CN1013277B - Improved addictive agent for fuel oil - Google Patents

Abstract

The present invention relates to the use as an additive for wax containing distillate fuel of a compound containing at least 2 substituent groups and having a spacing and configuration.

Description

Improved addictive agent for fuel oil

The mineral oil that contains wax resembles and is used as distillating fuel oil of diesel engine fuel oil and oil fuel and has characteristics with the low and mobile variation of oily temperature drop.Mobile variation is because wax crystallization is a tabular crystal, the final fluffer that is being mingled with oil that forms of the latter.Temperature when wax crystalls begins to form is called cloud point, and the temperature that wax stops oil to incline when is called pour point.

People just know for a long time, can be used as pour point reducer after many additives and the content of wax mineral oil.These compositions can change the shape and the size of wax crystalls and weaken between the wax crystalls and wax and oil between bounding force, thereby make oil can still keep mobile at a lower temperature so that can incline to and pass through coarse filter.

The document book has been introduced multiple pour point reducer, wherein has some to obtain industrial application.For example, United States Patent (USP) 3,048 is introduced in 479, can be with ethene and C _1-5The multipolymer of vinyl acetate (for example vinyl-acetic ester) is as the pour point reducer of some fuel, particularly heater oil, diesel engine oil and jet fuel oil.Also known poly-hydrocarbon based on ethene and high alpha-olefin (for example propylene) can be used as pour point reducer.United States Patent (USP) 3,252,771 have introduced C _16-18The purposes of alpha-olefinic polymer and aluminum chloride/pour point reducer that alkyl fontanel catalyzer conduct " wide boiling range " (" broad boiling ") distillates fuel; Above-mentioned " wide boiling range " distillates fuel is a kind of easy-to-handle fuel that the U.S. produces at early sixties.In sixties end, early seventies, people more are devoted to improve the filtrability of oil under temperature between boiling point and the pour point; This filtrability is to measure with stricter cold filter stoppage point (CFPP, Cold Filter Plugging Point) test (IP309/80).From that time, many patent documentations about the performance of improvement fuel in above-mentioned test have appearred.United States Patent (USP) 3,961 is introduced in 916, a kind of mixed copolymer can be used to control the size of wax crystalls.English Patent 1,263,152 propose, and the less a kind of multipolymer of available side chain is controlled the size of wax crystalls.

The somebody proposes, for example see English Patent 1,469,016, the fumaric acid two nalka esters of the former pour point reducer that is used as lubricating oil and the multipolymer of vinyl-acetic ester, can be used as the common additive of ethylene, be used for handling and have distillating fuel oil of high final boiling point, to improve its fluidity at low temperature matter.

The somebody proposes, and can use the additive based on alkene/maleic anhydride copolymers.For example United States Patent (USP) 2,542,542 use alkene (for example octadecylene) with by the multipolymer of the maleic anhydride of a kind of alcohol (for example lauryl alcohol) esterification as pour point reducer; English Patent 1,468,588 use C _22-28Alkene and the common additive that is distillated fuel oil by the conduct of the multipolymer of the maleic anhydride of behenyl alcohol esterification.Similarly, Japanese Patent discloses 5,654, and 037 use and the reacted alkene/maleic anhydride copolymers of amine are as pour point reducer.Japanese Patent discloses 5,654, and 038 derivative with alkene/maleic anhydride copolymers uses with traditional middle distillate stream improving agent (for example ethylene).Japanese Patent discloses 5,540, and 640 introduce, and can use nonesterified alkene/maleic anhydride copolymers, also say and should adopt the alkene that contains the carbon atom more than 20 to reach the CFPP characteristic.English Patent 2,192, what use in 012 is the alkene/maleic anhydride copolymers of some esterification and the mixture of low molecular weight polyethylene, this esterified copolymer is invalid when adding separately.

Add the additive that above-mentioned patent is introduced, by changing the size and the shape of wax crystalls, make it to become the utmost point and be bordering on acicular crystal, its particle diameter is generally 30～100 microns method improvement CFPP characteristic generally more than 10 microns or 10 microns.When diesel motor moved under low temperature, these crystal can not pass through the oil fuel paper filter of diesel engine, but formed a filter cake that can see through liquid fuel on strainer.After engine and fuel temperature rose, wax crystalls can dissolve thereupon; It can be by due to most of fuel of circulating fuel heating that engine and fuel temperature rise.Yet be deposited in wax energy blocking filter together, cause the variety of issue when the cold day diesel-engine road vehicle starts obstacle and brings into operation or cause fuel-heating system to lose efficacy.

By means of computer, can be with simply, method accurately calculates the geometrical shape of normal alkane wax crystalls lattice and the favourable geometrical shape of energy of possible interpolation molecule very easily.The gained result utilizes plotter subsequently or describes end and illustrates out, and is just clear especially.This method is called " molecular designing method ".

The computer program that is used for this purposes is on sale on the market; (technical director: a series of programs of E.K.Divies) selling are especially suitable in the compound design company limited of England Oxford.

As shown in Figure 1, during the paraffin crystal growth, single paraffin molecule is that the side that it is long connects together with the paraffin platelet edge that is just forming.The bottom surface or the end face that are connected platelet are disadvantageous on energy, because this moment, the paraffin molecule chain had only an end and established crystal to interact.Connect and mainly on 001 crystal face, (see figure 2) takes place.(001) face contains the key between the strongest molecule of maximum numbers, and therefore arranging crystal reciprocally forms big flat rhombus plate (Fig. 3).The most stable next face is (11X) (for example (110)) on the crystal.The local moleculartie approaching at the normal alkane molecular weight is the most firm, so this (100) sheet of (110) sheet is stronger.

Stretch along (001) face during crystal growth.So (001) edge of face is to strengthen very fast surface, and (11X) (for example (110)) and (100) face are to increase those slower surfaces, point out that this point is very important.Therefore, crystal growth can be controlled by making the increase of (11X) face to a great extent.

Since " head to head " key a little less than, so we generally only consider a molecule (001) face.Therefore we can suppose that for our purpose, faces such as (110), (111) are of equal value, because the relative orientation between the neighboring molecule of crystal situation on these faces and arrangement shoulder to shoulder is the same (Fig. 4).

Fig. 3 is a kind of acale wax crystalline photo.Fig. 3 shows that the microcosmic appearance of these platelets is subjected to the domination of (001) face.These platelets can stop up the strainer on the fuel passage of vehicle for example just.

According to the present invention,, can address the above problem by suppressing or being to significantly reduce the growth of crystal on (001) face and (110) and (111) direction at least.

Can obtain containing under the low temperature waxy fuel of enough little wax crystalls that can be by strainer used in diesel engine and the oil fuel system like this, and method is to add some additive.

Therefore the invention provides and can be used as distillate fuel a kind of compound of oil additives of the content of wax.This compound has at least two following substituting groups: these two substituent spacings and configurational energy make them occupy the position of the wax molecule in (001) face that intersects with (110) and/or (111) face in the wax crystalls; Said substituting group is alkyl, alkoxyalkyl or the multi-alkoxy alkyl that contains at least 10 atoms in the main chain.

