CN1110538C - Multi-effect additive for diesel oil - Google Patents
Multi-effect additive for diesel oil Download PDFInfo
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- CN1110538C CN1110538C CN 00124808 CN00124808A CN1110538C CN 1110538 C CN1110538 C CN 1110538C CN 00124808 CN00124808 CN 00124808 CN 00124808 A CN00124808 A CN 00124808A CN 1110538 C CN1110538 C CN 1110538C
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Abstract
The present invention relates to a multi-effect additive for diesel oil which is prepared by a method that hydroxy aromatic acid reacts with alkenyl succinimide according to a molar ratio of 0.5 to 5:1 in the existence of an organic solvent at the temperature of 60 to 200 DEG C for 0.5 to 20 hours. The structural formula of the hydroxy aromatic acid is HOOC-[Ar]-(OH) b, wherein [Ar] represents an aromatic ring. In the present invention, the multi-effect additive for diesel oil is a polyfunctional compound containing a phenolic group, macromolecule alkyl and a succinyl group. The additive not only has a preferable antioxidation capability, but also has purification and dispersion performance, and a generation of oxidation sediments in diesel oil is greatly reduced.
Description
The invention belongs to diesel oil multi-efficient additive, definite saying so both can be used as diesel oil stabilizing agent, also can be used as the multipurpose additive of diesel oil ashless dispersant.
As everyone knows, non-hydrocarbon compounds such as the alkene in the diesel oil, diolefin and sulfide, nitride can generate a series of intermediate oxidation products under the effect of oxygen, further generate infusible precipitate through condensation again.These insoluble particles that generate in the diesel oil storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; influence oil atomizing; cause incomplete combustion, even in engine, form too much carbon deposit, make spray nozzle clogging.
The problems referred to above can be alleviated by add additive in diesel oil.It is generally acknowledged that diesel oil stabilizing agent can stop, weakens or disturb above-mentioned various reaction, rotten to suppress diesel oil, improve its stability; Diesel cleaning and dispersing agent can wash down established carbon deposit on the nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, and also can disperse established sediment in the diesel oil simultaneously, eliminates purifier and spray nozzle clogging, and improves exhaust emissions.
US4648885 discloses a kind of with N-(2-aminoethyl) piperazine, N, the mixture of N-diethyl hydroxylamine and triethylene tetramine is as the diesel oil stabilizing agent of main ingredient, can stop diesel colour to deepen formation with particulate matter, but this stablizer only improves the stability in storage of straight-run diesel oil, and is relatively poor to the diesel oil effect that the catalytic cracking component is more.GB2 245,588 discloses the replacement triazine that generates with primary amine, secondary amine and formaldehyde reaction, has replaced the diesel oil stabilizing agent of methane compound as main ingredient.This class additive has certain stabilization to color, but accelerating under the oxidizing condition (SH/T0175-94,95 ℃, logical oxygen 16 hours), the diesel oil oxidation sediment is suppressed indifferent, and the solubleness in oil is also not so good simultaneously.And above-mentioned diesel oil stabilizing agent does not have peace and quiet dissemination.
US3, disclosed allyl butyrate imide such as 024,237,3,172,892,3,202678,3,257554 are lubricating oil and the oil fuel ashless dispersants that are most widely used at present.Its typical structure is to react the mono butonediimide that obtains, two succimide and many succimides (being commonly called as single extension, two extension, hang) etc. in varing proportions by polyisobutylene butanedioic anhydride and tetraethylene pentamine more.But such additive antioxygenation a little less than, generally all will with oxidation inhibitor or the compound use of stablizer, this has not only increased the consumption of additive, also can cause the compatibleness problem between additive.
Succimide is carried out chemical modification can make its dispersed enhancing, or make it have multi-efficiencies such as dispersion, antioxygen.As US4,482,464 disclose single, double succimide and hydroxy fatty acid such as oxyacetic acid, 2, and the reaction product of 2 '-two hydroxymethyl propionic acid is as lubricating oil dispersant; US4,780,111 reaction product that disclose with allyl butyrate imide and phthalic acid (acid anhydride) reduce the oil fuel sediment weight, improve the nozzle deposition.US5,069, the 684 half ester product that discloses fragrance or fat diacid and polyethers reacts with the allyl butyrate imide again, as fuel or lubricating oil multipurpose additive.US5,435,812 disclose with single, double succimide and fragrance three sour two polyether ester reaction product and have acted as a fuel or antioxygen, the detergent-dispersant additive of lubricating oil.
