CN102295963A - Novel preparation method of nonpolymeric pour-point depressant for diesel fuels - Google Patents

Abstract

The invention relates to a novel preparation method of a nonpolymeric pour-point depressant for diesel fuels. The invention provides a preparation method of a new diesel oil additive capable of depressing the pour point, dropping the cold filter plugging point and improving the cold flow properties, comprising the following steps: using ethylene diamine tetraacetic acid (EDTA), aminotriacetic acid, 1,2,3,4- cyclobutane tetracarboxyl dianhydride (CBDA), 12-22 alcohol, 12-20 primary amine and primary amine as raw materials, using a small amount of solvent, using cation exchange resin (D001, D002, HD8) and strong acidic cation exchange membrane (HF1) as catalyst, carrying out amidation, esterification and amination to obtain a nonpolymeric macro-molecule compound. The compound can react directly with other polyethylene-vinyl acetate to obtain an excellent cold flow improver for diesel oils. The preparation method has the advantages of easy removal of catalysts, rapid reaction, simple process, high yield, recycled catalysts and solvent and the like. The prepared compound and its mixtures have significant effect on 0# diesel oil and 5# diesel oil of Shanghai Oil Refinery Factory with the additive amount of 200-800 ppm.

Description

The novel preparation method of non-polymeric type diesel pour inhibitor

The research of diesel oil pour point depression turbidity removal agent is used and is started from the beginning of the thirties in last century.50～sixties, growing along with world's waxy crude oil output, and people are to the deepening continuously of pour point depression mechanism research, pour point depression turbidity removal agent product has had significant progress both at home and abroad.In addition, compounded technology has also obtained using widely.

China from 1986 from external import pour point depressant, concentration is low and price is high, but this can not satisfy the needs of China's energy and industrial development.Therefore, developing homemade pour point depressant is one of important topic in petrochemical complex, the derived energy chemical.At present at home and abroad in the R﹠D process,, and methods such as High Temperature High Pressure, chemical polymerization in R﹠D process, have been adopted mostly often according to the difference of original place of production and quality and needs improve the performance of oil product with different respective additive.Complex manufacturing, condition are harsh, and for the requirement of raw material, also there is the place that need update in the environmental friendliness fermentation.Finding a kind of new synthetic, preparation method, and realize various original degradeds, fall turbid effect, is the direction that we study.

Diesel pour inhibitor is also referred to as middle runnings cold flow improver (PPD) simultaneously, and diesel oil PPD the earliest is the Paradyne20 that U.S. EXXON company produced in nineteen sixty, and this is a kind of ethylene-vinyl acetate copolymer.After this, countries in the world have been developed a series of polymkeric substance such as a series of ethylene-vinyl acetates, methacrylic ester-acrylate and methacrylic ester-styrene-maleic anhydride copolymer in succession.Over past ten years, develop the following three kinds of pour point depressants that mainly contain that use both at home and abroad:

1. ethylene-vinyl acetate polymkeric substance (EVA) (method for high pressure polymerization);

2. allyl butyrate diamide Barbiturates (chemical synthesis);

3. higher hydrocabon compounds (chemical synthesis).

The present invention relates to second class, be the synthetic of amido acid salt pour point depressant, at this, the invention provides a kind of new synthetic method, in reaction process, the present invention does not relate to acid catalysts such as tosic acid, has reduced the distillation of a step solvent, solid catalyst can repeat to recycle, and is a kind of method of saving the energy environment close friend.About the synthetic method of this compounds, existing both at home and abroad many relevant reports through self check and the retrieval of patent retrieval service center, do not find to influence novelty of the present invention and creationary article and patent.As: US3598736,1971; US3840352,1974; US3982909,1976; US3957659,1976; US4661120,1987; US4661122,1987; US4670516,1987; US4900569,1990; US5330545,1994; US6017370,2000; CN1057290A, 1991; CN1059157A, 1992; CN1060297A, 1992; US5376155,1994; DE4410196,1995; DE4410198,1995; DE19622052,1997; JP10245574,1998; US5002588,1991; US5000758,1991; US5039309,1991; WO9209674,1992; WO9209673,1992; DE4237662,1994; DE4324394,1995.

Content of the present invention is following technical scheme:

One, A component composition feed composition proportioning:

Ethylenediamine tetraacetic acid (EDTA) (nitrilotriacetic acid, CBDA) 1～5 part

0.5～10 part of lauryl alcohol～behenyl alcohol

1～15 part of ten di-primary amine～20 di-primary amines

1～20 part of 12 secondary amine～18 secondary amine

Solvent is a small amount of

0.1～3 part of solid strong acid catalyst

Two, the empirical formula of low temperature flow improver for diesel fuel of the present invention is:

Y wherein ₁, Y ₂, Y ₃, Y ₄Be OH or OR or NHR or OHN ⁺H ₂R; R is C ₁₂～C ₂₂Chain alkyl.

Diesel pour inhibitor of the present invention is respectively with ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 12～V-1326,12～two amino dodecanes are raw material, toluene, dimethylbenzene, normal heptane, n-decane, N, dinethylformamide, kerosene etc. are solvent, with large porous strong acid cation exchange membranes such as D-001, D-002, HF-1 strong-acid type cation exchange membrane, consumption is 1%, carries out esterification, amidation, salinization reaction under 50～200 ℃, deionizing exchange resin or ion-exchange membrane, cold filtration, through recrystallization promptly.Add an amount of EVA multipolymer and tensio-active agent, stir 5～10hr down, promptly make corresponding low temperature flow improver for diesel fuel at 100～200 ℃.

