CN100460488C - Preparation process of multi-efficient additive of low sulphur diesel oil - Google Patents
Preparation process of multi-efficient additive of low sulphur diesel oil Download PDFInfo
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- CN100460488C CN100460488C CNB2006100007044A CN200610000704A CN100460488C CN 100460488 C CN100460488 C CN 100460488C CN B2006100007044 A CNB2006100007044 A CN B2006100007044A CN 200610000704 A CN200610000704 A CN 200610000704A CN 100460488 C CN100460488 C CN 100460488C
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Abstract
The process of preparing multifunctional low sulfur diesel oil additive includes mixing polyethylene-vinyl acetate of number average molecular weight 500-3000 and monomer with polymerization activity in the molar ratio of 1 to 0.05-10, and grafting polymerization reaction at 50-300 deg.c. The monomer with polymerization activity is one or several of acrylate, acrylamide, maleic ester, maleic amide, maleic imide, alpha-olefin, etc. The multifunctional diesel oil additive of the present invention is used as diesel antiwear agent and diesel oil flowability improver.
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 preparation method of the multipurpose additive of diesel flow improver.
Technical background
In order to reduce the pollution of diesel oil to environment, the trend of modern petroleum refining industry is that the production sulphur content is low, and it is low to contain aromatic hydrocarbons, cetane value height, the clean diesel that cut is light.Owing to generally adopted harsh hydrogenation technique, the content that polarity in the diesel oil contains oxygen, nitrogenous compound and many rings, double ring arene also decreases, thereby make the natural lubricity variation 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 its work-ing life.
The diesel fuel lubricity problem comes across the Sweden in Northern Europe as far back as the early 1990s in last century, when low-sulfur diesel-oil was sold on market, the oil injection pump wear problem had appearred in the diesel vehicle that begins nearly 70 light loads.The lubrication problem of low-sulfur low-coagulation diesel oil has almost in the same period also appearred in the U.S. and Canada.It is the easiest adding additive and be the method that diesel antiwear additive improves diesel fuel lubricity, also is the effective ways of extensive employing at present.California, USA was just recommended to adopt in 1994 to add additive method, improved the oilness of diesel oil.Each major oil companies of the world and additive company have all developed commercial anti-wear agent.
Though the standard GB/252-2000 of the existing solar oil of China limits the diesel oil sulphur content
0.2% (m) do not do requirement to oilness, and still, China derv fuel oil standard GB/T19147-2003 has required the diesel oil sulphur content
0.05% (m), the provincial standard DB11/239-2004 of derv fuel oil Beijing (in July, 2005 enforcement) regulation diesel oil sulphur content
0.035% (m), and oilness and Europe with diesel oil standard such as EN590-2004 require identically, promptly grinding defect diameter is not more than 460um (60 ℃), evaluation method ISO/FDIS 12156-1.U.S. diesel oil standard ASTMD975-04b (in January, 2005 enforcement) requires grinding defect diameter to be not more than 520um (60 ℃), evaluation method ASTM D-6079.Therefore, the oilness problem of diesel oil has also become serious, an anxious to be solved problem in China.
Simultaneously, the low temperature flowability that how much has determined oil product that also contains the alkane, particularly long-chain n-praaffin of various different quantitiess in the diesel oil.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.The adding 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.Cost is little, production is flexible, pollute advantages such as few but also have, and payes attention to widely and uses for many years 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 consistency 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.
US5, the mixture or the graftomer of 178,641 open ethylene copolymers and acrylate-copolymer-maleic anhydride amination derivative are made diesel flow improver, and US 5, the graftomer of the long-chain amination derivative of 439,981 open ethylene copolymers and maleic anhydride is made diesel flow improver.But its effect to diesel fuel lubricity is also not mentioned.
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.
The preparation method of multi-effect additive of low-surface diesel provided by the invention comprises: with number-average molecular weight is 500～3000 polyethylene vinyl acetate ester and the monomer with polymerization activity, count the mixed of 1:0.05～10 according to vinyl acetate and monomer molar, carry out graft polymerization reaction at 50～300 ℃, obtain polymerisate.