The purpose of this invention is to provide a kind of multipurpose additive with functions such as antioxygen/stable, dispersions, it can not only stop the condensation between alkene, diolefin oxidation and the non-hydrocarbon compound in the diesel oil, and the gathering between the small oxidation products that can also prevent to have produced, make it to be dispersed among the diesel oil, thereby improve the stability of diesel oil, delay engine filter and spray nozzle clogging.
Diesel oil multi-efficient additive provided by the invention prepares by following method:
With phenol acids and allyl butyrate imide according to 0.5～5: 1, preferred 1～4: 1 mol ratio in the presence of organic solvent in 60～200 ℃, preferred 80～160 ℃ of reactions 0.5～20 hour down, preferred 1～10 hour.
Said organic solvent can be benzene,toluene,xylene, aromatic hydrocarbons thinning oil (boiling range is 159～185 ℃), industrial naptha or mineral oil (boiling point is more than 120 ℃), or their mixture.Solvent load generally is 30～150% of a monomer material gross weight.Available nitrogen protection in the reaction system perhaps allows system carry out under the condition of solvent refluxing.This reaction can not add catalyzer, also can add a small amount of (0.01～1%) acidic cpd such as sulfuric acid, tosic acid or acidic white earth as catalyzer, so that fast reaction speed.For the ease of postorder operation and storage, last product can be made into about 50% diluent with the aromatic hydrocarbons thinning oil.
Said phenol acids has the structure shown in the formula (I):
HOOC-[Ar]-(OH)
b (I)
In the formula, [Ar] represents aromatic ring, comprises phenyl ring and naphthalene nucleus, and b is 1～4 integer.The preferred Whitfield's ointment of said phenol acids (salicylic acid), m-Salicylic acid, P-hydroxybenzoic acid, 3-hydroxyl 2-naphthoic acid, 3,4,5-trihydroxybenzoic acid (gallic acid) or the like.
Said allyl butyrate imide is to be made by enetutanedioic acid anhydride and polyamines polyene reaction.Thiazolinyl wherein comes from C
3～C
4The multipolymer of monoolefine or homopolymer can be polyisobutene, Atactic Polypropelene or ethylene-propylene copolymer.Its number average relative molecular mass is 300～5000, and is preferred 800～2500, more preferably 500～2000.The substitution value of enetutanedioic acid anhydride is generally 0.5～1.0.The structural formula of polyamines polyene 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 triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
Mol ratio when polyamines polyene and alkenyl succinic acid anhydride reactant can be 1: 1～2, and temperature of reaction is preferably within 110～160 ℃ of scopes between 100～200 ℃.Reaction medium can be organic solvent such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil (boiling range is 159～185 ℃), industrial naptha or mineral oil (boiling point is more than 120 ℃), or their mixture.Solvent load generally is 30～150% of a monomer material gross weight.The preparation method is at US2, and 992,708, US3,172,892, US3,272,746, US5, in 286,823 documents such as grade description is arranged all.
The addition of additive provided by the invention in diesel oil generally is 50～2000ppm, preferred 100～1000ppm.
According to using needs, additive provided by the invention can also with other additive, use simultaneously as FLOW IMPROVERS, cetane number improver, metal passivator, sanitas etc.
Additive provided by the invention also can be used as the antioxygen ashless dispersant and is used for lubricating oil.
Diesel oil multi-efficient additive provided by the invention is the polyfunctional compound that contains phenolic group, polymer alkyl and succinyl; not only has resistance of oxidation preferably; also has the detergent-dispersant performance energy; colloid isopolarity compound and fine particles had very strong absorption and capturing ability; can stop its further oxidation, gathering, thereby significantly reduce the generation of oxidation sediment in the diesel oil.
