CN1743433A - Method for preparing multi-effect additive of low-surface diesel - Google Patents
Method for preparing multi-effect additive of low-surface diesel Download PDFInfo
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Abstract
A preparation method for a low S diesel oil multi-effect additive includes 1, mixing PE-ring 1 acetate and C6-C50 fatty acid with the number-average molar mass of 1500-3000 according to the alkyl radical mole proportion of 1:001~10 and carrying out graft polymerization reaction under 60-200deg.C in the evocator and non-polar solvent to get a polymer, 2, adding an aminate or an esterified product in the polymer in the alkyl radical mole number ratio to fatty acid in step 1 of 0.1~5:1 to be reacted under 60~200deg.C to get a multi-effect additive, in which, the aminate or esterified reactor is selected from C1-C18 alkanol, C2-C18 epoxide, C1-C18 organic amine, C2-C6 alkamine and alkoxyl multi-amine.
Description
Technical field
The invention belongs to diesel-dope, definite saying so both can be used as diesel antiwear additive, also can be used as the multipurpose additive of diesel flow improver.
Technical background
Along with the pay attention to day by day of countries in the world to environmental issue, pollute in order to reduce diesel exhaust gas, produce high-quality clean diesel, become the developing direction of modern petroleum refining industry.This diesel oil has generally that sulphur content is low, and it is low to contain aromatic hydrocarbons, cetane value height, characteristics such as cut is light.Studies show that sulphur is the harmful element that increases CH, CO, particularly pellet (PM) in the diesel engine emissions, so it is particularly important to improving topsoil to reduce in the diesel oil sulphur content.The diesel oil specification of the U.S., Canada, every Western Europe country is all stipulated diesel oil S content less than 0.05% now, and country that has even regulation diesel oil S content are no more than 0.0015%, and aromaticity content is also lower.Because they have generally adopted harsh hydrogenation technique, the content that polarity in the diesel oil contains oxygen, nitrogenous compound is all very low, the content of many rings, double ring arene is also less, thereby reduced the natural lubricity of diesel oil, some oil injection pumps that rely on diesel oil itself to be lubricated have been caused, wearing and tearing occur as rotor pump (rotary pumps), proportioning pump (distributor pumps), reduced their work-ing life.
The low temperature flowability that how much has determined oil product of the alkane that contains various different quantitiess in the diesel oil, particularly long-chain n-praaffin.When temperature reduces, normal paraffin is separated as plate crystal, they interact to form and wherein still seal the tridimensional network that liquid oil is arranged, make the viscosity of oil product increase and mobile decline, this phenomenon can cause the oil circuit filter screen to stop up, influence vehicle and normally use, also influence the accumulating and the loading and unloading of diesel oil.
As everyone knows, these problems can be alleviated by add additive in diesel oil.Diesel antiwear additive (also being oiliness additive) can improve the oilness of low-sulfur diesel-oil; Diesel flow improver can improve the low temperature flowability of diesel oil, reduces cold filter clogging temperature, the condensation point of diesel oil, makes diesel oil be able to normal use in low temperature environment.Use the method for additive to have advantages such as cost is little, production is flexible, pollution is few, pay attention to widely industrial being subjected to.
The lipid acid anti-wear agent that rocket engine fuel is used, as the acid additives of dimerization acids, since bad with the composite performance of lubricating oil, can not be applied to diesel oil.Therefore, diesel antiwear additive mostly is the derivative of fatty acid ester, acid amides or salt.EP773279 discloses and has used the carboxylicesters of dimeracid and hydramine prepared in reaction as diesel antiwear additive.EP798364 discloses with the salt of lipid acid and aliphatic amide prepared in reaction or acid amides as diesel antiwear additive.EP1209217 discloses C
6～C
50The reaction product of saturated fatty acid and dicarboxylic acid and short chain oils dissolubility primary, the second month in a season, tertiary amine is as diesel antiwear additive.WO9915607 discloses the reaction product of dimer (fatty acid) yl and epoxide as diesel antiwear additive.But above additive all can not improve the low-temperature fluidity of diesel oil.
The multipolymer of ethene and unsaturated ester, as US 3,048,479 disclosed polyethylene vinyl acetate esters (EVA) are to use more a kind of diesel flow improver at present.The Paradyne20 of EXXON company, 25, ECA5920,5966,8400,8401, home-made T1804, T1805 etc. belong to this additive types, but above diesel flow improver is to the DeGrain that improves of diesel fuel lubricity.