Crystal face occupy available Fig. 4 explanation.Fig. 4 provides the top view of the paraffin lamellar lattice of amplification.Direction of observation is consistent with the long axis direction of paraffin chain.Have only two carbon atoms and four hydrogen atoms (latter only marks) to see in each paraffin molecule because other atom shown in below the atom, this be since all carbon atoms of molecule all on a molecule plane of symmetry.As seen from Figure 4, the distance that is distributed between per two molecules on (110) face and (110) face is practically identical.

These letters are apart from being marked with " b " and " d " respectively among Fig. 4; B=4.9A; D=4.5A.(110) face and (110) face (or be (11X) face more strictly speaking, wherein X be 0 or integer) between main difference be relative orientation between neighboring molecule.In (110) face, the molecule plane of symmetry of each molecule all is parallel to each other, and promptly interfacial angle is 0 °, and in (110) crystal face, the interfacial angle between the molecule plane of symmetry of adjacent molecule is about 82 °.

According to the present invention, additive therefor should occupy the position of the paraffin molecule that marks with " C " and " D " in Fig. 4.This have only be only under the following conditions possible: the distance between substituting group is about 4.5～5.0A, and corresponding conformation can realize on energy, and two substituting groups separately the interfacial angle between the plane of symmetry be about 82 °, preferably 75 °～90 °.

By the known atomic coordinate of molecule being recorded the method in the computer, or, utilize computer to set up the method for molecular structure, can design desired molecule by according to the chemical physics rule.Can adopt for example following method that this result is done further research subsequently:

(a) calculate the Partial charge on each atom according to electronegativity difference (field of force method) or quantum mechanics method (for example seeing CNDO, Q.C.P.E.141, Indiana University);

(b) adopt molecular mechanics method (see " Molecular Mechanics, U.Burkert and N.L.Allinger, ACS, 1982) to make this structural optimization;

(c) adopt that to make conformation optimization (promptly by making the method for rotation key rotation) that total energy is reduced to minimum.It should be noted that the environment the when environment on wax crystalls surface is different from gas phase or liquid phase this moment, might not be best conformation on its energy in gas phase so additive molecule forms the crystalline conformation with paraffin.Must consider that also additive can not take to be subjected to the conformation of space or electronic factor obstruction.

Adopt following standard, can check an additive molecule whether to be suitable for entering and occupy desirable C and the D position at (001) face of paraffin crystal lattice:

(1) in the molecule distance between above-mentioned two substituting groups must and and (11X) distance between the paraffin molecule of two vicinities in (001) face of intersecting of face about equally 4.5A is arranged approximately promptly.These two substituent relative orientations should be complementary with the configuration of normal alkane on (110) direction, promptly two substituting groups separately the interfacial angle between the plane of symmetry should be about 82 °.This distance and this angle are tried to achieve easily by means of computer program.

(2) additive molecule should be suitable for entering the wax crystalls crystalline network, and " butt joint " is on two lattice vacancies.

The compound that proposes as additive was the derivative of some phthalic acid, toxilic acid, succsinic acid and vinylidene alkene in the past.Institute quotes that none can satisfy above-mentioned standard (1) in the compound.This can illustrate as follows.

(a) conformation of phthalic diamide under best-case be as existing shown in Figure 5, and distance and interfacial angle between two substituting groups are too little.This conformation is disadvantageous on energy, because have living space obstruction.Again reach that energy is minimum then to produce guache conformation shown in Figure 6.

(b) situation of Malaysia diamide is also similar, sees Fig. 7.Because steric restriction, the conformation that energy is minimum is twisted, and sees Fig. 8.

(c) owing to steric restriction, the conformation (see figure 9) that succsinic acid can not take peculiar set-up according to the invention substantially to require, but serve as the axle rotation and remain on the conformation shown in Figure 10 with the C-C singly-bound.

Adding the described existing additive of above-mentioned patent, is to be bordering on acicular crystal by the size and the pole of figure that changes wax crystalls, thereby reaches the purpose of improving the CFPP characteristic; The granularity of this needle-like crystal is not less than 10000 millimicrons, generally is 30000～100000 millimicrons.When the diesel motor cold operation, these crystal can not pass through the vehicle fuel oil paper filter, but form a permeable filter cake on strainer; Liquid fuel can pass through this filter cake.Wax crystalls can dissolve with diesel engine and fuel heating; Engine and fuel temperature rising can be to be recycled due to a large amount of fuel of fuel heating.Yet the wax that is deposited in together can stop up filter, the problem when causing cold day diesel engine starting difficulty and bringing into operation, or cause fuel-heating system to lose efficacy.

The application adopts following each test method.

The wax precipitation piont of fuel (Wax Appearance Temperatur(WAT)) be to measure with differential scanning calorimeter (DSC).In this test, small specimen of fuel (25 milliliters) is similar to thermal capacity with 2 ℃/minute speed but control sample (for example kerosene) do not separate out wax in interested temperature range together cools off.Can be observed exothermic phenomenon when beginning crystallization in the sample.For example, on Mettler TA2000B, adopt extrapotation can record the WAT of fuel.

The fuel wax content is obtained according to the DSC scintigram, and method is to obtain the area that baseline and exotherm are surrounded when the specified temp by integration.Proofread and correct with the known sample of crystalline wax amount in advance.

The survey method of wax crystalls mean particle size is as follows, and analyzing fuel sample is 4000～8000 times description electron micrograph at ratio of enlargement, measures the longest dimension of at least 40 points in 88 points with predetermined grid (grid).We find, as long as mean particle size is lower than 4000 millimicrons, wax crystalls just can begin with the common paper filter of oil fuel by using on the diesel motor, although we require the wax crystalls granularity to be lower than 3000 millimicrons, be more preferably and be lower than 2500 millimicrons, preferably be lower than 2000 millimicrons, especially be lower than 1000 millimicrons, this moment, wax crystalls can bring practical advantages by the fuel filter of papery.In fact the granularity that can reach depends on the original character of oil fuel and the character and the consumption of additive therefor, and we find that above-mentioned granularity and littler granularity can reach.

Adopt additive of the present invention, in fuel, can obtain so little wax crystalls, thereby can from improved diesel engine service performance, obtain sizable benefit.This point can confirm with following method: at below at least 5 ℃ of wax precipitation piont, have at least this moment the 0.5%(heavy) oil fuel exist with the solid wax form, with the speed of 8～15 milliliters/second and the flow of every square metre of filter surface-area of 1.0～2.4 Liter Per Minutes, with the diesel oil filter paper of oil fuel pumping under stirring by using in V.W.Golf or the Cummins diesel motor.If satisfy following one or more standard, think that then fuel oil and wax have all successfully passed through strainer.

(ⅰ) after 18～20 liters of oil fuel passed through strainer, the pressure drop of filter both sides was no more than 50 kPas, better is to be no more than 25 kPas, is more preferably and is no more than 10 kPas, preferably is no more than 5 kPas.

(ⅱ) according to aforementioned DSC test determination, the wax content that leaves the fuel of filter be in the crude fuel wax content at least 60%, better be at least 80%, better at least 90%.

(ⅲ) when 18～20 liters of fuel oils of pumping passed through filter, flow velocity always remained on more than 60% of threshold speed, preferably more than 80%.

