore, 30～99%(mole of 3～40 moles ethene and 1 mole) unsaturated ester and 70～1%(mole) the multipolymer of mixture of alkene also can use.

Formed these multipolymers are random copolymerss of mainly being made up of the ethene polymers main chain of the side chain that is distributed with the hydrocarbon that hydrocarbon or oxygen replaces.

Preparing the used alcohol of above-mentioned ester is (as C by alkene ₃～C ₄The polymkeric substance of monoolefine and multipolymer) heterogeneous mixture of side chain primary aliphatic alcohols of preparation, alkene and carbon monoxide and H-H reaction in the presence of cobalt-containing catalyst (as cobalt-carbonyl), temperature of reaction is 300 °F～400 °F, reaction pressure is 1000～3000psi, generate aldehyde, then the aldehyde product hydrogenation that obtains is generated alcohol, pure available distillating method reclaims from hydrogenation products.

Also preferentially select the multipolymer of the low branching of those side chains for use, particularly those contain in per 100 methyl and are less than 10, preferably be less than the multipolymer that 8 methyl stop side chain (except the ester group), it uses nmr for the determination, the most handy 500 megahertz proton nuclear magnetic resonance analysis.

The working concentration of FLOW IMPROVERS is about 0.001～2wt% by processed distillate fuel oil, preferably about 0.005～0.2wt%.

Second kind of additive provides greater than C ₂₄Normal paraffin, and preferably carbon atom is distributed in about 20～40 wax.Although also can contain a spot of branched-chain hydrocarbon in the wax, we wish that still wax mainly is made up of straight-chain paraffin.The wax that adds can be the logistics of pure wax or refinery, ballast gas oil as usual, vacuum gas oil or cracking heavy gas oil, and these refinery logistics contain the wax of carbonatoms limited amount within the required range.Can think that the wax that adds is the nucleus of n-alkane crystallization in oil fuel, and with the normal paraffin cocrystallization that from oil fuel, is precipitated out at first.Therefore, the preferred distribution of normal alkanes of the wax of interpolation depends on specific fuel.Though C ₂₄More the high-grade normal paraffin component should be greater than the 0.35wt% of oil fuel weight, but we recommend its value should be greater than the 0.5wt% of oil fuel weight.

Also can use other additive further to improve low-temperature performance, hydrazine for example, the preferably half amide of dicarboxyl acid or anhydride (as Tetra hydro Phthalic anhydride), half amine salt and can add the secondary amine that alkyl preferably contains 12～20 carbon atoms.Particularly preferred compound is half amide, half amine salt and the dihydro fat amine-positive C of the nearly 4wt% of Armeen 2HT(of phthalic acid ₁₄Alkyl, the positive C of 30wt% ₁₆Alkyl, the positive C of 60wt% ₁₈Alkyl, all the other then are unsaturatess).The addition of hydrazine, half amide, half amine salt is 0.001～2wt% of distillate fuel weight of oil, preferably 0.005～0.2wt% normally.

The example of other additive is a glycol ester, as defined those esters in our EP0061895B; The multipolymer of the amine of these esters and maleic anhydride is as defined those multipolymers in the EP publication number 0214786; The amine of polyolefine and chlorinatedpolyolefins and alkyl succinic anhydride or acid amides.

In distillate fuel oil, add the low-temperature fluidity that wax-naphthalene condenses can further improve distillate fuel oil.Typical condenses is the C that contains normal chain and side chain by chlorination ₁₈～C ₃₉(average out to C ₂₆) wax of alkane, obtain containing the have an appointment chlorinated wax of 15wt% chlorine and prepare.The chlorinated wax that obtains like this obtains a kind of applicable alternately wax and unitary condenses of naphthalene of containing through alkylated reaction and naphthalene polymerization.

The amount of the condenses that adds is generally 0.00005～0.1wt% in the weight of distillate fuel oil.

Additive of the present invention usually merges in the main fuel as enriched material, the present invention further provides a kind of enriched material, it comprises and contains 30～70wt%, the solution of the multipolymer of the ethene of best 40～60wt% and the unsaturated monomer of other alkene and the mixture of chloroflo.