WO 9618708 open EVA multipolymers and the compound use of fatty acid ester diesel antiwear additive can improve diesel fuel lubricity, but this simple composite is little to the low temperature flowability improvement of diesel oil, and promptly anti-wear agent can be offset the partial action of FLOW IMPROVERS.
Summary of the invention
The invention provides the preparation method of multi-effect additive of low-surface diesel, this additive can improve the oilness of diesel oil, can improve the diesel oil at low-temperature flowability again.
Multi-effect additive of low-surface diesel provided by the invention can be by following two kinds of methods preparation.
Method one:
(1) with number-average molecular weight is 500～3000 polyethylene vinyl acetate ester (EVA) and C
6～C
50Lipid acid mixes, and is reinforced with the ratio of the carboxyl mole number 1: 0.01～10 of lipid acid according to the vinyl acetate in the polyethylene vinyl acetate ester (VA), carries out graft polymerization reaction in 60～200 ℃ in the presence of initiator and solvent, obtains polymerisate;
(2) adding the ratio that adds the carboxyl mole number of lipid acid with step (1) in polymerisate is 0.1～5: 1 the C that is selected from
1～C
18Fatty Alcohol(C12-C14 and C12-C18), C
2～C
18Epoxide, C
1～C
18Organic amine, C
2～C
6At least a amination or the reactant of esterification of amino alcohol and alkoxy polyamine react under 60～200 ℃, obtain multipurpose additive.
Specifically:
In the step (1), the ratio of the mole number of carboxyl is 1: 0.01～10 in the vinyl acetate among the EVA and the lipid acid, preferred 1: 0.05～5, be preferably 1: 0.1～and 1.The graft polymerization reaction temperature is 60～200 ℃, preferred 80～180 ℃.2～10 hours reaction times, preferred 3～7 hours.Lipid acid can be once all to add, and also can be to add in batches.
The reaction of step (2) can be carried out with reference to conventional esterification or amination reaction.In the reaction, C
1～C
18Fatty Alcohol(C12-C14 and C12-C18), C
2～C
18Epoxide, C
1～C
18Organic amine, C
2～C
6Amino alcohol or alkoxy polyamine are according to adding the carboxyl mole number 0.1～5: 1 of lipid acid with step (1), and preferred 0.2～3: 1 mol ratio adds.Temperature of reaction is 60～200 ℃, preferred 80～180 ℃.2～10 hours reaction times, preferred 3～7 hours.
The reaction of step (2) can be carried out in the presence of acid or alkaline catalysts, but does not generally need catalyzer with the reaction of organic amine, generally needs basic catalyst with the reaction of epoxide.Acid catalyst can be sulfuric acid, tosic acid, acidic ion exchange resin, acidic white earth etc.; Basic catalyst can be sodium hydroxide, potassium hydroxide, sodium methylate (being dissolved in the methyl alcohol), dimethylcyclohexylamine etc.Catalyst consumption generally is 0.5～5% of a reactant weight.
Method two:
(1) with C
6～C
50Lipid acid be selected from C
1～C
18Fatty Alcohol(C12-C14 and C12-C18), C
2～C
18Epoxide, C
1～C
18Organic amine, C
2～C
6One or more aminations or reactant of esterification in amino alcohol and the alkoxy polyamine react under 60～200 ℃, obtain derivative of fatty acid;
(2) be that 500～3000 polyethylene vinyl acetate ester mixes with the product of step (1) with number-average molecular weight, reinforced according to vinyl acetate among the EVA with the mol ratio of the carboxyl mole number 1: 0.01～10 of (1) middle lipid acid, in the presence of initiator and solvent, carry out graft polymerization reaction in 60～200 ℃, obtain multipurpose additive.
Specifically:
The reaction of step (1) can be carried out with reference to conventional esterification or amination reaction.In the reaction, C
1～C
18Fatty Alcohol(C12-C14 and C12-C18), C
2～C
18Epoxide, C
1～C
18Organic amine, C
2～C
6Amino alcohol or alkoxy polyamine and C
6～C
50The ratio of the carboxyl mole number of lipid acid is 0.1～5: 1, preferred 0.2～3: 1, and temperature of reaction is 60～200 ℃, preferred 80～180 ℃.2～10 hours reaction times, preferred 3～7 hours.