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 monomer with polymerization activity is selected from one or more in acrylate, acrylamide, maleic acid ester, maleoyl (Asia) amine, the alpha-olefin etc.
Said acrylate is vinylformic acid and C
2～C
22The esterification reaction product of Fatty Alcohol(C12-C14 and C12-C18) also can be the C of vinylformic acid and hydroxyl
6～C
40The esterification reaction product of organic acid derivative.
Said acrylamide is vinylformic acid and C
2～C
22The amination reaction product of aliphatic amide also can be vinylformic acid and the C that contains amino
6～C
40The amination reaction product of organic acid derivative.
Said acrylate or acrylamide can also be the reaction product of vinylformic acid and amino alcohol, or vinylformic acid and amino alcohol and C
6～C
40The organic acid reaction product.When the hydroxyl of amino alcohol linked to each other with vinylformic acid, product was an acrylate; When the amino of amino alcohol linked to each other with vinylformic acid, product was an acrylamide.
Said maleoyl (Asia) amine is maleic anhydride and C
2～C
22The amination reaction product of aliphatic amide also can be maleic anhydride and the C that contains amino
6～C
40The amination reaction product of organic acid derivative.
Said maleic acid ester is maleic anhydride and C
2～C
22Fatty Alcohol(C12-C14 and C12-C18) esterification reaction product also can be the C of maleic anhydride and hydroxyl
6～C
40The esterification reaction product of organic acid derivative.
Said maleoyl (Asia) amine or maleic acid ester can also be the reaction product of maleic anhydride and amino alcohol, or maleic anhydride and amino alcohol and C
6～C
40The organic acid reaction product.When the hydroxyl of amino alcohol linked to each other with maleic anhydride, product was a maleic acid ester; When the amino of amino alcohol linked to each other with maleic anhydride, product was maleoyl (Asia) amine.
Said a-alkene is C
5～20Normal olefine can be a monoolefine, also can be diolefine, isoprene for example, a-laurylene, a-tetradecene, a-hexadecylene, a-octadecylene etc.
Specifically, C wherein
6～C
40Organic acid can be organic aromatic acid, naphthenic acid or lipid acid, preferred naphthenic acid or lipid acid, more preferably lipid acid.Lipid 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, oleic acid, linolic acid, linolenic acid, stearic acid, Palmiticacid, ricinoleate acid, arachidonic acid, eicosenoic acid, 20 acid, erucic acid (docosenoic acid), wych-elm acid, dimeracid (oleic acid and linoleic dimerisation products), linoleic acid dimer etc. for example; Can also be mixing acid, as various vegetable fatty acids, as Zoomeric acid, soybean oleic acid, arachic acid, vegetable seed oleic acid, tall oil acid etc., preferably normal temperature be liquid C down
14～C
36Unsaturated acid is as oleic acid, linolic acid, linolenic acid, linoleic acid dimer, ricinolic acid etc.
C wherein
2～C
22Fatty Alcohol(C12-C14 and C12-C18) can be a monohydroxy-alcohol, also can be polyvalent alcohol.Monohydroxy-alcohol refers to contain in the molecule alcohol of a hydroxyl, preferred C
6～C
20, C preferably
8～C
18Alkanol.For example octanol, decyl alcohol, dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol or its mixture.Polyvalent alcohol refers to contain in the molecule two hydroxyls and above C
2～C
22Fatty Alcohol(C12-C14 and C12-C18) is as the propylene glycol of ethylene glycol, glycerol, various isomer, butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, tetramethylolmethane, sorbyl alcohol, anhydrous sorbitol, TriMethylolPropane(TMP) etc.It also can be the condensation product of above-mentioned alcohol and oxyethane, 1,2 epoxy prapane.Preferred C
2～C
8Polyvalent alcohol.
C wherein
2～C
22Aliphatic amide can be monoamine, diamine or polyamines polyene.Monoamine refers to contain in the molecule amine of an amino, can be primary amine, also can be secondary amine, preferred C
6～C
20, C preferably
8～C
18Primary amine, especially straight chain linear alkyl primary amine.For example octylame, decyl amine, amino dodecane, tetradecy lamine, cetylamine, stearylamine or its mixture.Diamine refers to contain in the molecule aliphatic amide of two amino, as quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine etc.Polyamines polyene is that structural formula is H
2N[(CH
2)
nNH]
mThe polyamine 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.