Use following additive in an embodiment:

The solution of the mixture of two kinds of vinyl-vinyl acetate copolymers of additive 1:63wt% is sold by Exxon (Exxon) chemical company, and commodity are called ECA8400.

Additive 2: additive 1 adds wax-naphthalene condenses of 10wt%.

Additive 3: a kind of half amide-half amine salt of the phthalic acid by (1) vinyl-vinyl acetate copolymer (2 parts of weights) (2) wax-naphthalene condenses and (3) 1 parts of weights and the mixture that dihydro fat amine (Armeen 2HT) is formed.The amount of wax-naphthalene condenses accounts for the 5wt% of multipolymer (1) and half amide-half amine salt (2) gross weight.

Additive 4: be about the vinyl-vinyl acetate copolymer of 2000 high branching according to the molecular weight of the 45wt% of French Patent 1461008 preparation, and the content of vinyl-acetic ester is the solution of 30wt%.

Additive 5: the commodity of being sold by Exxon Corporation are called the vinyl-vinyl acetate copolymer of paraflow (Paraflow) 206 and the concoction of fumaric acid-vinyl acetate copolymer.

Additive 6: a kind of enriched material as arene diluent is made up of the mixture of two kinds of vinyl-vinyl acetate copolymers of about 50wt%, the wax growth hold back agent of the 75wt% that has an appointment in this multipolymer and about 25wt% nucleator.Wax growth hold back agent is made up of ethene and about 38wt% vinyl-acetic ester, and its number-average molecular weight is about 25～35.Nucleator is made up of ethene and about 16wt% vinyl-acetic ester, and its number-average molecular weight is about 3000(VPO).This multipolymer is represented with multipolymer H in English Patent 1374051.

Embodiment 1

To cloud point is+3 ℃, and pour point is for-3 ℃ and have following ASTM D-86 feature:

244 ℃ of initial boiling points

10% 256℃

20% 263℃

50% 294℃

90% 340℃

95% 351℃

358 ℃ of final boiling point

And wax content is about in the distillate fuel of 5.7wt% and adds 1500ppm additive 1 10 ℃ the time below cloud point.

The ability of oil fuel by strainer stopped up experimental tests (CFPPT) evaluation with filter at low temperature, and the operation steps of test is at " Institute of Petroleum's will " volume 52, and No.510 has detailed description in the 173rd～185 page of June in 1966.Briefly, exactly the 40 milliliters of oil samples that will test are put into and maintained approximately-34 ℃ cryostat and cool off, periodically (by being not less than more than the cloud point 1 ℃ of 5 ℃ of every reduction of beginning) test refrigerative oil is surveyed it flows through the pore screen cloth in the regular hour ability.The equipment that the test cryogenic properties is used is made up of a transfer pipet, and its low end links to each other with a upside down funnel that is positioned at test oil liquid level below.The mouth of the expansion of funnel is 350 mesh sieve that area is about 0.45 square inch.Routine test is when beginning the upper end of transfer pipet to be vacuumized at every turn, enters transfer pipet thereby oil drawn up by sieve, up to the mark that indicates 20 milliliters of oil.The every reduction of temperature repeats single test for 1 ℃, till shortage of oil is with the mark of filling with 20 milliliters of oil in the transfer pipet.

1 ℃ of revision test of the every reduction of temperature once, up to oil can not be filled with transfer pipet in 60 seconds till.Temperature when record begins to filter for the last time, and note is done filter at low temperature obstruction point.

Untreated fuel and the ethylene solution that contains 1500ppm are-1 ℃ as the CFPP value of the fuel of unique additive.

The wax adding of following commercially available different amounts is contained in the fuel of ethylene.