Wax crystalls by the vehicle filter part and the benefit of the service performance aspect brought by small-crystalline depend on crystalline length to a great extent, although crystal shape also has considerable influence.We find that cube shaped crystal is easier to by strainer slightly than flat crystal, and when cube shaped crystal can not pass through filter, they were lighter to the obstruction degree of fuel stream.It is better that yet crystal is flats, along with temperature descends, generally can separate out more wax, and before reaching critical crystallographic dimension, compare with onesize cube shaped crystal like this, has more wax to precipitate.

Passed through to add conventional additive and improved distillating fuel oil of cold flowability and compare with former, the oil fuel that obtains with the inventive method has outstanding advantage.For example, these fuel can use under the temperature near pour point, and do not have and can because they can be tested by CFPP, perhaps need to carry out this test under quite low temperature by the problem of CFPP test at all.These fuel also have the cold-start performance under low temperature very, thereby need not to rely on the circulation of warm fuel to remove undesirable wax deposit.Moreover wax crystalls easily is suspended in the fuel oil, and not sedimentation also forms the wax layer in storage vessel, and this always takes place in the fuel of handling with conventional additive.

Belong to boiling point and be 120～500 ℃ the distillating fuel oil of general classes, its boiling range characteristics, alkane distribute and wax content widely different.Originate from the northern oil fuel in Europe and compare with originating from meridional oil fuel, its final boiling point and cloud point are lower.Wax content generally be higher than 1.5%(below WAT 10 ℃), similarly, the oil fuel that originates from other countries in the world with its separately the difference of weather also produce difference with the same manner, and wax content also depends on the source of crude oil.The wax content that originates from the crude oil in the Middle East may be lower than the wax content that originates from China and Australian wax crude oil.

The character that very little crystalline degree depends on oil fuel itself can be obtained,, perhaps minimum crystal can not be produced for some oil fuel.In this case, can this small-crystalline be produced with for example adjusting the rectifying condition and mixing the method improvement fuel oil properties of using suitable additive.

Because the wax of separating out from distillate fuel oil is that (this point for example sees following document: A.Muller, Proc.Roy.Soc.A.114,542, (1927) with orthorhombic unit cell crystalline normal alkane by means of rotator or sexangle mostly; Having of same source: 120,437, (1928), 127,417, (1930), 138,514, (1932); A.E.Smith, Acta.Cryst., 12,294, (1959)), as mentioned above, additive molecule and wax crystalls coupling have two important factors; First factor is the distance between the nalka hydrocarbon chain on the selected crystal face; On these crystal faces, important distance to be matched is mainly on (110) and faces such as (111) or direction, secondly on (100) face.

The chain of additive must occupy lattice point (more than 1), and it should meet at right angles with the axle of nalka hydrocarbon chain in the crystal.These distances are about 4.5～5.5A.Chain on the additive is more near these distances, and the additive effect is just good more.Second factor (although may be more less important) be, the relative orientation of additive molecule chain preferably and in the crystal relative orientation of normal alkane match.N-alkyl chain on the additive must with wax crystalls in closely mate (above-mentioned crystal face is crossing with (001) face) along the intermolecular distance of the normal alkane on (110) and/or (110) and (111) face, and can take the close conformation of normal alkane in the orientation angle of cut of its chain and the above-mentioned crystal face.This spacing of the chain on the additive molecule and orientation find can be by these chains being arranged on cisoid conformation ring-type or the method on the adjacent carbons of olefinically unsaturated compounds reach.

In addition, coupling is preferably carried out on the nalka hydrocarbon chain of wax, thereby the total length of additive chain is preferably identical with the order of magnitude of mean chain length of alkane in the wax.Therefore the normally various normal alkane of the wax of separating out from fuel or oil is to be standard with the mean length.

So additive generally contains alkyl chain, n-alkyl chain or be called segment preferably, these additives can with wax one syncrystallization.We find on each additive molecule chain two or more this chains to be arranged, and these chains should be in the same side of additive molecule.Additive molecule preferably has the distinct both sides of character.One side contain can cocrystallization alkyl chain, opposite side contains the minimized number alkyl; These alkyl are at the additive molecule cocrystallization and after entering the lattice point of wax crystalls, might hinder or prevent to continue crystallization.In addition, this " blocking-up " group is preferably can half length below the n-alkyl chain of cocrystallization on the additive or be about on the position of half length.

Its general formula of the additive that we select for use is as follows:

In the formula-Y-R ²Be SO ^{(-) (+)}NR ³ ₃R ²,-SO ^{(-) (+)} ₃HNR ³ ₂R ²,

-SO ^{(-) (+)} ₃H ₂NR ³R ²,-SO ^{(-) (+)}H ₃NR ²,-SO ₂NR ³R ²Or-SO ₃R ²;

-X-R ¹For-Y-R ²Or-CONR ³R ¹,-CO ^{(-) (+)} ₂NR ³ ₃R ¹,

-CO ^{（-）（+）} ₂HNR ³ ₂R ¹、-CO ^{（-）（+）} ₂H ₂NR ³R ¹、-CO ^{（-）（+）} ₂H ₃NR ¹、

-R ⁴-COOR ¹、-NR ³COR ¹、-R ⁴OR ¹、-R ⁴OCOR ¹、-R ⁴R ¹、

-N(COR ³) R ¹Or Z ^{(-) (+)}NR ³ ₃R ¹; Z ^(-)Be SO ^(-) ₃Or-CO ^(-) ₂; R ¹And R ²Be alkyl, alkoxyalkyl or multi-alkoxy alkyl, its main chain contains at least 10 carbon atoms; R ³Be alkyl, each R ³Can be identical or inequality; R ⁴Or do not exist, or C _1-5Alkylidene group; And

In, the one-tenth annular atoms of this ring compound is carbon atom preferably, but also can comprise N, S or O atom, thereby obtains heterogeneous ring compound.

The example that can be used to prepare the aromatics of above-mentioned additive has

Aryl wherein can be substituted.

Above-mentioned additive also can be made by polynuclear compound, is promptly made by the compound that can get various ways, have two or more ring structures.They can be that (a) condenses the benzene structure, and (b) all rings are not or not all are the condensed ring structures of benzene, (c) " end connects " ring, (d) heterogeneous ring compound, (e) non-aromatic ring, or the ring system of fractional saturation, or (f) three-dimensional structure.

The preparation above-claimed cpd is used condense the benzene structure comprise naphthalene, anthracene, phenanthrene and.

All rings be not or not all be the condensed ring structure of benzene for example comprise Austria, indenes, hydrogen indenes,, diphenylene.End concatemerization compound comprises for example biphenyl.Can be used to prepare the heterogeneous ring compound that additive uses and comprise for example quinoline, pyridine, indoles, 2,3-indoline, cumarone, tonka bean camphor, an unusually sweet smell beans naphthalene, thionaphthene, carbazole and thiodiphenylamine.The suitable non-aromatic or the ring system of fractional saturation comprise naphthalane, α-Pai Xi, cadinene, bornylene.Suitable three-dimensional compound comprises for example norbornylene, norbornane, double-octane and dicyclo octene.

When ring is only arranged, two substituent X and Y must be connected on the adjacent ring atom on the ring; When this compound is a polynuclear compound, these two substituting groups must be connected on the adjacent ring atom of a ring in many rings.The latter means that if use naphthalene these two substituting groups can not be connected 1, and 8-or 4 on the 5-position, and must be connected 1,2-, 2, and 3-, 3,4-, 5,6-, 6,7-or 7 is on the 8-position.