Amino alcohol wherein (or hydramine) can be C
2～C
10Amino alcohol, 2-amino-1 for example, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, Monoethanolamine MEA BASF, diethanolamine, N methyldiethanol amine, trolamine or its mixture.
The C of hydroxyl wherein
6～C
40Organic acid derivatives is meant C
6～C
40The esterification products of organic acid and polyvalent alcohol, epoxide contains nonesterified hydroxyl in the derivative.
The polyvalent alcohol here is identical with the implication of polyvalent alcohol above.The epoxide here 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.
The preparation method of the organic acid derivatives of hydroxyl can use conventional esterification or amination method, specifically, organic acid and polyvalent alcohol, epoxide, when amino alcohol (hydramine) carries out esterification, an acidic catalyst such as sulfuric acid, the tosic acid etc. that can add reactant weight about 1%, perhaps basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate/methyl alcohol, dimethylcyclohexylamine etc. are with fast reaction speed, and divide water or nitrogen purging to dewater 2～10 hours at 80～160 ℃ of following solvent refluxings, add an amount of alkali or sour catalyst neutralisation then.When reaction feeds intake; the hydroxyl mole number that contains in polyvalent alcohol, the epoxide should be greater than the acyl group mole number that contains in the organic acid; preferably the hydroxyl mole number approximates two times of acyl group mole number, makes in the ester group of each organic acid acetic molecule that reaction generates all to contain hydroxyl.The reaction of organic acid and amino alcohol (hydramine) can be carried out with reference to above-mentioned feed ratio.
The amino organic acid derivatives that contains wherein refers to C
6～C
40The aminate of organic acid and diamine, polyamines polyene or alkoxy polyamine.
The diamine here, polyamines polyene are identical with above implication.The alkoxy polyamine here is by polyamines polyene and C
2～C
18Epoxide is with 1:0.5～10, the reaction product of preferred 1:1～5 mol ratios.Epoxide optimization ethylene oxide wherein, 1,2 epoxy prapane, 1, the 2-butylene oxide ring.
Organic acid and diamine, polyamines polyene, when alkoxy polyamine carries out amination reaction, can not add catalyzer and also can add the basic catalyst of reactant weight about 1% such as sodium hydroxide, potassium hydroxide, sodium methylate/methyl alcohol, dimethylcyclohexylamine etc. and divide water or nitrogen purging to dewater 2～10 hours, as be added with catalyzer and then need add an amount of acidic substance neutralization at 80～100 ℃ of following solvent refluxings.When reaction feeds intake; the ammonia mole number that contains in polyamine, the alkoxy polyamine should be greater than the acyl group mole number that contains in the organic acid; preferably amino mole number approximates two times of acyl group mole number, all contains amino in each organic amide molecule that reaction is generated.
The graft polymerization reaction of polyethylene vinyl acetate ester and above-mentioned polymerization single polymerization monomer can carry out according to the polyreaction of routine, as can preferably being undertaken by free radical solution polymerization by mass polymerization, letex polymerization, free radical solution polymerization.
In the free radical solution polymerization reaction, available solvent has 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.Available 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 0.1～10% of an EVA weight, preferred 0.5～5%.Initiator can once all join in the reactor, also can slowly drip.
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, the number-average molecular weight of EVA 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 the GB510-83 method.
Example 1～2nd, the preparation of EVA.
Example 1
21g vinyl acetate, 90g60～90 ℃ sherwood oil 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, 100g120
#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
Example 3
This example is the preparation of acrylate.
With 37.8g vinylformic acid and 135.0g stearyl alcohol (mol ratio of vinylformic acid and stearyl alcohol is about 1.05:1), 55g120
#Industrial naptha and the agent of 1.8g Catalyzed by p-Toluenesulfonic Acid and 0.4g Resorcinol stopper place a reactor that electric mixer, thermometer, water trap, reflux condensing tube be housed, the heated and stirred temperature rising reflux divides water reaction 5 hours, be cooled to 80 ℃ then, add 118g 120
#Industrial naptha is washed till neutrality with the 5%NaOH aqueous solution, and it is inferior to give a baby a bath on the third day after its birth with distilled water again, uses anhydrous CaCl
2The decompression of dry back steams solvent and promptly gets product.