In addition, additive of the present invention also has other function, as improves the copper corrosion of diesel oil, reduces the discharging of diesel motor exhaust.Compared with prior art, additive of the present invention also has raw material and is easy to get, and is cheap, and reaction is simple, do not have characteristics such as " three wastes " pollution.
Accompanying drawing is tinsel sedimentation evaluation equipment synoptic diagram.
The present invention is further illustrated below by example.
Example 1
This example is the preparation of allyl butyrate imide.
In three-necked bottle; add 200 gram (0.14mol) polyisobutylene butanedioic anhydride (polyisobutene number average relative molecular mass Mn=1200; 80 milligrams of KOH/ grams of saponification value; substitution value is 1.0) and 200 gram boiling ranges be 159～185 ℃ aromatic hydrocarbons thinning oil (platinum reforming still bed material); be heated to 80 ℃ and stir, slowly add 20.2 gram (0.138mol) triethylene tetramines, under nitrogen protection, be warming up to 150 ℃ of dehydration reactions 6 hours; make intermediates 1, its nitrogen content is 1.9 heavy %.Add 25 gram aromatic hydrocarbons thinning oils again and be made into about 50% diluent.
Example 2
This example is the preparation of allyl butyrate imide.
In three-necked bottle, adding 18.2 gram (0.096mol) tetraethylene pentamine, 20 gram toluene and 200 gram boiling ranges are 159～185 ℃ aromatic hydrocarbons thinning oil (platinum reforming still bed material), heated and stirred to 50 ℃, in the presence of nitrogen, slowly add 200 gram (0.107mol) polyisobutylene butanedioic anhydride (polyisobutene number average relative molecular mass Mn=900,60 milligrams of KOH/ grams of saponification value, substitution value is 0.65), be warming up to 110 ℃ of reactions 3 hours, heating steams toluene, reacted 2 hours at 145 ℃ again, make intermediates 2, its nitrogen content is 2.0 heavy %.Add 20 gram aromatic hydrocarbons thinning oils then and be made into about 50% diluent.
Example 3～7th, the preparation of diesel oil multi-efficient additive of the present invention.
Example 3
In three-necked bottle, the intermediates and 6.0 that adding 50 grams are prepared by example 1 restrain salicylic acids, and (salicylic acid and triethylene tetramine mol ratio are about 2.8: 1, the mole number of triethylene tetramine is the mole number of correspondence when the total reaction raw material (comprising solvent) in the example 1 is 50 grams), and 6 gram aromatic hydrocarbons thinning oil, in the presence of nitrogen, reacted 2 hours in 120 ℃, be cooled to room temperature then, make product 1 of the present invention.
Example 4
In three-necked bottle, add intermediates and the 3.9 gram P-hydroxybenzoic acid (P-hydroxybenzoic acid and triethylene tetramine mol ratio be about 1.8: 1) of 50 grams by example 1 preparation, and 4 gram aromatic hydrocarbons thinning oils, logical nitrogen, reacted 5 hours down at 100 ℃, be cooled to room temperature then, make product 2 of the present invention.
Example 5
In three-necked bottle, add intermediates and the 3.0 gram salicylic acids (salicylic acid and tetraethylene pentamine mol ratio be about 2.0: 1) of 50 grams by example 2 preparations, and 3 gram aromatic hydrocarbons thinning oil, in the presence of nitrogen, reacted 2 hours in 150 ℃, be cooled to room temperature then, make product 3 of the present invention.
Example 6
In three-necked bottle, add intermediates and 2.4 gram P-hydroxybenzoic acid and the 3 gram aromatic hydrocarbons thinning oils (P-hydroxybenzoic acid and tetraethylene pentamine mol ratio be about 1.6: 1) of 50 grams by example 2 preparations, in the presence of nitrogen, reacted 6 hours in 90 ℃, be cooled to room temperature then, make product 4 of the present invention.
Example 7
With 3.0 grams 3,4,5-trihydroxybenzoic acid (gallic acid) is substituted in 2.4 gram P-hydroxybenzoic acid in the example 6, reacts 1 hour down at 120 ℃, is cooled to room temperature then, makes product 5 of the present invention.