Reaction can be carried out in the presence of acid or alkaline catalysts, but does not generally need catalyzer with the reaction of organic amine, generally needs basic catalyst with the reaction of epoxide.Acid catalyst can be being as sulfuric acid, tosic acid, acidic ion exchange resin, acidic white earth etc.; Basic catalyst can be sodium hydroxide, potassium hydroxide, sodium methylate (being dissolved in the methyl alcohol), dimethylcyclohexylamine etc.Catalyst consumption generally is 0.5～5% of a reactant weight.
In the step (2), the ratio of the carboxyl mole number of lipid acid is 1: 0.01～10 in vinyl acetate among the EVA and the step (1), preferred 1: 0.05～5, be preferably 1: 0.1～and 1.Temperature of reaction is 60～200 ℃, preferred 80～180 ℃.2～10 hours reaction times, preferred 3～7 hours.Derivative of fatty acid can once all add, and also can be to add in batches.
In method one and method two:
Said initiator can be superoxide or azo compound, and is fine etc. as ditertiary butyl peroxide, diisopropylbenzyl superoxide, lauroyl peroxide, benzoyl peroxide, di-cyclohexylperoxy dicarbonate, azo two isobutyls.The consumption of initiator generally is 0.5～20% of an EVA weight, preferred 1～10%.Initiator can once all join in the reactor, also can slowly drip.
Said solvent is a non-polar solvent, as toluene, dimethylbenzene, ethylbenzene, normal hexane, hexanaphthene etc., also can be the aromatic hydrocarbons thinning oil, and boiling range is 159～185 ℃, and the latter is preferred.Solvent load generally is 30～150% of a material gross weight.
Said polyethylene vinyl acetate ester (EVA) FLOW IMPROVERS is at present domestic and international widely used a kind of additive.Its structure is as shown below:
The number-average molecular weight of EVA is 500～3000 (gas-phase permeation platen presses), and is preferred 1000～2500, is preferably 1500～2000.Vinyl acetate among the EVA (VA) content is 20～45%, and between preferred 25～40%, the side chain degree is not more than 6, and (the side chain degree refers to per 100-CH in the multipolymer
2Contain in-the group-CH
3The group number).
EVA can be according to US 3,048, and 479 or other pertinent literature disclosed method self-control, also can buy from market.The Paradyne20 of EXXON company, 25, ECA5920,5966,8400,8401, home-made T1804, T1805 etc. all can.
Said lipid acid, preferred C
10～C
40Lipid acid.Can be monocarboxylic acid or polycarboxylic acid; Can be saturated acid or unsaturated acid.One or more in caproic acid, hexanodioic acid, sad, isocaprylic acid (2 ethyl hexanoic acid), capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, oleic acid, linolic acid, linolenic acid, stearic acid, Palmiticacid, ricinolic acid, arachidonic acid, icosa alkene, 20 acid, erucic acid, docosenoic acid, dimerization oleic acid, linoleic acid dimer etc. for example; Can also be mixing acid, as various vegetable fatty acids, as palmitinic acid, soybean oleic acid, arachic acid, vegetable seed oleic acid etc., preferably normal temperature be liquid C down
14～C
40Unsaturated acid is as oleic acid, linolic acid, linolenic acid, linoleic acid dimer, arachidonic acid, ricinolic acid etc.
The preferred C of said Fatty Alcohol(C12-C14 and C12-C18)
2～C
10Alkanol can be monohydroxy-alcohol or polyvalent alcohol.Monohydroxy-alcohol such as ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol etc., just structure and isomery all can.Polyvalent alcohol such as ethylene glycol, polyoxyethylene glycol, 1,2-propylene glycol, 1, the butyleneglycol of ammediol, glycerol, various structures, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, tetramethylolmethane, sorbyl alcohol, anhydrous sorbitol etc.Preferred C in the alcohol
2～C
8Polyvalent alcohol, preferably C
2～C
5Polyvalent alcohol.
Said epoxide can be C
2～C
18Epoxide, as oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 1,2-epoxy octadecane etc. or their mixture.Preferred C
2～C
8Epoxide.