Example 4
This example is the preparation of acrylate.
100g ricinolic acid and 30.8g glycerol (mol ratio of ricinolic acid and glycerol is about 1:1) and the agent of 2.0g Catalyzed by p-Toluenesulfonic Acid are placed a reactor that electric mixer, thermometer, water trap, reflux condensing tube and nitrogen ingress pipe be housed, heated and stirred is warming up to 140 ℃, feed nitrogen and divide water reaction 3 hours, add 24.1g vinylformic acid, 0.4g Resorcinol stopper then, kept thermotonus 3 hours, be cooled to 80 ℃, add 1.0g CaO neutralization, add super-cell while hot and filter, filtrate is product.
Example 5
This example is the preparation of acrylamide.
100g oleic acid, 67.0g tetraethylene pentamine (mol ratio of oleic acid, tetraethylene pentamine is about 1:1) are placed a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, heated and stirred is warming up to 130 ℃, logical nitrogen divides water reaction 2 hours, add 25.5g vinylformic acid, 0.4g Resorcinol stopper then, keep temperature to continue reaction 4 hours, cooling promptly gets product.
Example 6
This example is the preparation of acrylate.
With 100g tall oil acid (trade names
Arizona company produces), 53.2g trolamine (mol ratio of tall oil acid, trolamine is about 1:1) and 1.2g NaOH place a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, heated and stirred is warming up to 140 ℃, logical nitrogen divides water reaction 2 hours, add 25.5g vinylformic acid, 0.4g Resorcinol stopper then, continue reaction 3 hours at 120 ℃, add in the acidic white earth and the back suction filtration, filtrate is product.
Example 7～11st, EVA and the preparation that does not contain the monomer-grafted polymkeric substance of maleic anhydride.
The different polyethylene vinyl acetate esters (EVA) of table 1 will be selected from, acrylic acid derivative in the example 3～6, a-alkene, initiator is selected ditertiary butyl peroxide for use, it is 159～185 ℃ aromatic hydrocarbons thinning oil that solvent is all used boiling range, solvent load is identical with the monomer total amount, and monomer, solvent and initiator splash into reactor.According to the conditioned response shown in the table 2, obtain different products.
Table 2
Example 12～16th, EVA and the preparation that contains the monomer-grafted polymkeric substance of maleic anhydride.
The different polyethylene vinyl acetate esters (EVA) of table 1 will be selected from, acrylic acid derivative in the example 3～5, maleic anhydride, a-alkene, initiator is selected ditertiary butyl peroxide for use, it is 159～185 ℃ aromatic hydrocarbons thinning oil that solvent is all used boiling range, solvent load is identical with the monomer total amount, other monomer, solvent and initiator except that maleic anhydride splash into reactor, and maleic anhydride directly adds.150 ℃ of polymerization temperatures, polymerization time 5 hours.The polymerization after product adds alcohol or amine and maleic anhydride again with mol ratio 1:1 reaction, according to the conditioned response shown in the table 3, obtains different products.
Table 3
Example 17
This example is the result of use of multipurpose additive in diesel oil that example 7～16 makes.Select the Yanshan Mountain-20 for use
#Blended diesel is as test oil, and its physicochemical property sees Table 4, adds that HFRR method (ISO12156-1) grinding defect diameter WS1.4, cold filter clogging temperature and the condensation point of diesel oil sees Table 5 before and after the agent, and when grinding defect diameter during less than 460um (60 ℃), then the oilness of diesel oil is qualified.
The physicochemical property of table 4 diesel oil
Table 5 multipurpose additive is to the improvement of diesel fuel lubricity and low-temperature fluidity
By table 5 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 acrylic acid derivative (example 4 products) separately and can improve diesel fuel lubricity, but to the diesel oil at low-temperature flowability to no effect.And diesel oil multi-efficient additive provided by the invention can fine its oilness of improving to low-sulfur diesel-oil, simultaneously diesel oil is had good filter, the pour point depression effect of falling.