The wax mark

The chemical wax A of A A Situo (Astor)

B shell (Shell) wax 130/135

C shell (Shell) wax 125/130

The chemical wax B of D A Situo (Astor)

The distribution of normal alkanes of these waxes is as follows:

Carbonatoms A B C D

17

18

19

20 0.194 0.028 0.230

21 1.220 0.245 1.155 0.031

22 4.120 1.309 2.733 0.094

23 7.940 3.750 5.771 0.258

24 11.760 7.118 9.095 0.570

25 12.490 8.370 10.300 0.970

26 12.650 9.996 11.052 1.606

27 10.730 8.847 9.998 2.530

Carbonatoms A B C D

28 8.460 8.083 8.521 3.930

29 6.300 6.769 6.762 6.470

30 3.560 5.703 4.055 8.760

31 1.840 4.343 1.944 10.290

32 1.104 3.533 0.849 9.280

33 0.603 2.520 0.377 7.770

34 0.384 1.788 0.203 5.790

35 0.320 1.093 0.175 4.450

36 0.225 0.655 0.093 3.390

37 0.361 0.102 2.650

38 0.190 0.054 1.680

39 0.078 1.390

40 0.044 1.090

41 0.730

42 0.560

43 0.320

44 0.200

The CFPP test of the fuel of handling obtains following result:

The wax usage quantity wt% CFPP value of using

(based on oil fuel) ℃

A 0.1 -3

0.3 -5

0.5 -11

B 0.1 -3

0.3 -7

0.5 -10

C 0.1 -2

0.3 -9

0.5 -12

D 0.1 0

0.3 -1

0.5 -1

Every kind of wax uses as unique additive, and the CFPP performance is not had influence.

Embodiment 2

The cloud point that is obtained by Chinese crude oil has following ASTMD-86 characteristic for+6 ℃ high waxy distillate fraction oil fuel:

212.8 ℃ of initial boiling points

5% 234.8℃

10% 243.8℃

20% 255.8℃

30% 263.4℃

40% 279.1℃

50% 288.8℃

60% 298.6℃

70% 303.3℃

80% 321.0℃

90% 334.8℃

95% 343.8℃

361.0 ℃ of final boiling point

And wax content is about 8wt% during following 10 ℃ of cloud point.Interpolation 7%(volume in this distillate fuel oil) vacuum gas oil (VGO), the normal paraffin of this vacuum gas oil is essentially C ₂₅～C ₃₅And following ASTM D-86 distillation characteristics arranged:

252.0 ℃ of initial boiling points

10% 301.5℃

50% 358.0℃

90% 435.0℃

480.0 ℃ of final boiling point

The distribution of normal alkanes of oil fuel and vacuum gas oil is as follows:

Oil fuel VGO

C ₁₂0.71

C ₁₃1.08

C ₁₄1.80

C ₁₅2.59

C ₁₆2.25

C ₁₈2.53 0.40

C ₁₉2.37 0.81

C ₂₀2.19 1.81

C ₂₁2.12 2.59

C ₂₂1.70 3.74

C ₂₃0.97 4.39

C ₂₄0.43 4.29

C ₂₅0.18 3.94

C ₂₆0.08 3.24

C ₂₇0.03 2.36

C ₂₈0.02 1.95

C ₂₉0.01 1.02

C ₃₀0.003 0.73

C ₃₁0.44

C ₃₂0.26

C ₃₃0.15

C ₃₄0.14

C ₃₅0.09

C ₃₆0.03

C ₃₇0.05

C ₃₈0.02

Basic fuel oil contains the C of 23.40wt% ₁₂High-grade normal paraffin more.

Use above-mentioned cut to prepare following concoction as basic fuel:

A B

Basic fuel wt% 100 95

Vacuum gas oil wt% 5

D.86 the distillation characteristics of concoction is:

IBP 212 210

20% 256 258

50% 289 292

90% 335 340

FBP 361 370

The C that adds ⁺ ₂₄Normal paraffin-0.93

To the CFPP susceptibility of additive 2 (℃)

0ppm +6 +6

1000ppm +5 +1

Containing 1250ppm additive 3-filter at low temperature obstruction point is-1 ℃.

Embodiment 3

In this embodiment, has the highest normal paraffin C in cloud point for adding respectively in+3 ℃ the basic fuel oil ₃₂, cloud point is that+12 ℃ vacuum gas oil (VGO) and cloud point is+35 ℃, normal paraffin is up to C ₃₃The cracking heavy distillate compare, said basic fuel oil is with Australian Bath Sterrett (Bass Strait) crude production, recording wax content with the wax precipitator method 10 ℃ the time below cloud point is 8.8wt%.