Said organic amine can be monoamine or polyamine.Monoamine can be C
1～C
18Aliphatic amide can also be Cycloalkyl amine or heterocyclic amine, and primary amine or secondary amine all can.The preferred C of aliphatic amide
2～C
16Aliphatic amide, just structure and isomery all can; Cycloalkyl amine can be cyclopentamine, hexahydroaniline etc.; Heterocyclic amine can be a morpholine etc.Polyamine can be C
2～C
18Polyamine, preferred C
2～C
12Polyamine as quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine etc., also can be that structural formula is H
2N[(CH
2)
nNH]
mThe polyamines polyene of H, wherein n is 2～4, and preferred 2～3 integer, m are 1～5, preferred 3～4 integer is as diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines etc.Preferred diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
Said amino alcohol (or hydramine) can be a 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, Monoethanolamine MEA BASF, diethanolamine, N methyldiethanol amine, trolamine or its mixture.
Said alkoxy polyamine be by polyamines polyene and epoxide with 1: 0.5～10, the reaction product of preferred 1: 1～5 mol ratios.Wherein the polyamines polyene structural formula is H
2N[(CH
2)
nNH]
mH, n are 2～4, and preferred 2～3 integer, m are 1～5, preferred 3～4 integer.As quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines etc.Preferred diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.Described epoxide optimization ethylene oxide, 1,2 epoxy prapane, 1, the 2-butylene oxide ring.
The addition of multi-effect composite additive provided by the invention in diesel oil generally is 20～2000ppm, preferred 50～1000ppm.
According to using needs, additive provided by the invention can also with other additive, use simultaneously as cetane number improver, detergent-dispersant additive, metal passivator, sanitas etc.
Embodiment
The present invention is further illustrated below by embodiment.In these embodiments, molecular-weight average all is to measure according to the gas-phase permeation platen press; The oilness of diesel oil according to CEC-F-06-A-96 or the described method of ISO/FDIS 12156-1 (American process is ASTMD-6079-97) at the reciprocal trier of high frequency (High-Frequency Reciprocating Rig, grinding defect diameter (Wear ScarDiameter when HFRR) upward (production of Britain PCS instrument company) measures 60 ℃, WSD), by the influence of temperature and humidity is proofreaied and correct the WS1.4 that reports the result. In the diesel oil at low-temperature fluidity evaluating, cold filter clogging temperature (CFPP) is measured according to the method for SH/T 0248-92, and condensation point (SP) is measured according to GB 510-83 method.
Example 1～2nd, the preparation of EVA.
Example 1
21g vinyl acetate, 60～90 ℃ of sherwood oils of 90g and 0.9g Diisopropyl azodicarboxylate are placed a 500ml high-pressure reactor that electric mixer, temperature control unit be housed, and heat temperature raising is also squeezed into ethylene gas, keeps ethylene pressure and is about 8.0MPa (80kgf/cm
2), 70 ℃ of reactions of temperature 6 hours.Reaction finishes postcooling to room temperature, emptying reactor overbottom pressure, and underpressure distillation removes and desolvates and unreacted reactant, gets polymerisate 25.2g, adds 25g aromatic hydrocarbons thinning oil and is made into about 50% diluent EVA1, and its analytical data is as shown in table 1.
Example 2
With 21g vinyl acetate, 100g 120
#Industrial naptha and 0.9g di-cyclohexylperoxy dicarbonate place a 500ml high-pressure reactor that electric mixer, temperature control unit be housed, and heat temperature raising is also squeezed into ethylene gas, keeps ethylene pressure and is about 8.0MPa (80kgf/cm
2), 80 ℃ of reactions of temperature 7 hours.Reaction finishes postcooling to room temperature, emptying reactor overbottom pressure, and underpressure distillation removes and desolvates, and gets polymerisate 23.1g, adds 23g aromatic hydrocarbons thinning oil and is made into about 50% diluent EVA2, and its analytical data is as shown in table 1.
The performance data of commodity EVA is also listed in the table 1.
Table 1
| EVA source polymer solvent number-average molecular weight VA content/% side chain degree |
| Synthetic 60～90 oil, 1,641 29.9 4.5 EVA2 synthetic 120 of EVA1 #Industrial naptha 1,734 33.8 2.4 EVA3 T1804 120 #Industrial naptha 1,800 35.9 3.0 EVA4 Paradyne25 hexanaphthenes 1,800 38.0 5.3 EVA5 ECA5920 hexanaphthenes 2,100 31.0 5.4 |
Example 3～6th, the preparation of derivative of fatty acid.