Claims (22)
1. the preparation method of a multi-effect additive of low-surface diesel, comprise: with number-average molecular weight is 500～3000 polyethylene vinyl acetate ester and the monomer with polymerization activity, according to polyethylene vinyl acetate ester and monomer mole ratio is the mixed of 1:0.05～10, carry out the free-atom aqueous solution graft polymerization reaction in 50～300 ℃, said monomer with polymerization activity is selected from one or more in acrylate, acrylamide, maleic acid ester, maleoyl (Asia) amine, the alpha-olefin.
2. according to the described preparation method of claim 1, it is characterized in that the vinyl acetate content in the said polyethylene vinyl acetate ester is 20～45%, the side chain degree is not more than 6.
3. according to the described preparation method of claim 1, it is characterized in that said acrylate is vinylformic acid and C
2～C
22The esterification reaction product of Fatty Alcohol(C12-C14 and C12-C18), or the C of vinylformic acid and hydroxyl
6～C
40The esterification reaction product of organic acid derivative.
4. according to the described preparation method of claim 1, it is characterized in that said acrylamide is vinylformic acid and C
2～C
22The amination reaction product of aliphatic amide, or vinylformic acid and contain amino C
6～C
40The amination reaction product of organic acid derivative.
5. according to the described preparation method of claim 1, it is characterized in that said acrylate or acrylamide are vinylformic acid and C
2～C
10The reaction product of amino alcohol, or vinylformic acid and C
2～C
10Amino alcohol and C
6～C
40The organic acid reaction product.
6. according to the described preparation method of claim 1, it is characterized in that said maleic acid ester is maleic anhydride and C
2～C
22The esterification reaction product of Fatty Alcohol(C12-C14 and C12-C18), or the C of maleic anhydride and hydroxyl
6～C
40The esterification reaction product of organic acid derivative.
7. according to the described preparation method of claim 1, it is characterized in that said maleoyl (Asia) amine is maleic anhydride and C
2～C
22The amination reaction product of aliphatic amide, or maleic anhydride and contain amino C
6～C
40The amination reaction product of organic acid derivative.
8. according to the described preparation method of claim 1, it is characterized in that said maleoyl (Asia) amine or maleic acid ester are maleic anhydride and C
2～C
10The reaction product of amino alcohol, or maleic anhydride and C
2～C
10Amino alcohol and C
6～C
40The organic acid reaction product.
9. according to the described preparation method of claim 1, it is characterized in that said a-alkene is C
5～
20Normal olefine.
10. according to the described preparation method of one of claim 3～8, it is characterized in that C wherein
6～C
40Organic acid is a lipid acid.
11., it is characterized in that organic acid is C according to the described preparation method of claim 10
14～C
36Unsaturated fatty acids.
12., it is characterized in that organic acid is oleic acid, linolic acid, linolenic acid, linoleic acid dimer or ricinolic acid according to the described preparation method of claim 10.
13., it is characterized in that Fatty Alcohol(C12-C14 and C12-C18) wherein is C according to claim 3 or 6 described preparation methods
6～C
20Monohydroxy-alcohol or C
2～C
8Polyvalent alcohol.
14., it is characterized in that Fatty Alcohol(C12-C14 and C12-C18) wherein is octanol, decyl alcohol, dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol according to claim 3 or 6 described preparation methods; Ethylene glycol, glycerol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, tetramethylolmethane, sorbyl alcohol, anhydrous sorbitol, TriMethylolPropane(TMP); Or the condensation product of above-mentioned alcohol and oxyethane, 1,2 epoxy prapane.
15., it is characterized in that aliphatic amide wherein is C according to claim 4 or 7 described preparation methods
6～C
20Kiber alkyl amine, diamine or polyamines polyene.
16., it is characterized in that aliphatic amide wherein is octylame, decyl amine, amino dodecane, tetradecy lamine, cetylamine, stearylamine or its mixture according to the described preparation method of claim 15; Quadrol, propylene diamine, butanediamine, pentamethylene diamine, diamines; Diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, two propylene triamines, three propylene tetramines, tetrapropylene five amine or five propylene hexamines.