Example 8
This example explanation multipurpose additive of the present invention is to the improvement of oxidation stability of diesel oil.
The above-mentioned product that obtains is added to respectively among diesel oil A and the B with doses, and with the oxidation stability of accelerating oxidation style (SH/T0175-94) evaluation oil product, the physicochemical property of diesel oil A, B sees Table 1, and test result sees Table 2.
BCFPP/ ℃ of 0 1SP/ ℃ of 24 initial boiling points of physicochemical property physicochemical property diesel oil A diesel oil of table 1 diesel oil A, B/℃ 203 198 20% heat up in a steamer a little/℃ 251 230 50% heat up in a steamer a little/℃ 282 274 90% heat up in a steamer a little/℃ 335 343 do/℃ 355 362 alkanes/% 54.6 43.9 cycloalkane/% 36.9 27.7 mononuclear aromatics/% 7.7 9.9 double ring arenes/% 0.7 13.9 polycyclic aromatic hydrocarbons/% 0.1 3.5 sulfur contents/mg.L-1132 1410 nitrogen contents/mg.L
-114.3 390 basic n contents/ppm 11.6 67
Table 2 multipurpose additive is to the improvement of oxidation stability of diesel oil
| Oil sample adds dosage oxidation sediment amount mgkg -1 mg.100ml -1 | Oil sample adds dosage oxidation sediment amount mgkg -1 mg.100ml -1 |
| Blank diesel oil A/3.5 A+ examples, 1 300 2.8 A+ examples, 2 300 2.2 A+ examples, 3 300 1.0 A+ examples, 4 300 1.2 A+ examples, 5 300 0.9 A+ examples, 6 500 1.6 A+ examples 7 300 1.5 | Blank diesel oil B/4.9 B+ examples, 1 300 3.4 B+ examples, 2 300 3.0 B+ examples, 3 300 1.5 B+ examples, 4 300 1.4 B+ examples, 5 300 0.8 B+ examples, 6 500 0.9 B+ examples 7 450 1.2 |
The allyl butyrate imide of example 1 and 2 preparations is traditional detergent-dispersant additive, and as known from Table 2, the diesel oil multi-efficient additive of the present invention's preparation has more outstanding oxidation stability than the product of example 1 and 2.
Example 9
This example adopts the tinsel sedimentation multipurpose additive to be carried out the simulation evaluation of detergent-dispersant performance energy.
Present method is at the character of diesel oil, and the tinsel sedimentation that the rotary oxygen bomb method that is used for measuring lubricating oil oxidation stability and SAE 872112 (Society of automotive engineers report) is used to evaluate the gasoline detergent dispersiveness has been carried out comprehensive improvement.Experimental installation as shown in drawings, 1 expression temp controlled meter, 2 expression autoclaves, 3 expression Glass tubings, 4 expression steel discs, 5 expression heating zones, 6 expressions add electrothermal stove.Experimentation is: formation testing is injected glass inner sleeve to scale marks (40ml), with the good A of mill that weighs in advance
34 of steel hang up properly with the stainless steel lancet and put into oil, go into the still sealing, oxygenation displacement three times, boost to 0.8MPa, be warming up to selected temperature (160 ℃) after installing by accompanying drawing, oxygen pressure in the assaying reaction device, and under this temperature, kept 6 hours, reaction terminating writes down oxygenmeter pressure again, and calculating pressure falls.Then autoclave is cooled to normal temperature, emits overbottom pressure in the still, at this moment take out tinsel, clean with 60～90 ℃ sherwood oils, dry up, weigh up the weightening finish (being accurate to 0.0001g) of steel disc, test-results sees Table 3, wherein deposits improvement rate=(blank value-experimental value)/blank value * 100%.
Table 3 tinsel sedimentation evaluation diesel oil deposition conditions sample on tinsel adds dosage tinsel deposition deposition improvement rate
Mgkg
-1The blank diesel oil B of mg % 0 40.9 0 B+ examples 1 300 34.6 15.4 B+ examples 2 300 34.0 16.8 B+ examples 3 300 30.6 25.2 B+ examples 4 300 29.0 29.1 B+ examples 5 300 32.0 21.7 B+ examples 6 300 29.5 27.8 B+ examples 7 300 31.8 22.2
Example 10
This example adopts the dispersiveness of estimating multipurpose additive with the spot test method.