These compound reactions are obtained being used as ester class, amine, amides, half ester class/half amide class, half ethers or the salt of additive.Preferred additives is the salt of secondary amine; This salt has the group of a hydrogeneous and carbon or contains at least 10, preferably the group of at least 12 carbon atoms.By making the reaction of acid described above or acid anhydrides and amine or can making this class amine or salt by secondary amine derivative and carboxylic acid or carboxylic acid anhydride are reacted.Prepare acid amides by acid and need remove water and heating usually.Perhaps can make carboxylic acid and contain the alcohol of 10 carbon atoms at least or the mixture reaction of alcohol and amine.

The group of hydrogeneous and carbon alkyl preferably although also can use fontanel for alkyl, preferably uses the fontanelle atom (as the chlorine atom) that only contains than small proportion in the substituting group, for example contains that to be lower than 20%(heavy) the fontanel of fontanelle atom for alkyl.Alkyl is preferably aliphatic, for example alkylidene group.They are straight chain preferably.Unsaturated alkyl also can use as alkenyl, but they are not preferred.

Alkyl should contain at least 10 carbon atoms, best at least 10 to 22 carbon atoms, 14 to 20 carbon atoms for example, and preferably straight chain or at 1 or 2 side chain is arranged.If the side chain in the alkyl chain surpasses 20%, then side chain must be a methyl.Other hydrogeneous and group carbon can be lacked, and for example is less than 6 carbon atoms, perhaps if desired, can have at least 10 carbon atoms.Suitable alkyl comprises methyl, ethyl, propyl group, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl.Suitable alkylidene group comprises hexylidene, octylene, inferior dodecyl and inferior hexadecyl, but these are not preferred.

In preferred specific embodiments, when intermediate and secondary amine reaction, one of substituting group is acid amides preferably, and other is the dialkyl ammonium salt of amine or secondary amine.

Particularly preferred additive is the amine salt of acid amides and secondary amine.

In order to obtain fuel of the present invention, generally these additives can be used in combination with other additive; Other additive comprises the additive that is called " profile of tooth " polymkeric substance, and its general formula is as follows:

D=R, COOR, OCOR, R ' COOR or OR in the formula

E=H or CH ₃Or D or R '

G=H or D

The m=1.0(homopolymer) to the 0.4(mol ratio)

J=H, R ', aryl or heterocyclic radical, R ' COOR

K＝H、CO·OR′、OCO·R′、OR′、CO ₂H

L=H, R ', COOR ¹, OCOR ¹, aryl, CO ₂H

N=0.0 to 0.6(mol ratio)

R≥C ¹⁰

R≥C ¹

If desired, another monomer can be carried out trimerization reaction.

When these other additives are the multipolymer of alpha-olefin and maleic anhydride; by solvent-free or in the solution of hydrocarbon solvent such as heptane, benzene, hexanaphthene or light oil; under being generally 20 ℃ to the 150 ℃ temperature in the scope; usually help under the catalysis at snperoxiaized or azo-type catalyzer such as benzoyl peroxide or even chloro-bis-isobutyronitrile; for getting rid of oxygen; in layer of inert,, can make at an easy rate as making the method for monomer polymerization in nitrogen blanket or the carbon dioxide layer.Though alkene is suitable with the mol ratio of maleic anhydride in 2 to 1 to 1 to 2 scope, best (and nonessential) uses the alkene and the maleic anhydride of equimolar amount.Can 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid be arranged with the example of the alkene of maleic anhydride copolymerization.

The multipolymer of alkene and maleic anhydride can be with any suitable method esterification, although the maleic anhydride of esterification at least 50% is better, this is optional.The example of operable alcohol has positive last of the ten Heavenly stems-1-alcohol, n-dodecane-1-alcohol, n-tetradecane-1-alcohol, n-hexadecane-1-alcohol, Octadecane-1-alcohol.The alcohol that on each chain, contains single methyl branch in addition, for example 1-methyl pentadecane-1-alcohol, 2-methyl tridecane-1-alcohol.This alcohol also can be the mixture of n-alkanol and single methyl branch alcohol.Every kind of alcohol may be used to the multipolymer of esterification maleic anhydride and above-mentioned any alkene, preferably use pure alcohol, and do not use commercially available alcohol mixture, if but use alcohol mixture, then R ' refers to the mean number of carbon atom on the alkyl, if the alcohol that uses contains side chain on 1 or 2, then R ' refers to the linear backbone part of alcohol.When using mixture, importantly, the R ' base with r '+2 values can not surpass 15%.Certainly, the selection of alcohol depends on and the selection of the alkene of maleic anhydride copolymerization that R+R ' is in the scope of 18-38.The preferred value of R+R ' depends on the boiling range characteristic of the fuel of additive to be used.

These profile of tooth polymkeric substance also can be fumarate polymkeric substance and multipolymer, for example those described in european patent application 0153176,0153177,85301047 and 85301048.Other suitable profile of tooth polymkeric substance is the polymkeric substance of alpha-olefin and the esterified copolymer of multipolymer and vinylbenzene and maleic anhydride.

The example of other additive that can use with ring compound has polyoxyalkylene esters, ether, ester/ether and composition thereof, particularly contains at least one, preferably at least two C ₁₁To C ₁₀Straight chain saturated alkyl and molecular weight be 100 to 5,000, be preferably those of 200 to 5000 polyoxyalkylene glycol base; The alkyl of said polyoxyalkylene glycol contains 1 to 4 carbon atom.European patent 0,061,895 B and relate to these materials.Other examples of such additives is at United States Patent (USP) 4,491, introduction arranged in 455.

The structure that can be used for preferred ester of the present invention, ether or ester/ether is shown below:

R and R in the formula " can be identical or different, and can be

ⅰ) positive alkyl

This alkyl is the saturated alkyl of straight chain and contains 10 to 30 carbon atoms; A represents the polyoxyalkylene base section (alkylidene group wherein has 1-4 carbon atom) of this glycol, for example polyoxymethylene, polyoxygenated ethylidene or polyoxygenated trimethylene part, and these parts are straight chain basically.A can also have the low alkyl group side chain (for example in polyoxypropylene ethylene glycol) of some amount, but preferred this glycol should be a line style basically, and A also can be nitrogenous.

Suitable glycol is the polyethylene glycols (PEG) and the polypropylene glycols (PPG) of line style usually basically, and its molecular weight is about 100 to 5000, preferably is about 200 to 2,000.Preferably corresponding ester; The lipid acid that contains 10 to 30 carbon atoms can be used for generating ester additive with these glycol reactions, preferably uses C ₁₈To C ₂₄Lipid acid, especially mountain acid.Ester can also prepare with the method for esterification polyethoxye lipid acid or polyethoxye alcohol.

Polyoxyalkylene dibasic acid esters, bis ether, ether/ester and composition thereof can also contain a spot of monoether and monoesters simultaneously as the suitable narrow-boiling range fraction that is applied to of additive (preferred dibasic acid esters) in above-mentioned additive; These monoethers and monoesters normally form in preparation process.The existence of a large amount of dialkyl compound is important to the performance of additive.Particularly preferably be the stearic acid diester Huo docosoic diester of polyoxyethylene glycol, polypropylene glycol or polyethylene/polypropylene glycol mixture.