Example 3
With 100g ricinolic acid and 25.5g 1,2-propylene glycol (ricinolic acid and 1, the mol ratio of 2-propylene glycol is about 1: 1) and the agent of 1.3g Catalyzed by p-Toluenesulfonic Acid place a reactor that electric mixer, thermometer, water trap, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep nitrogen gas stream, heated and stirred to be warming up to 140 ℃, divide water reaction 5 hours, be cooled to 80 ℃ then, add 0.6g Ca (OH)
2, in and half an hour after-filtration, the filtrate acid number is 3.8mgKOH/g.
Example 4
The 100g linolic acid is placed a reactor that electric mixer, thermometer, reflux condensing tube and dropping funnel be housed, heated and stirred is warming up to 120 ℃, with 41.4g 1,2-propylene oxide (linolic acid and 1, the mol ratio of 2-propylene oxide is about 1: 2) and 2.5g methyl cyclohexane amine catalyst in 2 hours, slowly be added drop-wise in the reactor, back flow reaction 6 hours is when temperature is elevated to 140 ℃ and quantity of reflux seldom the time, cooling promptly gets product, and its acid number is 7.4mgKOH/g.
Example 5
100g oleic acid, 52.8g trolamine (mol ratio of oleic acid and trolamine is about 1: 1) and 2.8g sodium methylate/catalyst for methanol are placed a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 160 ℃, reacted 5 hours, be cooled to 90 ℃ then, add neutralization of 3.2g acidic white earth and filtration and promptly get product, recording its acid number is 8.3mgKOH/g.
Example 6
100g linolic acid, 15.5g morpholine and 26.1g triethylene tetramine (mol ratio of linolic acid, morpholine, triethylene tetramine is about 1: 0.5: 0.5) are placed a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140 ℃, divide water reaction 7 hours, cooling promptly gets product.
Example 7～11 prepares multipurpose additive according to method two.
To be selected from the different polyethylene vinyl acetate esters (EVA) of table 1, the derivative of fatty acid in the example 3～6, initiator is selected ditertiary butyl peroxide for use, and it is 159～185 ℃ aromatic hydrocarbons thinning oil that solvent is all used boiling range, and solvent load is identical with derivative of fatty acid.According to the conditioned response shown in the table 2, obtain different products.
Table 2
| Example | EVA | Derivative of fatty acid | VA and lipid acid mol ratio | Initiator accounts for ratio/% of EVA | Temperature of reaction/℃ | Reaction times/hr |
| 7 8 9 10 11 | EVA1 EVA2 EVA3 EVA4 EVA5 | Example 3 examples 4 examples 5 examples 6 examples 4 | 1∶0.5 1∶0.25 1∶0.2 1∶0.3 1∶0.4 | 8 5 3 6 4 | 145 150 155 145 150 | 4.5 6.0 4.0 5.5 5.0 |
Example 12
This example is according to method one preparation multipurpose additive.
Place one electric mixer is housed 100.0g T1804 (EVA3) and 19.1g oleic acid (VA and oleic mol ratio 3: 1), thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140～150 ℃, 5.0g ditertiary butyl peroxide and 19g aromatic hydrocarbons thinning oil mixture are splashed into reactor from dropping funnel, 1.5 drip off in hour, keep 140～150 ℃ of reactions of temperature 3 hours, add 7.1g diethanolamine (diethanolamine and oleic mol ratio are 1: 1) and 7.1g aromatic hydrocarbons thinning oil, blow water at 140 ℃ with nitrogen and got final product in 3 hours.
Example 13
This example is according to method one preparation multipurpose additive.
Place one electric mixer is housed 100.0g EVA2 and 14.5g ricinolic acid (mol ratio of VA and ricinolic acid 4: 1), thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 145～150 ℃, 6.0g ditertiary butyl peroxide and 15g aromatic hydrocarbons thinning oil mixture are splashed into reactor from dropping funnel, 1.5 drip off in hour, keep 145～150 ℃ of reactions of temperature 4 hours, add 8.9g amino dodecane (mol ratio of amino dodecane and ricinolic acid is 1: 1) and 9.0g aromatic hydrocarbons thinning oil, blow water at 100 ℃ with nitrogen and got final product in 3 hours.
Example 14
This example is the result of use of multipurpose additive in diesel oil that example 7～13 makes.Select the Yanshan Mountain-20 for use
#Blended diesel is as test oil, and its physicochemical property sees Table 3, adds HFRR method (ISO12156-1) the grinding defect diameter WS of agent front and back diesel oil
1.4, cold filter clogging temperature and condensation point see Table 4, when grinding defect diameter during less than 460um (60 ℃), then the oilness of diesel oil is qualified.