17., it is characterized in that, wherein the C of hydroxyl according to claim 3 or 6 described preparation methods
6～C
40The organic acid derivative is meant C
6～C
40Organic acid and C
2～C
22Polyvalent alcohol or C
2～C
18The esterification products of epoxide.
18., it is characterized in that C according to the described preparation method of claim 17
2～C
22Polyvalent alcohol is ethylene glycol, glycerol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, tetramethylolmethane, sorbyl alcohol, anhydrous sorbitol or TriMethylolPropane(TMP).
19., it is characterized in that C according to the described preparation method of claim 17
2～C
18Epoxide is oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 1,2-epoxy octadecane or their mixture.
20., it is characterized in that the C that contains amino wherein according to claim 4 or 7 described preparation methods
6～C
40The organic acid derivative is C
6～C
40Organic acid and C
2～C
22The aminate of diamine, polyamines polyene or alkoxy polyamine.
21., it is characterized in that diamine is quadrol, propylene diamine, butanediamine, pentamethylene diamine, diamines according to the described preparation method of claim 20; Polyamines polyene is diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, two propylene triamines, three propylene tetramines, tetrapropylene five amine or five propylene hexamines; Alkoxy polyamine is by polyamines polyene and C
2～C
18The reaction product of epoxide.
22. according to claim 5 or 8 described preparation methods, it is characterized in that, amino alcohol wherein 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.
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|---|---|---|---|---|
| CN102510878A (en) * | 2009-09-25 | 2012-06-20 | 赢创罗曼克斯添加剂有限公司 | Composition to improve cold flow properties of fuel oils |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3048749A (en) * | 1958-03-06 | 1962-08-07 | Bull Sa Machines | Electric relay |
| US5178641A (en) * | 1990-11-14 | 1993-01-12 | Basf Corporation | Middle distillates of crude oil having improved cold flow properties |
| US5439981A (en) * | 1992-12-12 | 1995-08-08 | Hoechst Aktiengesellschaft | Graft polymers, their preparation and use as pour point depressants and flow improvers for crude oils, residual oils and middle distillates |
| WO1996018707A1 (en) * | 1994-12-13 | 1996-06-20 | Exxon Chemical Patents Inc. | Fuel oil compositions |
| CN1306074A (en) * | 2000-01-20 | 2001-08-01 | 陕西省西北新技术实业有限责任公司 | Environment protection type multifunctional diesel oil additive |
-
2006
- 2006-01-10 CN CNB2006100007044A patent/CN100460488C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3048749A (en) * | 1958-03-06 | 1962-08-07 | Bull Sa Machines | Electric relay |
| US5178641A (en) * | 1990-11-14 | 1993-01-12 | Basf Corporation | Middle distillates of crude oil having improved cold flow properties |
| US5439981A (en) * | 1992-12-12 | 1995-08-08 | Hoechst Aktiengesellschaft | Graft polymers, their preparation and use as pour point depressants and flow improvers for crude oils, residual oils and middle distillates |
| WO1996018707A1 (en) * | 1994-12-13 | 1996-06-20 | Exxon Chemical Patents Inc. | Fuel oil compositions |
| CN1306074A (en) * | 2000-01-20 | 2001-08-01 | 陕西省西北新技术实业有限责任公司 | Environment protection type multifunctional diesel oil additive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102510878A (en) * | 2009-09-25 | 2012-06-20 | 赢创罗曼克斯添加剂有限公司 | Composition to improve cold flow properties of fuel oils |
| CN102510878B (en) * | 2009-09-25 | 2015-08-05 | 赢创罗曼克斯添加剂有限公司 | Improve the composition of oil fuel cold flow properties |
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| CN100999685A (en) | 2007-07-18 |
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Assignee: Yueyang Jucheng Chemical Co., Ltd. Assignor: China Petroleum Chemical Co|China Petroleum Chemical Co; Research Institute of petrochemical industry; Contract record no.: 2011430000156 Denomination of invention: Preparation process of multi-efficient additive of low sulphur diesel oil Granted publication date: 20090211 License type: Exclusive License Open date: 20070718 Record date: 20110829 |