The composition of each component is:

The heavy cracked oil basic fuel of VGO

The distillation gas chromatography D.86

IBP 221 230 224

10% 295 336 247

20% 319 348 256

50% 361 366 276

90% 430 387 316

95% 446 400 325

FBP 491 334

Wax content wt% 3.0 15.4 8.8

Distribution of normal alkanes (accounting for the wt% of fuel)

C ₁₀0.21

C ₁₁0.41

C ₁₂0.06 0.83

C ₁₃0.13 0.03 2.24

C ₁₄0.27 0.10 3.52

C ₁₅0.44 0.14 3.75

C ₁₆0.65 0.17 3.71

C ₁₇0.87 0.22 3.51

C ₁₈1.04 0.27 3.26

C ₁₉1.20 0.53 3.08

C ₂₀1.46 1.16 2.17

C ₂₁1.28 2.75 0.96

C ₂₂1.13 3.50 0.19

C ₂₃0.88 4.25 0.04

C ₂₄0.64 7.94 0.01

C ₂₅0.47 2.87

C ₂₆0.40 1.76

C ₂₇0.35 1.08

C ₂₈0.28 0.48

C ₂₉0.25 0.24

C ₃₀0.14 0.09

C ₃₁0.08 0.04

C ₃₂0.02 0.01

C ₃₃- 0.01

This basic fuel contains 27.3wt%C ₁₂High-grade alkane more.

Prepare following concoction:

1 2 3

Kerosene wt% 10 10-

Basic fuel wt% 75 75 100

VGO wt% 15 - -

Cracking last running wt%-15-

The D-86 distillation characteristics of this concoction is as follows:

IBP 201 202 224

20% 250 251 256

50% 279 281 276

90% 335 350 316

FBP 370 391 334

The C that adds ⁺ ₂₄Normal paraffin 0.39 2.18-

CFPP susceptibility to following additive is as follows;

Amount concoction 1 concoction 2 concoctions 3 of additive

Additives additives additives

4 5 4 5 4 5

0 ppm -1 -1 5 5 -3 -3

500 ppm -1 -1 2 -2 -3 -3

1000 ppm -2 -2 -1 -9 -3 -3

1500 ppm -2 -2 -1 -10 -3 -3

Embodiment 4

In this embodiment, add C in cloud point respectively in+7 ℃ the basic fuel ₃₂～C ₃₃Normal paraffin and compare by the heavy gas oil logistics that contains higher grade normal paraffin (HGO-1 and HGO-2) that Chinese grand celebration waxy crude oil obtains.

The characteristic of these components is as follows:

Basic fuel VGO-A VGO-B HGO-1 HGO-2

The distillation type is GC GC GC GC D.86

IBP 194 207 309 159 151

10% 241 270 351 295 278

20% 257 292 368 332 312

50% 289 325 400 397 391

90% 342 380 447 461 485

95% 353 401 460 475 504

FBP 361 449 488 509 544

Distribution of normal alkanes

C ₁₀0.25

C ₁₁0.71

C ₁₂1.45 0.12

C ₁₃2.10 0.35 0.25

C ₁₄2.89 1.00 0.23 0.47

C ₁₅3.22 1.55 0.60 0.81

C ₁₆3.42 2.68 0.86 1.24

C ₁₇3.33 3.76 0.64 1.60

C ₁₈3.14 5.02 1.28 1.74

C ₁₉2.90 5.23 0.78 2.17 1.85

C ₂₀2.67 4.16 1.98 2.22 1.97

C ₂₁2.29 2.95 3.27 2.28 2.15

C ₂₂1.75 1.92 3.91 3.17 2.17

C ₂₃1.34 1.46 4.85 3.66 2.16

C ₂₄0.73 0.87 4.33 3.47 2.00

C ₂₅0.45 0.74 4.22 3.98 2.19

C ₂₆0.22 0.44 3.06 3.37 1.84

C ₂₇0.09 0.30 2.26 3.09 1.78

C ₂₈0.04 0.19 1.52 2.47 1.54

C ₂₉0.01 0.11 0.94 1.90 1.37

C ₃₀0.07 0.55 1.17 1.07

C ₃₁0.04 0.31 0.83 1.01

C ₃₂0.01 0.13 0.48 0.78

C ₃₃0.01 0.10 0.30 0.62

C ₃₄0.05 0.19 0.47

C ₃₅0.11 0.42

C ₃₆0.03 0.24

C ₃₇0.03 0.21

C ₃₈0.14

C ₃₉0.11

C ₄₀0.07

C ₄₁0.05

C ₄₂0.04

C ₄₃0.03

This basic fuel contains the C of 32wt% ₁₂High-grade alkane more.

Prepare following concoction:

A B C D E F G H I

Basic fuel (wt%) 100 97 95 97 95 97 95 97 95

VGO-A（wt%） 3 5 - - - - - -

VGO-B（wt%） - - 3 5 - - - -

HGO-1（wt%） - - - - 3 5 - -

HGO-2（wt%） - - - - - - 3 5

D.86 distillation

IBP 194 192 192 194 195 190 189 191 188

20% 257 242 258 258 259 258 258 258 258

50% 289 290 290 292 294 291 293 291 292

90% 342 343 343 346 348 346 348 346 348

FBP 361 361 362 369 375 369 375 369 371

The C that adds ⁺ ₂₄Positive structure-0.08 0.14 0.52 0.87 0.64 1.07 0.48 0.80

Alkane

The CFPP value is when handling with additive 2: (℃)

0 ppm +6 +7 +7 +6 +9 +7 +8 +4 +4

1000 ppm +6 +6 +6 +5 +4 0 0 +1 +4

1500 pppm +5 +6 +6 +2 +1 -1 -1 -2 +4

Embodiment 5

This embodiment illustrates that basic fuel oil 1 cloud point is-1 ℃ with the susceptibility improvement situation of cracking heavy gas oil (HCO) replacement normal pressure heavy gas oil (HGO) to FLOW IMPROVERS, and basic fuel oil 2 cloud points are-2 ℃.

The characteristic of each used component is as follows:

The basis combustion of recirculating is fired on the basis

HGO

Expect 1 oil (HCO) material 2

The distillation type D.86

IBP 226 276 230 220

10% 248 300 336 249

20% 256 310 348 258

50% 272 326 366 276

90% 304 346 400 314

95% 312 350 400 322

FBP 322 360 330

10 ℃ of wax contents 9.9 21.50 15.40 below cloud point

Distribution of normal alkanes

C ₁₂0.93 0.08 0.70

C ₁₃2.31 0.25 0.03 1.94

C ₁₄3.77 0.47 0.10 3.48

C ₁₅3.13 0.75 0.14 3.85

C ₁₆3.15 1.15 0.17 3.52

C ₁₇3.02 1.96 0.22 3.20

C ₁₈2.66 3.47 0.27 3.11

C ₁₉2.00 6.02 0.53 3.25

C ₂₀1.22 8.82 1.16 2.59

C ₂₁0.44 8.09 2.75 1.59

C ₂₂0.13 5.35 3.50 0.32

C ₂₃0.03 2.70 4.25 0.04

C ₂₄1.30 7.94 0.02

C ₂₅0.53 2.87

C ₂₆0.20 1.76

C ₂₇0.08 1.08

C ₂₈0.02 0.48

C ₂₉0.01 0.24

C ₃₀0.003 0.09

C ₃₁0.04

C ₃₂0.01

C ₃₃0.01

C ₃₄

Basic fuel 1 contains the C of 22.8wt% ₁₂High-grade normal paraffin more, basic fuel 2 contains the C of 27.6wt% ₁₂High-grade normal paraffin more.