Used additive can also contain ethene unsaturated ester multipolymer flow ability modifying agent.Can comprise unsaturated monoesters and the dibasic acid esters that general formula is following with the unsaturated monomer of ethylene copolymer:

R in the formula ⁶Be hydrogen or methyl; R ₅Be-OOCR ₈Base, wherein R ₈Be hydrogen or C ₁To C ₂₈, C normally ₁-C ₁₇, C preferably ₁-C ₈The straight or branched alkyl; Or R ₅Be-COOR ₈, R wherein ₈Except that be not the hydrogen as previously mentioned; R ₇Be hydrogen or as preceding defined-COOR ₈Work as R ₆And R ₇Be hydrogen, R ₅Be-OOCR ₈The time, this monomer comprises C ₁-C ₂₉Be generally C ₁-C ₁₈The ester that become with vinyl alcohol of monocarboxylic acid, better be C ₂-C ₂₉The ester that monocarboxylic acid is become with vinyl alcohol; C more usually ₁To C ₁₈The ester that monocarboxylic acid is become with vinyl alcohol, preferably C ₂-C ₅The ester that monocarboxylic acid is become with vinyl alcohol.Can vinyl-acetic ester, propionate and vinyl butyrate or isopropylformic acid vinyl acetate be arranged with the example of the vinyl ester of ethylene copolymer, preferred vinyl-acetic ester.When using these vinyl ester, it is heavy that we recommend to contain 20-40%() the multipolymer of vinyl ester, be more preferably that to contain 25-35%(heavy) the multipolymer of vinyl ester.These multipolymers can also be the mixtures of two kinds of multipolymers, as United States Patent (USP) 3,961, and the mixture of those multipolymers described in 916.With vapor infiltration instrumentation amount, the number-average molecular weight of these multipolymers is 1,000-10, and 000 is better, is more preferably 1,000 to 5,000.

Additive therefor also can contain other polar compound (can be ionic, also can be non-ionic type), and they can play the effect of wax crystalls growth inhibitor in fuel.Have been found that when nitrogenous polar compound uses with above-mentioned diol ester, ether or ester/ether effective especially.These polar compounds are generally amine salt and/or amides; To be the amine that replaces of the alkyl by at least 1 molar ratio with the hydrocarbon that 1 to 4 carboxylic acid group is arranged of 1 molar ratio sour or its anhydride reaction makes for acid amides.Ester/the acid amides that contains 30 to 300 carbon atoms altogether also can use, and preferably uses the ester/acid amides that contains 50 to 150 carbon atoms altogether.United States Patent (USP) 4,211,534 have described this class nitrogen compound.Suitable amine is C normally ₁₂To C ₄₀Long-chain primary, the second month in a season, uncle or quaternary amine or its mixture, the short amine of chain length also can use, as long as corresponding nitrogen compound is oil-soluble, so generally can contain 30 to 300 carbon atoms of having an appointment altogether.Preferred nitrogen compound contains at least one straight chain C ₈To C ₂₄Moieties.

Suitable amine has primary, secondary, uncle or quaternary amine, but secondary amine preferably.Tertiary amine and quaternary amine can only form amine salt.The example of amine has tetradecy lamine, coconut amine, hydrogenated ester amine etc.The example of secondary amine has dioctadecylamine, methyl mountain amine etc.The mixture of amine also suits, and a lot of amine that is obtained by crude substance is mixture.Preferable amine is that the formula that fatty hydrogenation is obtained is HNR ₁R ₂Para-hydrogenation ester amine, R in the formula ₁And R ₂Be alkyl, the composition of fat is roughly 4%C ₁₄, 31%C ₁₆59%C ₁₈

The example that is used to prepare the suitable carboxylic acid (with their acid anhydrides) of these nitrogen compounds has hexanaphthene-1,2-dicarboxylic acid, tetrahydrobenzene-1,2-dicarboxylic acid, pentamethylene-1,2-dicarboxylic acid, naphthalic acid etc.These sour loop sections generally have about 5 to 13 carbon atoms.Because the preferred phthalic acid of acid of the present invention, for example phthalic acid, m-phthalic acid and terephthalic acid.Particularly preferably be phthalic acid or its acid anhydrides.Particularly preferred compound is by 1 mole of Tetra hydro Phthalic anhydride and 2 moles of acid amides-amine salt that the reaction of two-hydrogenated fat amine makes.Another preferred compound is the dehydration of this acid amides-amine salt and the diamide that obtains.

Hydrocarbon polymer also can be used as the part in the mixed additive, and to prepare oil fuel of the present invention, their available following general formulas are represented:

T=H in the formula, or R '

U=H, T or aryl

V=1.0 to 0.0(mol ratio)

W=0.0 to 1.0(mol ratio)

R ' is an alkyl.

These polymkeric substance can directly be made by olefinic insatiable hunger monomer, and also the method for the polymkeric substance that can be made by other monomer (as isoprene and divinyl) by hydrogenation for example makes indirectly.

Particularly preferred hydrocarbon polymer is the multipolymer of ethene and propylene, its ethylene content be preferably in 50% and the 60%(weight ratio) between.

The consumption of producing the desired additives that distillates fuel oil of the present invention is different with oil fuel, but is benchmark with the weight of oil fuel, is generally 0.001 to 0.5%(heavy), for example 0.01 to 0.1%(is heavy) (active substance).Additive should be dissolved in the The suitable solvent, it is 20 to 90%(heavy that it is formed in this solvent), for example 30 to 80%(is heavy) concentrated solution.The suitable solvent comprises kerosene, aromatic petroleum naphtha, mineral lubricating oils etc.

The present invention will illustrate with the following example.In an embodiment, the size of the wax crystalls in the oil fuel is measured with following method: the oil fuel sample in 2 ounces of bottles is remained on than oil fuel cloud point in temperature placed 1 hour in high about 8 ℃ box, make fuel temperature stable.Then box was cooled off 1 hour at 1 ℃,, keep this temperature again up to being reduced to test temperature.

Then the pre-prepd carriage that is placed with strainer is placed on the vacuum unit: this carriage is made of the sintered ring of 10 millimeters of diameters, the annular metal circle surrounded by 1 mm wide of this ring, supporting 200 millimicrons of specified silverskin filters, this membrane filter is fixed with two vertical needle.The vacuum tightness of using is at least 80 kPas.With the dropping pipette of a cleaning the refrigerative fuel oil particle on above-mentioned film, just in time cover above-mentioned film up to little dome-shaped drift (puddle).Slowly drip oil fuel then, make drift keep several minutes.After oozing about 10 to 20 oil fuel, allow the oil in the drift drain, thereby on film, stay the wet wax cake layer of very thin, matt, coarse oil fuel.Thick wax layer is not suitable for washing, and very thin wax layer can be washed off.Best bed thickness is relevant with crystal shape, and the optimum thickness of " sheet " crystal layer should be lower than " needle-like " crystal layer.It is very important that final filter cake has coarse appearance this point.The filter cake of " light " shows that oil fuel and crystal that excess residual is arranged " blur ", should discard.