Spotting method is with (specific practice is with the 0.5000g additive samples after carbon black ointment (or engine sludge) and the dispersant, 0.2g carbon black ointment and 19.3g150SN base oil mix), disperse through high-speed stirring and sonic oscillation, in 50 ℃ of baking ovens, left standstill 18 hours then, drop on the filter paper after the taking-up, the oil droplet amount is controlled at 0.02～0.025g, filter paper is placed in 50 ℃ of baking ovens again and left standstill 2 hours, get then. go out to measure diffusion circle diameter (d) and greasy filth loop diameter (D), its ratio r=d/D * 100 are as the index of weighing dispersive ability, the r value is big more, and dispersiveness is good more.Experimental result is listed in table 4.
Table 4 spot test result
| Sample r | Sample r |
| Blank sample 22 examples 1 68.8 examples 2 69.0 examples 3 65.4 | Example 4 69.0 examples 5 69.4 examples 6 69.8 examples 7 67.5 |
From table 3 and table 4 as can be seen, the detergent-dispersant performance of the diesel oil multi-efficient additive of the present invention's preparation can be better than traditional succimide detergent-dispersant additives of example 1 and 2 preparations, or suitable with it.
Claims (6)
1. diesel oil multi-efficient additive, it is characterized in that by the preparation of following method: with phenol acids and allyl butyrate imide according to 0.5～5: 1 mol ratio was reacted 0.5～20 hour in 60～200 ℃ in the presence of organic solvent, and said phenol acids structure is: HOOC-[Ar]-(OH)
b, [Ar] represents aromatic ring, and b is 1～4 integer, and said thiazolinyl comes from C
3～C
4The multipolymer of monoolefine or homopolymer, its number average relative molecular mass is 300～5000.
2. according to the described additive of claim 1, it is characterized in that by following method preparation: with phenol acids and allyl butyrate imide according to 1～4: 1 mol ratio was reacted 1～10 hour in 80～160 ℃ in the presence of organic solvent.
3. according to the described additive of claim 1, it is characterized in that said phenol acids is selected from salicylic acid, m-Salicylic acid, P-hydroxybenzoic acid, 3-hydroxyl 2-naphthoic acid and 3,4,5-trihydroxybenzoic acid.
4. according to the described additive of claim 1, it is characterized in that said allyl butyrate imide is to be made by polyamines polyene and alkenyl succinic acid anhydride reactant, the mol ratio of polyamines polyene and enetutanedioic acid anhydride is 1: 1～2, temperature of reaction is 100～200 ℃, and the structure of said polyamines polyene is H
2N[(CH
2)
nNH]
mH, n are 2～4 integer, and m is 1～5 integer.
5. according to the described additive of claim 1, it is characterized in that thiazolinyl wherein comes from polyisobutene, Atactic Polypropelene or ethylene-propylene copolymer, its number average relative molecular mass is 800～2500, and the substitution value of enetutanedioic acid anhydride is 0.5～1.0.
6. according to the described additive of claim 4, it is characterized in that n is 2～3 integer, m is 3～4 integer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00124808 CN1110538C (en) | 2000-09-15 | 2000-09-15 | Multi-effect additive for diesel oil |
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|---|---|---|---|
| CN 00124808 CN1110538C (en) | 2000-09-15 | 2000-09-15 | Multi-effect additive for diesel oil |
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| CN1110538C true CN1110538C (en) | 2003-06-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323143C (en) * | 2004-10-28 | 2007-06-27 | 中国石油化工股份有限公司 | Diesel fuel antiwear additive with dispersion property |
| CN100378207C (en) * | 2005-07-26 | 2008-04-02 | 中国石油化工股份有限公司 | Preparation method of cleaning fuel additive |
| CN111676080A (en) * | 2020-06-23 | 2020-09-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of novel efficient soot dispersant |
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