The physicochemical property of table 3 diesel oil
| Project | Numerical value |
| Density (20 ℃)/gcm -3Viscosity (20 ℃)/mm 2·s -1S content/total the double ring arene of the total mononuclear aromatics/m% of the total cycloalkane/m% of ppm alkane/m%/m% thrcylic aromatic hydrocarbon/m% CFPP/ ℃ SP/ ℃ initial boiling point/℃ 20% heats up in a steamer a little/℃ 50% heat up in a steamer a little/℃ 90% heat up in a steamer a little/℃ do/℃ WS1.4/um | 0.8298 3.229 0.5 44.8 31.6 21.9 1.7 0 -23 -29 193 226 249 276 286 619 |
Table 4 multipurpose additive is to the improvement of diesel fuel lubricity and low-temperature fluidity
| Additive | Add dosage/mg.kg -1 | WS 1.4 /um | CFPP /℃ | SP /℃ |
| EVA2 (example 2) example 4 product E VA2 (example 2) example 4 product examples 8 product examples 7 product examples 9 product examples 10 product examples 11 product examples 12 product examples 13 products | 750 150 750 150 1050 900 1000 800 700 750 800 | 594 433 406 319 308 342 367 334 327 341 | -27 -22 -24 -28 -27 -29 -29 -27 -28 -29 | ＜-35 -28 ＜-35 ＜-35 ＜-35 ＜-35 ＜-35 ＜-35 ＜-35 ＜-35 |
By table 4 as can be seen, add EVA multipolymer (example 2 products) separately,, the oilness of diesel oil is not almost had improvement though can reduce cold filter clogging temperature, the condensation point of diesel oil.Add derivative of fatty acid (example 4 products) separately,, make the low temperature flowability variation of diesel oil though can improve the oilness of diesel oil.From the contrast of example 8 and example 2 and 4 as can be seen, diesel oil multi-efficient additive provided by the invention is to fine its oilness of improving of low-sulfur diesel-oil energy, simultaneously diesel oil is had good filter, the pour point depression effect of falling, its effect is better than the simple composite of EVA multipolymer and derivative of fatty acid.
Claims (19)
1. the preparation method of a multi-effect additive of low-surface diesel comprises:
(1) with number-average molecular weight is 500～3000 polyethylene vinyl acetate ester and C
6～C
50Lipid acid is according to the mixed of carboxyl mole number in vinyl acetate in the polyethylene vinyl acetate ester and the lipid acid 1: 0.01～10, carries out graft polymerization reaction in 60～200 ℃ in the presence of initiator and non-polar solvent, obtains polymerisate;
(2) add in polymerisate that to add the ratio of carboxyl mole number in the lipid acid with step (1) be 0.1～5: 1 at least a amination or reactant of esterification, react under 60～200 ℃, obtain multipurpose additive, amination or reactant of esterification are selected from C
1～C
18Fatty Alcohol(C12-C14 and C12-C18), C
2～C
18Epoxide, C
1～C
18Organic amine, C
2～C
6Amino alcohol and alkoxy polyamine.
2. according to the described preparation method of claim 1, it is characterized in that in the step (1), the ratio of carboxyl mole number is 1: 0.05～5 in vinyl acetate and the lipid acid, the graft polymerization reaction temperature is 80～180 ℃, 2～10 hours reaction times.
3. according to the described preparation method of claim 1, it is characterized in that, in the step (2), amination or reactant of esterification according to lipid acid in the ratio of carboxyl mole number 0.2～3: 1 add, temperature of reaction is 80～180 ℃, 2～10 hours reaction times.
4. the preparation method of a multi-effect additive of low-surface diesel comprises:
(1) with C
6～C
50Lipid acid and at least a amination or reactant of esterification react under 60～200 ℃, obtain derivative of fatty acid, and amination or reactant of esterification are selected from C
1～C
10Fatty Alcohol(C12-C14 and C12-C18), C
2～C
18Epoxide, C
1～C
18Organic amine, C
2～C
6The ratio of carboxyl mole number is 0～1～5: 1 in amino alcohol and the alkoxy polyamine, amination or reactant of esterification and lipid acid;
(2) with number-average molecular weight be 500～3000 polyethylene vinyl acetate ester and derivative of fatty acid mixed according to carboxyl mole number 1: 0.01～10 in the lipid acid of vinyl acetate in the polyethylene vinyl acetate ester and step (1), in the presence of initiator and non-polar solvent, carry out graft polymerization reaction in 60～200 ℃, obtain multipurpose additive.