Use several methylethylketone washing leaching cakes then, allow the complete drip-dry of methylethylketone.Repeatedly repeat this process.After washing was finished, methylethylketone can very fast disappearance, stayed the surface of " coarse brilliant white ", and this surface can grizzle when dripping another methylethylketone.

Then washed sample is placed in the refrigerative moisture eliminator, in order on the SEM(sweep electron microscope, adorning sample (coating).May need freezing sample to preserve wax, in this case, sample should be stored in the refrigerative box to avoid forming ice crystal on the surface of sample to SEM in transfer (in suitable sample transfer container).

In dress sample process, must cool off sample as much as possible, make the ruined degree of crystal reduce to minimum.Compressing by a standing screw and to abut on the Stage microscope design and be used for making the sample face to be in the annular collar at the pocket edge on the instrument focal plane, can make with electrically contacting of Stage microscope to be in optimum regime.Also can use electroconductive paints.

The dress sample finishes, and can obtain microgram by sweep electron microscope according to a conventional method.By will suitable microgram being fixed on methods analyst Photomicrograph on the transparent slide to measure the average crystalline size; Above-mentioned slide glass has 88 circular point shape punctuates, and these punctuates are regular, intersection points of uniform 8 grid line and 11 grid files at interval.Ratio of enlargement should make the crystal that has only several maximums to contact with 1 above round dot, confirmed 4000 to 8000 times more suitable.On each grid point,, then can measure this crystal if round dot touches the crystal of a clear-cut.Also can adopt " dispersion " method of masurement of Gaussian crystal length standard deviation form, use the Bessel correction method simultaneously.

Use differential scanning calorimeter (DSC) (for example) Du Pont 9900 types) measure the wax content before and after filtering, the area under a curve that this calorimeter is retouched out is equivalent to have in the oil fuel 1% to be that form with wax exists for per 100 square centimeters, and the standard deviation that the output that is caused by the noise of instrument changes is less than 2% of average output signal.

Proofread and correct DSC with a kind of additive, the macrocrystal that this additive produces is sure to be isolated with strainer.In this device, under test temperature, test this and demarcate oil fuel, and on DSC, measure the wax precipitation piont (WAT) of the dewaxed fuel of gained.On DSC, analyze then test oil tank oil fuel and filter the sample of back oil fuel, to every kind of oil fuel, obtain the area under the curve more than the baseline before the wax precipitation piont of demarcating oil fuel.

Filter percentage composition=(filtering the DSC area of back sample)/(the DSC area of oil tank sample) * 100% of the remaining wax in back

Measure the cloud point that distillates fuel oil with standard cloudy test (IP-219 or ASTM-D2500).Other measuring method that crystallization begins has wax precipitation piont (WAP) test (ASTMD.3117-72).And measure wax precipitation temperature (WAT) by different scanning calorimeter calorimetry with Mettler TA 2000 B differential scanning calorimeters.

Measure the ability of fuel on the device that exemplary diesel engine master's strainer in by the standard valve casing that is contained on the fuel conduit on the fuel oil pipe constitutes by diesel-engine road vehicle master strainer; Be used for the 1980VWGolf diesel engine and hold the Bosch type of car and be used in Cummins NTC that to mobilize the Cummins FF105 of type be suitable.Use fuel tank and plenum system,, from oil tank, extract fuel out, make it to pass through strainer with constant flow rate as in vehicle; Above-mentioned fuel tank and plenum system can provide half of common oil tank fuel, and link to each other with the same oil fuel oil injection pump that is used for VW Golf.Lay various instruments, to measure pressure drop, the flow velocity of oil injection pump oil spout and the temperature of device of strainer both sides.Settle several vessels to reclaim the oil fuel of pump cupboard, the i.e. oil fuel of " ejection " and excessive fuel.

In this test, 19 kilograms of oil fuel are charged in the oil tank, and check whether leak.After qualified, oily temperature is stabilized under the air themperature that is higher than 8 ℃ of fuel cloud points.Then this device is cooled to required test temperature with 3 ℃/hour speed, placed at least 3 hours again, make fuel temperature stable.This oil tank of concuss so that the wax of separating out fully disperse; From oil tank, take a sample, and a sample export place on the urgent delivery pipeline that is connected on behind the oil tank given off 1 liter of oil fuel and it is backed in the oil tank.Then pump is started, the rotating speed of pump is fixed on is equivalent to 110 kilometers/hour pump speeds (rpm) under the travel speed.Under the situation of VW Golf, this pump speed is 1900 rev/mins (rpm), and corresponding therewith motor speed is 3800rpm.The pressure drop of monitoring strainer both sides and from the flow velocity of the effusive oil fuel of oil injection pump till running out of gas, generally needs 30-35 minute.

If the speed of fueling can be fixed on 2 milliliters/second (excess of fuel oil is about the 6.5-7 milliliters/second) in the oil injection pump, the result then is " qualified ".The fuel stream flow velocity that feeds to oil injection pump descends and represents " result is indeterminate ", and flow velocity is zero expression " failure ".

If the result is " qualified ", then normal part is along with the pressure drop of strainer both sides increases, and this pressure drop can rise to up to 60 kPas.Generally to reach the result of " qualified ", must make the wax of suitable vast scale pass through strainer." result is better " is characterised in that the pressure drop of strainer both sides can not rise to and surpasses 10 kPas, and this at first means most of wax by strainer, and optimum to be pressure drop be lower than 5 kPas.

In addition, in entire test, preferably from " excessive " oil fuel and " oil thrower supply " oil fuel, got the oil fuel sample once every 4 minutes.The oil tank sample one that these samples and test is preceding is reinstated DSC and is compared, to determine to pass through the ratio of the supply wax of strainer.Also get the oil fuel sample before the test, and after test, be made into the SEM sample, so that these two contrasts in actual performance to the size of wax crystalls and type.

Used additive is:

Additive 1

This be by 1 mole of o-sulfobenzoic acid cyclic anhydride and 2 mole two-(hydrogenant) fat amine in xylene solvent, in the 50%(w/w) concentration under the N of the 2-dialkyl amide base Phenylsulfonic acid that makes of reaction, the N-dialkyl ammonium salt, wherein alkyl is C _16-18H ₃₇Reaction mixture is stirred under the temperature between 100 ℃ and the reflux temperature.Solvent for use and pharmaceutical chemicals are should be as far as possible dry, make the acid anhydrides can not hydrolysis.

Analyze this product with 500 megahertz nuclear magnetic resonance spectrometers, confirm that product structure is

The molecular model of this compound is seen Figure 11.

Additive 2

This is that a kind of ethene and content are 17%(weight) multipolymer of vinyl-acetic ester, molecular weight is 3500, measures through 500 megahertz nuclear magnetic resonance spectrometers, per 100 alkylidene groups have 8 methyl chains.

Embodiment 3

In every mole acid anhydride base group, with the C of 1: 1 mol ratio of vinylbenzene-maleic anhydride copolymers of 1: 1 mole and 2 moles ₁₂H ₂₅OH and C ₁₄H ₂₉The mixture esterification of OH prepares vinylbenzene-dialkyl maleate copolymer, this multipolymer is used for esterification process, (excessive slightly, ethanol with 5%) make catalyzer with 1/10 mole P-toluenesulphonic acids, with dimethylbenzene is solvent, molecular weight is 50000, and contains 3%(weight) the ethanol that is untreated.