Prepare following concoction:

A B

Basic fuel 1wt% 85 85

HGO wt% 15 -

HCO wt% - 15

Distillation D-86

IBP 227 227

20% 260 260

50% 279 280

90% 318 340

FBP 339 390

The C that adds ⁺ ₂₄Normal paraffin 0.32 2.18

CFPP susceptibility to additive 5

0 ppm -2 +3

300 ppm - -4

1000 ppm -2 -9

Embodiment 6

The following concoction of basic fuel 2 preparations with embodiment 5:

Concoction

J K

Kerosene wt% 15 15

Basic fuel 2 wt% 70 70

HCO wt% - 15

MGO wt% 15 -

CFPP susceptibility

0 ppm 1 3

200 ppm additives 4-3

1000 ppm additives 4 1-4

200 ppm additives 6--5

1000 ppm additives 6 1-8

200 ppm additives 5--5

1000 ppm additives 5 1-10

The C that adds ⁺ ₂₄Normal paraffin 0.32 2.18

In this embodiment, the quantity of specified additive is the actual amount of polymkeric substance.

Also estimated the result of use of other several commercially availabie cold flow improvers, the result is as follows:

The additive J K that used activity group is used

The amount ppm that divides

200 additives 3 1-4

1000 additives 3 1-10

200 Amoco 2052E 1 -6

1000 Amoco 2042E 1 -9

200 Keroflux H 1 -4

1000 Keroflux H 1 -7

200 BASF CE 5323 1 -6

1000 BASF CE 5323 1 -8

200 BASF CE 5486 1 -3

1000 BASF CE 5486 1 -9

200 Bayer FI 1814 1 -7

1000 Bayer FI 1814 1 -9

200 Hoechst Dodiflow 3592 1 -2

1000 Hoechst Dodiflow 3592 1 -4

200 Sumitomo FI 20 1 -5

1000 Sumitomo FI 20 1 -9

200 Elf 8320 1 0

1000 Elf 8320 1 -5

200 Elf 8327 1 4

1000 Elf 8327 1 1

Embodiment 7

This embodiment represents that adding wax to obtained by Chinese crude oil cloud point is the effect in+5 ℃ the basic distillate fuel.The D-86 distillation characteristics of cut is as follows:

IBP 205

10% 233

20% 245

50% 278

90% 335

FBP 355

The distribution of normal alkanes of the wax of fuel and interpolation is as follows:

Normal paraffin basic fuel wax B wax E wax F wax G

C ₁₀0.36

C ₁₁1.02

C ₁₂2.13

C ₁₃2.89

C ₁₄2.80

C ₁₅2.92

C ₁₆2.81

C ₁₇2.82

C ₁₈2.71

C ₁₉2.53

C ₂₀2.36 0.03 0.20

C ₂₁2.02 0.25 0.10 0.14 0.13

C ₂₂1.56 1.31 0.60 0.87 0.56

C ₂₃1.19 3.75 3.00 2.83 1.74

C ₂₄0.63 7.12 8.63 6.15 3.81

C ₂₅0.39 8.73 13.08 9.66 7.26

C ₂₆0.19 10.00 15.43 13.44 10.72

C ₂₇0.08 8.85 12.16 14.47 13.91

C ₂₈0.04 8.08 9.20 13.92 15.12

C ₂₉0.01 6.77 6.24 11.17 11.50

C ₃₀0.004 5.70 4.23 6.65 7.19

C ₃₁4.34 2.67 3.13 3.12

C ₃₂3.53 1.62 1.22 1.13

C ₃₃2.52 1.11 0.43 0.81

C ₃₄1.79 0.69 0.20 0.50

C ₃₅1.09 0.39 0.04 0.36

C ₃₆0.66 0.25 0.05 0.27

C ₃₇0.36 0.12 0.02 0.19

C ₃₈0.19 0.14

C ₃₉0.08 0.10

C ₄₀0.04 0.07

C ₄₁

This basic fuel contains the C of 30.1wt% ₁₂High-grade normal paraffin more.

Prepare following concoction:

The wax wt% wt% CFPP that adds improves CFPP and improves

C ⁺ ₂₄Additive 5 usefulness additives 5 are used BASF

5486

500ppm 1000ppm 500ppm 1000pp

Do not have 000000

B 0.30 0.21 0 1 1 8

0.50 0.35 2 5

1.00 0.69 3 8

E 0.30 0.23 0 0

0.50 0.38 2 1

0.75 0.57 2 8

1.00 0.76 5 9

F 0.25 0.2 1 1

0.50 0.4 2 2

0.75 0.6 3 6

G 0.25 0.19 0 1

0.50 0.38 1 4

1.00 0.76 2 7

n C ₂₈0.30 0.30 2 0

0.50 0.50 3 10

Annotate: in this embodiment, the amount of additive is the amount of polymkeric substance.