5. according to the described preparation method of claim 4, it is characterized in that in the step (1), the ratio of carboxyl mole number is 0.2～3: 1 in amination or reactant of esterification and the lipid acid, temperature of reaction is 80～180 ℃, 2～10 hours reaction times.
6. according to the described preparation method of claim 4, it is characterized in that in the step (2), the ratio of the mole number of carboxyl is 1: 0.05～5 in vinyl acetate and the lipid acid, temperature of reaction is 80～180 ℃, 2～10 hours reaction times.
7. according to claim 1 or 4 described preparation methods, it is characterized in that said initiator is superoxide or azo compound, the consumption of initiator is 0.5～20% of a polyethylene vinyl acetate ester weight.
8. according to the described preparation method of claim 7, it is characterized in that, said initiator is that ditertiary butyl peroxide, diisopropylbenzyl superoxide, lauroyl peroxide, benzoyl peroxide, di-cyclohexylperoxy dicarbonate or azo two isobutyls are fine, and the consumption of initiator is 1～10% of a polyethylene vinyl acetate ester weight.
9. according to claim 1 or 4 described preparation methods, it is characterized in that said solvent is that toluene, dimethylbenzene, ethylbenzene, normal hexane, hexanaphthene or boiling range are 159～185 ℃ aromatic hydrocarbons thinning oil, solvent load is 30～150% of a material gross weight.
10. according to claim 1 or 4 described preparation methods, it is characterized in that the number-average molecular weight of said polyethylene vinyl acetate ester is 1000～2500, vinyl acetate content wherein is 20～45%, and the side chain degree is not more than 6.
11., it is characterized in that said lipid acid is C according to claim 1 or 4 described preparation methods
10～C
40Lipid acid.
12., it is characterized in that said lipid acid is C according to the described preparation method of claim 11
14～C
40Unsaturated fatty acids.
13., it is characterized in that said Fatty Alcohol(C12-C14 and C12-C18) is C according to claim 1 or 4 described preparation methods
2～C
10Alkanol.
14., it is characterized in that said Fatty Alcohol(C12-C14 and C12-C18) is C according to the described preparation method of claim 13
2～C
8Polyvalent alcohol.
15., it is characterized in that said epoxide is C according to claim 1 or 4 described preparation methods
2～C
8Epoxide.
16., it is characterized in that said organic amine is C according to claim 1 or 4 described preparation methods
1～C
18Monoamine or C
2～C
18Polyamine.
17., it is characterized in that said organic amine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines according to the described preparation method of claim 16.
18. according to claim 1 or 4 described preparation methods, it is characterized in that said amino alcohol is a 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, Monoethanolamine MEA BASF, diethanolamine, N methyldiethanol amine, trolamine or its mixture.
19., it is characterized in that said alkoxy polyamine is according to 1: 0.5～10 molar ratio reaction products therefroms by polyamines polyene and epoxide according to claim 1 or 4 described preparation methods.
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| CNB2004100736454A CN100478373C (en) | 2004-08-31 | 2004-08-31 | Method for preparing multi-effect additive of low-sulfur diesel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100736454A CN100478373C (en) | 2004-08-31 | 2004-08-31 | Method for preparing multi-effect additive of low-sulfur diesel |
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| Publication Number | Publication Date |
|---|---|
| CN1743433A true CN1743433A (en) | 2006-03-08 |
| CN100478373C CN100478373C (en) | 2009-04-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619249B (en) * | 2009-06-15 | 2013-03-27 | 孙广玉 | Alcohol-based fuel modifier, enhancer, alcohol-based liquid fuel after modification and enhancement and production process thereof |
| CN103725337A (en) * | 2013-12-22 | 2014-04-16 | 山西华顿实业有限公司 | High-cleanness diesel lubricant |
-
2004
- 2004-08-31 CN CNB2004100736454A patent/CN100478373C/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619249B (en) * | 2009-06-15 | 2013-03-27 | 孙广玉 | Alcohol-based fuel modifier, enhancer, alcohol-based liquid fuel after modification and enhancement and production process thereof |
| CN103725337A (en) * | 2013-12-22 | 2014-04-16 | 山西华顿实业有限公司 | High-cleanness diesel lubricant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100478373C (en) | 2009-04-15 |
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