Additive 4

Mix generation 2-N, the dialkyl ammonium salt of N-dialkyl Aminobenzoate with the dihydro fat amine of 2 mol ratios at 60 ℃ of phthalate anhydrides with 1 mol ratio.

The result is as described below.

Embodiment 1

Fuel characteristic

Cloud point-14 ℃

Temperature-18.6 ℃ appears in wax

178 ℃ of initial boiling points

20%????230℃

90%????318℃

355 ℃ of full boiling points

The content of wax (25 ℃) 1.1%(weight)

Add additive 1,2 and 3 in fuel, its amount is about 250 P.P.M., and experimental temperature is-25 ℃.The crystallite size of wax is 1200 millimicrons long, and 90%(weight) wax can pass through Cummins FF105 strainer.

In experiment, can prove further that by the pressure drop of observing strainer wax has passed through strainer, pressure drop only increases 2.2kpa.

Embodiment 2

Repeat embodiment 1, the crystallite size of wax is 1300 millimicrons, reduces to 3.4kpa by the maximum final pressure of strainer.

Embodiment 3

Fuel characteristic

0 ℃ of cloud point

Temperature-2.5 ℃ appears in wax

182 ℃ of initial boiling points

20%????220℃

90%????354℃

385 ℃ of full boiling points

The content of wax (25 ℃) 1.6%(weight)

Add additive 1,2 and 3 in fuel, its amount is about 250 P.P.M..After measured, the crystallite size of wax is 1500 millimicrons ,-8.5 ℃ the nearly 75%(weight under the temperature of putting into practice) wax by Bosch 14543106 strainers.Maximum pressure drop by strainer is 6.5kpa.

Embodiment 4

Repeat embodiment 3, the crystallite size of wax is 2000 millimicrons long after measured, and it has 50%(weight) by strainer, maximal pressure is reduced to 35.3kpa.

Embodiment 5

The fuel that will be used for embodiment 3 is tested at-8 ℃ as the mode of embodiment 3 with the mixture process of the additive 2 of the additive 1 of 400ppm and 100ppm, and the content of wax is 1.4%(weight under this temperature condition).The size of wax is 2500 millimicrons after measured, 50%(weight) wax by strainer, the highest final pressure is reduced to 67.1kpa.

When this fuel is used to test boring tower owing to the pressure drop too fast test failure that makes that rises.We be sure of, this is just by shown in the photo, xln be flats institute extremely.Can not be by the topped impervious thin layer that on strainer, forms of the flats crystallization of strainer.On the other hand, the crystallization of " cubic " (or the nodular) by strainer does not form more open " filter cake ", fuel still can pass this layer " filter cake " up to be full of filter cake at strainer and reach certain thickness owing to the filter cake of wax pressure drop is gone beyond the limit once more before, fuel still can pass the loose filter cake of this layer.

Embodiment 6(comparative example)

With the fuel among the mixture process embodiment 3 of 4 parts of additives 4 of 500ppm and 1 part of additive 2, test at-8 ℃.After measured, the size of wax crystallization is 6300 millimicrons, 13%(weight) wax pass through strainer.

This embodiment is an extraordinary embodiment in prior art, and the gained result is good, and no crystallization is passed through.

Fig. 1-6 shows the scanning electron microscopy sheet of the wax crystallization that generates in fuel embodiment 1-6.

If embodiment 1-4 shows crystal energy successfully by strainer, to compare with existing level, good cold warm nature can improve the fuel wax content, and simultaneous temperature also further is lower than the wax appearance point (Appearance Point) of fuel.This does not relate to fuel system, as the Fuel cycle ability of the charging fuel from the engine to the preheating, extracted out from tanks, the ratio of charge raw material stream and circulating fuel, main filter surfaces long-pending with the ratio of charging fuel stream and the size and the position of prefilter and screen cloth.

These embodiment show that the crystallization length of strainer test is lower than 1800 millimicrons, has obtained better fuel performance.

Embodiment 7

In the present embodiment, additive 1 is added in the distillate fuel with following characteristics:

180 ℃ of initial boiling points

20%????223℃

90%????336℃

365 ℃ of full boiling points

5.5 ℃ of temperature appear in wax

Cloud point-3.5 ℃

In order to compare, also be added to following additives in the fuel:

Additive A:

The mixture of ethylene/vinyl acetate multipolymer, one of them be additive 2(1 part by weight) vinyl acetate/content of another additive (3 parts are by weight) is 36%(weight), molecular weight is 2000, use 500MHZ NMR to measure, per 100 methylene groups have 2 and 3 branched building blocks.

Additive B:

Additive 4 and 2(mol ratio are 4: 1) and mixture.

Addition of C:

The mixture of the Er docosoic ester of polyoxyethylene glycol, molecular-weight average is 600.

Additive D:

Ethylene/propene copolymer, ethylene content 56%(weight), molecular-weight average about 60000.

Following table has provided the add-on of additive, tests according to PCT, and PCT is described in detail as follows:

Programming cool test (PCT)

This is a refrigeration test slowly, and the heated oil of storing for input designs.Measure the cold fluid character of the fuel that contains additive with following PCT method.With 1 ℃/hour linear speed 300 milliliters of oil fuel are cooled to test temperature, make its weighing apparatus fixed then.After 2 hours, 20 milliliters upper layer is fallen in suction, is influenced by irregular bulk wax crystallization to prevent test, and this crystallization during cooling forms at oil/aerosphere face easily.Stir gently,, inject CFPPT filter assembly then settled wax dispersion in this bottle.Open the joint door, connect the negative pressure of 500mmHg, when 200 milliliters of fuel arrive the scale receptor by filter, close the joint door.If with collecting these 200 milliliters by given Fall mesh size 10 seconds, record passes through, if flow velocity is too slow, the expression filter stops up.

Be recorded in the grit number that experimental temperature is passed through.

(1) CFPPT is that cold filter stops up the real abbreviation of some examination, and (June 1966 for " Journal of the Institute of Petroleum " Vol.52, No.510, describe in detail to some extent in pp.173-185) at document.

Embodiment 8

Fuel used in the present embodiment have a following characteristic (ASTM-D86):

190 ℃ of initial boiling points (IBP)

20%????246℃

90%????346℃

374 ℃ of full boiling points (FBP)

Temperature-1.5 ℃ appears in wax

Cloud point+2.0 ℃

Amount by 1000 parts/per 1,000,000 is handled fuel with the active ingredient of following additives:

(E) mixture of the additive 4 of the additive 2 of 1 weight part and 9 weight parts;

(F) commodity ethylene vinyl acetate copolymer additive (trade mark is ECA5920, EXXON Chemicals);

(G) mixture of 3,1 parts of additive D of 1,1 part of additive of 1 part of additive and 1 part of additive K;

(H) (trade mark is 2042E to commodity ethylene vinyl acetate copolymer additive, Amoco);

(I) (trade mark is Keroflux 5486 to commodity ethene propionic acid ethylene copolymer additive, BASF);

(J) additive-free;

(K) reaction product of 4 moles of dihydro tallow amines and 1 mole of pyromellitic anhydride.Reaction is at 150 ℃, carries out in nitrogen atmosphere 6 hours under the solvent-free and stirring condition.