Claims

1, a kind of liquid fuel combination mainly comprises distillate fuel oil, and this distillate fuel oil contains 4～10% wax and is substantially free of the paraffinic hydrocarbons of being longer than positive triacontane 10 ℃ the time below cloud point; 0.002～2.0% cold flow improver (by the weight of distillate fuel oil) and the normal paraffin that adds are to provide the C greater than 0.35% ₂₄Higher alkane hydrocarbon (based on the weight meter of this oil fuel) more.

2, according to the composition of claim 1, wherein be added to the C in the distillate fuel oil ₂₄The amount of higher grade normal paraffin is greater than the 0.5Wt% of distillate fuel oil mass.

3, according to the composition of claim 1 or 2, wherein the consumption of FLOW IMPROVERS is 0.005～0.2Wt% of distillate fuel weight of oil.

4, according to the composition of claim 1 or 2, wherein the carbon number distribution of the normal paraffin of Tian Jiaing is 20～40.

5, according to the composition of claim 1 or 2, wherein distillate fuel oil contains the wax of about 8Wt% 10 ℃ the time below cloud point.

6, according to the composition of claim 1, wherein add normal paraffin by blending distillate and a kind of vacuum gas oil, a kind of cracked heavy gas oil or a kind of normal pressure heavy gas oil.

7, according to the composition of claim 6, wherein the consumption of vacuum gas oil or normal pressure heavy gas oil is 5～10wt%.

8, according to the composition of claim 6, wherein vacuum gas oil comprises and is essentially C ₂₅～C ₃₅Normal paraffin.

9, according to the composition of claim 6, wherein the normal pressure heavy gas oil comprises and is essentially C ₁₄～C ₃₇Normal paraffin.

10, according to the composition of claim 1 or 2, wherein the final boiling point of oil fuel is lower than 370 ℃.

11, be used for the application of the cold flow improver of distillate fuel oil, this distillate fuel oil contains the wax of 4～10Wt% 10 ℃ the time below cloud point, do not contain the normal paraffin of being longer than positive triacontane, and this cold flow improver comprises:

(a) a kind of mixture, it provides 0.35%(at least in the weight of oil fuel) C ₂₄And more the high-grade paraffinic hydrocarbons and

(b) 0.001～2%(is in the weight of oil fuel) a kind of cold flow improver.

12,, wherein provide the C of 0.5Wt% at least according to the application of claim 11 ₂₄Higher alkane hydrocarbon more.

13, according to the application of claim 11 or 12, normal paraffin wherein adds as a component in vacuum gas oil and the heavy gas oil.

14, according to the application of claim 11 or 12, wherein normal paraffin contains 20～40 carbon atoms.

15, a kind of liquid fuel combination mainly comprises distillate fuel oil, and this distillate fuel oil contains 5～10% wax 10 ℃ the time below cloud point, and is substantially free of the paraffinic hydrocarbons of being longer than positive triacontane; 0.001 the multipolymer of～2.0% ethene and alkene formula unsaturated monomer (by the weight of distillate fuel oil); And contain the multipolymer (pressing the volumeter of distillate fuel oil) of 5～10% vacuum gas oil, cracked heavy gas oil or normal pressure heavy gas oil.

16, improve the method for the low-temperature fluidity of distillate fuel oil, this distillate fuel oil contains 4～10% waxes 10 ℃ the time below cloud point, and be substantially free of the paraffinic hydrocarbons of being longer than positive triacontane, this improvement comprises, adds a kind of cold flow improver (in the weight of oil fuel) of 0.001～2.0Wt% and the C of its amount greater than 0.35Wt% can be provided in distillate fuel oil ₂₄The normal paraffin of higher alkane hydrocarbon (in the weight of oil fuel) more.