Example:

Prescription 1: ethylenediamine tetraacetic acid (EDTA) 1mol, 12～tetradecanol 1mol, cetylamine 3mol, dimethylbenzene or n-decane are solvent, and DH-8 large porous strong acid cation exchange membrane is as acid catalyst, 150～200 ℃ of esterifications, amidation, salinization, the water azeotropic that reaction generates steams, the product that obtains is used the butanols recrystallization once, 70～71 ℃ of fusing points.With 1～5 part of this product, add EVA1～5 part, 1～5 part of nonionogenic tenside is heated to 120 ℃, keeps 8hr, cooling packing.

Prescription 2: nitrilotriacetic acid 1mol, behenyl alcohol 2mol, 16-18 secondary amine 12mol, dimethylbenzene or n-decane are solvent, and HF-1 large porous strong acid cation exchange membrane is as acid catalyst, 150～200 ℃ of esterifications, amidation, salinization, the water azeotropic that reaction generates steams, the product that obtains is used ethanol-butanols mixed solvent recrystallization once, 68～70 ℃ of fusing points.With 1～5 part of this product, 1～5 part of nonionogenic tenside is heated to 120 ℃, keeps 8hr, cooling packing.

With ion-exchange and acid base titration, measure catalyst activity such as following table 1 through us

The exchange capacity of table 1. catalyzer and the relation of access times

It is investigated, D-001, D-002, DH-8, the manufacturer of HF-1 all illustrates in operation instruction and temperature≤120 ℃ can keep about 10hr under 120 ℃ of situations.Our result think it can be increased to 〉=160 ℃, use about secondary, use for the third time because that exchange capacity descends is excessive, aufhellung obviously appears in color of resin.

The present invention has following advantage:

1. all raw materials of the present invention are easy to get, and conventional chemical plant installations is used in reaction, and technological process is simple.

2. use strongly-acid ion-exchange membrane or resin, after reaction is finished, need not boil off solvent, direct filtration is taken out and is got final product, and product is separated out under the room temperature in internal solvent, filters and crystallization, has saved the energy, has not also avoided three-waste pollution because of there being washing.

3. low temperature flow improver for diesel fuel of the present invention, the foreign study person is all as falling turbid and the dispersion agent use, we are with it and EVA, tensio-active agents etc. are composite, the susceptibility that broad is arranged, for factory of shanghai refinery, the low-temperature fluidity character of 0# diesel oil such as Shandong Qilu Petrochemical all has improvement in various degree, and the some of them oil product can promote a trade mark.

The non-polymeric type diesel pour inhibitor of table 2. is to the action effect of different diesel oil

Table 3. non-polymer diesel pour inhibitor is to the action effect of last refining 5# diesel oil

The mensuration of cold filter point of diesel oil is according to the standard SY 2413-83 of Sinopec (cold filter point of diesel oil assay method) in table 2 and the table 3.The mensuration of condensation point of diesel oil is according to State Standard of the People's Republic of China GB/T 510-83 (petroleum products questionable points assay method).

Claims (9)

1. low temperature flow improver for diesel fuel, it forms (by weight) by following prescription:

1～5 part of ethylenediamine tetraacetic acid (EDTA) (or nitrilotriacetic acid, CBDA) amidation, esterification, amine salt product

1～5 part of ethylene-vinyl acetate copolymer

1～5 part in tensio-active agent

2. the preparation of right 1 described low temperature flow improver for diesel fuel, its technical characterictic is: 1～5 part of ethylenediamine tetraacetic acid (EDTA) (or nitrilotriacetic acid, CBDA), 0.5～10 part of 12-22 alcohol, 1～15 part of 12～22 primary amine, 1～10 part of 12～18 secondary amine, 0.1～3 part of highly acidic cation exchange membrane (storng-acid cation exchange resin), solvent is some, 50～200 ℃ of temperature, reaction times 2～10hr.

3. to prepare the solvent of usefulness be toluene, dimethylbenzene, normal heptane, decane, N to the described low temperature flow improver for diesel fuel of claim 1, dinethylformamide, kerosene etc. any one or its mixture.

4. the preparation of the described low temperature flow improver for diesel fuel of claim 1, the prepolymer that utilizes right 2 to make is respectively 1: 1～4,1 with carboxylic acid molecules and ratio pure, amine as required: 1～4, employed alcohol is C ₁₂～C ₂₂N-alkanes alcohol, amine is C ₁₂～C ₂₂Fat primary amine, secondary amine or its mixture.

5. the described low temperature flow improver for diesel fuel of claim 1, its feature is non-polymeric type macromolecular cpd at it, its structural formula is

Y wherein ₁, Y ₂, Y ₃, Y ₄Be OH or OR or NHR or OHN ⁺H ₂R; R is C ₁₂～C ₂₂Chain alkyl.

6. the described reaction of claim 2 is used strongly-acid ion-exchange membrane (HF-1) or strong-acid ion exchange resin (D001, D002, HD-8 etc.) to carry out acid catalyzed reaction and is obtained.

7. the low temperature flow improver for diesel fuel described in the claim 1 is characterised in that its tensio-active agent is a nonionogenic tenside, and the HLB value is 1～12.

8. the described polyethylene vinyl acetate ester of claim 1, its molecular weight is 2000～15000.

9. the preparation of the low temperature flow improver for diesel fuel described in the claim 1 is after i.e. esterification, amidation, salinization are finished, successively with addings such as polyethylene vinyl acetate ester, tensio-active agents, stir, be heated to 100～120 ℃, continue to stir 1～3hr, cooling packing.