Measure these fuel following performance characteristics arranged:

(ⅰ) fuel passes through the still ability of Sai Er fuel master strainer at-9 ℃, and wax is as follows by the per-cent of this filter:

The percentage ratio (%) that additive passes through to time (branch) wax that stops up

E????11????18～30

F????16????30

G does not stop up 90～100

H????15????25

I????12????25

J????9????10

(ⅱ) main filter pressure fall with the result of time relation as shown in Figure 12.

(ⅲ) the wax sedimentation in the fuel is measured by cooling off 100 milliliters of fuel in the calibration gauge graduated cylinder.Preferably from being higher than 10 ℃ of fuel cloud points, but be not less than the fuel cloud point more than 5 ℃,,, and keep the described time in this temperature up to experimental temperature with 1 ℃ of/hour cooling graduated cylinder.Experimental temperature and extraction time are described by the application, promptly refer to diesel oil and heated oil.Reasonablely be, experimental temperature is minimum to be lower than 5 ℃ of cloud points, and minimum at the minimum extraction time of this temperature is 4 hours.Best, experimental temperature is lower 10 ℃ or more than the fuel cloud point, and extraction time is 24 hours or longer.

After leaching period, the sight gauge graduated cylinder, the degree of crystalline wax is separated out in range estimation, and promptly the wax floor height goes out the height of the metering letter end (0 milliliter), represents with the percentage ratio of cumulative volume.Can see limpid fuel on the crystalline of separating out, this measuring method often is enough to judge the wax of separating out.

Sometimes, the fuel on the wax layer of separating out is muddy, perhaps, because wax crystalls only sees that near the tube end it is denser.In this situation, adopt the quantitative analysis method of revising and deciding.At this moment, the 5%(5ml at earlier careful sucking-off top) fuel, store; Sucking-off 45% fuel carefully from the top is thrown away again; Sucking-off 5% is carefully again stored; Inhaling 35% again throws away; Heat the wax in last 10% is dissolved.The sample of storing be called later on the top, in, bottom sample.Should emphasize that the used negative pressure of sucking-off sample is very low, is the 200mm water column, and the head of suction pipe the surface of fuel to be just be placed on, the liquid of wax concentration stream in the different layers can be confused in the graduated cylinder to avoid producing.Then, sample is heated to 60 ℃ with 15 minutes, uses the wax content in heating differential analysis (DSC) the method measure sample as described above.

In this example, used Mettler TA 2000B heating differential analysis instrument.25 liters of samples are put into the sample chamber, and the standard kerosene is put into reference to the chamber; With 22 ℃/per minute they are cooled to from 60 ℃ then higher 10 ℃ than the temperature that wax occurs at least, preferably high 20 ℃, temperature; Then, be cooled to be less than about the temperature of 20 ℃ of wax appearance points with 2 ℃/per minute.

Must there be contrast interpolation, that do not have refrigerative sedimentation fuel.The degree of separating out wax relevant with wax appearance point (WAT) (or △ WAT=sedimentation sample wax appearance point one original wax appearance point).Negative value is represented the fuel dewaxing, on the occasion of representing by the sedimentation fuel rich content of wax.Also the content of available wax measures the amount of separating out from these samples.The original wax % of wax %-of the △ %=sedimentation reason sample of the △ %(wax of the % of this available wax or wax) illustrates that same, negative value is represented the fuel dewaxing, is rich in wax on the occasion of expression by sedimentation.

In this example, fuel is cooled to-9 ℃ with 1 ℃/hour from+10 ℃, and this experiment cold soaking is gone out the time is 48 hours.The result is as follows:

The visible wax precipitation sedimentation sample wax appearance point of additive ℃

5% end 10% in the top 5%

E complete muddy-10.80-4.00-3.15

The F bottom is dense, top 50% clear-13.35-0.80-0.40

G????100%????-7.85????-7.40????-7.50

H top 35% clear-13.05-8.50+0.50

I top 65% is clear

J 100% half glue-6.20-6.25-6.40

(result also is shown in Figure 13)

Wax appearance point wax appearance point ℃ (settled sample) originally

5% end 10% in (not settled fuel) top 5%

E????-6.00????-4.80????+2.00????+2.85

F????-5.15????-8.20????+4.35????+4.75

G????-7.75????-0.10????+0.35????+0.25

H????-5.00????-8.05????+3.50????+4.50

J????-6.20????0.000????+0.05????-0.20

(noting: can control sulphur effectively with effective additives G and temperature occur).

The settled sample of the %(of additive wax)

5% end 10% in the top 5%

E????-0.7????+0.8????+0.9

F????-0.8????+2.1????+2.2

G????±0.0????+0.3????+0.1

H????-1.3????-0.2????+1.1

J????-0.1????±0.0????±0.1

These results show that along with existing crystal size to reduce because of additive, crystalline wax is separated out and accelerated.As, the fuel of sedimentation is cooled to below its cloud point when inciting somebody to action not, can not in liquid, freely overturn because of the mutual locking of tabular crystal, occurring the grain body easily separates out, form gel-like texture, still, add used mobile innovative approach after, can change crystalline state, plate crystal reduces and tendency forms the needle-like crystalline form of size at several 10 micrometer ranges.The needle-like crystalline form can free movement in liquid, also separates out with fast speed.Separating out these crystallizations makes troubles for storage tank and delivery system.The wax layer that concentrates can sop up, and when particularly low or storage tank stirs when level of fuel (as feed angle), this moment, strainer may be plugged.

Be lower than 10 nanometers if the size of wax crystalls can be reduced to again, so, crystallization is separated out can be slower, and compare anti-wax settlement action with the fuel of sedimentation wax crystalls and can make fuel that preferable performance is arranged.Be less than 4 nanometers if the size of wax crystalls is reduced to, so,, almost can eliminate the settled tendency of crystallization of wax in storage period.If the wax crystalls size is reduced to most preferably less than 2 nanometers, so, wax crystalls inner maintenance of several weeks in fuel suspends, and satisfies the requirement of some storage system, has eliminated the settled problem of wax basically.

(ⅳ) character of CFPP is as follows:

Addition of C FPP temperature (℃) CFPP decline (℃)

E????-14????11

F????-20????17

G????-20????17

H????-20????17

I????-19????16

J????-3????-

(CFPP is the abbreviation that cold filter stops up point)

(ⅴ) average crystalline size is as follows:

Additive size (nanometer)

E????4400

F????10400

G????2600

H????10800

I????8400

The J thin slice surpasses 50000

Claims (2)

1, will be used for the using method that the content of wax distillates fuel as the compound of additive, this method comprises: this additive compound directly is added to distillates fuel, this additive dissolves in this fuel, maybe this additive compound is dissolved in earlier in the suitable solvent to form enriched material, then this enriched material is added to and distillates fuel, additivated amount be the heavy 0.001-0.5wt% that distillates fuel.

2, according to the using method of claim 1, wherein said additive compound contains at least two substituting groups and has one sterie configuration, this sterie configuration makes them occupy wax molecule position in (001) plane and (II X) plane point of intersection, for example (110) plane and (111) plane in the wax crystallization, substituting group for contain at least more than 2 of 10 carbon atoms just-alkyl, substituent distance is 4.5-5.5A, two just-interfacial angle between the local symmetry of alkyl is 75 ° to 90 °.

Images