CN107794097A - A kind of low acid type diesel oil multi-efficient additive and Dresel fuel compositions - Google Patents
A kind of low acid type diesel oil multi-efficient additive and Dresel fuel compositions Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/1915—Esters ester radical containing compounds; ester ethers; carbonic acid esters complex esters (at least 3 ester bonds)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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Abstract
The present invention relates to a kind of low acid type diesel oil multi-efficient additive composition, including a) the ring hydrazides of fourth two of alkyl substitution, b) polyol esters of fatty acids, wherein a and b weight ratio are 1:0.1~20.Additive of the present invention not only has preferable anti-wear effect, also with stainless property, and to the Effect of Acidity On Absorption very little of diesel oil.
Description
Technical field
The present invention relates to Dresel fuel compositions, are exactly diesel oil multi-efficient additive composition and Dresel fuel compositions.
Background technology
As countries in the world are to the pay attention to day by day of environmental issue, in order to reduce diesel exhaust gas pollution, the clear of high quality is produced
Cleaning diesel oil, it has also become the developing direction of modern petroleum refining industry.This diesel oil is typically low with sulfur content, hexadecane low containing aromatic hydrocarbons
The features such as value is high, and cut is light.Research shows that sulphur is CH, CO, particularly pellet in increase diesel engine emissions
(PM) most harmful element, so it is particularly important to improving atmosphere pollution to reduce sulfur content in diesel oil.The present U.S., Canada,
The diesel oil regulation of every Western Europe country, all provide that diesel oil amount containing S is less than 0.05%, some countries have even been arrived less than 0.0015%；
Arene content is relatively low.Because they generally employ harsher hydrogenation technique, polarity in diesel oil is oxygen-containing, nitrogen-containing compound
Content it is all very low, polycyclic, double ring arene content is also less, thus reduces the natural greasy property of diesel oil, causes one
A bit by diesel oil in itself come the injection pump being lubricated, such as rotary pump (rotary pumps), dispensing pump (distributor
Pumps) there is abrasion, reduce their service life.
Above mentioned problem can be alleviated by adding additive into diesel oil.It is generally believed that diesel antiwear additive can make up because
Diesel oil it is hydrogenated processing and cause to play the loss of Lubrication Composition in oil, improve diesel fuel lubricity.
Aliphatic acid antiwear additive used in jet fuel, such as the acid additives of dimerization acids, due to compound with lubricating oil
Performance is bad, it is impossible to which applied to diesel oil, therefore diesel antiwear additive is mostly the derivative of fatty acid ester, acid amides or salt.US588236
Disclose the carboxylate prepared by the use of the monocarboxylic acid with unsaturated chain and polyol reaction and be used as diesel antiwear additive.US4242099
Disclose with branched succinic anhydride or acid, C1~C5Monohydric alcohol, the mixed mixture of nitrate be used as diesel fuel additives
Diesel fuel lubricity and ignition performance can be improved.CN1766067 discloses a kind of polyolefin-based succinic anhydride and polyalcohol, polynary
One or more reacted products in amine, amino alcohol are as diesel antiwear additive.WO9915607 disclose dimer (fatty acid) yl with
The reaction product of epoxides is as diesel antiwear additive.
As sulfur content gradually reduces in diesel oil standard, increasing of the composition also with hydrogenation depth of anti-corrosion is played in diesel oil
Add and be removed, therefore, the corrosion sex chromosome mosaicism of diesel oil is also more and more obvious.Spot is often occurred by the metal surface of corrosion, and
Corrosion product can also block filter, even the accurate parts such as valve, sleeve, piston be blocked sometimes, so as to destroy fuel system
Normal work.Existing industrial antirust agent such as T746 acid number is too high, is added to the increasing that can cause oil product acidity in diesel oil
Add.
The content of the invention
It is an object of the invention to based on prior art, there is provided one kind can improve that low-sulfur diesel-oil is wear-resistant, resistant to rust energy
The low acid type multi-effect composite additive of power.
The present invention also provides a kind of with the good wear-resistant and low-sulfur diesel-oil composition of resistant to rust ability.
The present invention also provides a kind of improvement, and low-sulfur diesel-oil is wear-resistant and the method for resistant to rust ability.
Low sulphur diesel oil multi-efficient additive composition provided by the invention includes：A) the ring hydrazides of fourth two of alkyl substitution；b)C8
~C24 polyol esters of fatty acids, wherein a and b weight ratio are 1:0.1~20, preferably 1:0.5~10, more preferably 1：1~6.
Alkyl substitution the ring hydrazides formula of fourth two be：
It is at least one in R1, R2, R3, R4 therein to be alkyl containing 1-50 carbon or also contain other heteroatomic alkyl,
Remaining is hydrogen.The alkyl is preferably C8-C18 alkenyl, double bond number 1-3, can come from C2~C4Monoolefine is total to
Polymers or homopolymer, such as polyisobutene, random polypropylene or ethylene-propylene copolymer.R5, R6 are selected from hydrogen or the hydrocarbon containing 1~20 carbon
Base or the also alkyl containing other heteroatom groups, preferably hydrogen and methyl, ethyl, pi-allyl, phenyl, benzyl, the tert-butyl group, etc..
Wherein, the ring hydrazides of fourth two of preferable alkyl substitution is：The ring hydrazides of hendecene base fourth two, the ring hydrazides of laurylene base fourth two, 13
The ring hydrazides of allyl butyrate two, the ring hydrazides of tetradecene base fourth two, the ring hydrazides of 15 allyl butyrate two, the ring hydrazides of hexadecylene base fourth two, 17
The ring hydrazides of allyl butyrate two, the ring hydrazides of octadecylene base fourth two, the ring formylhydrazine of hendecene base base fourth two, the ring formyl of laurylene base fourth two
Hydrazine, the ring formylhydrazine of tridecylene base fourth two, the ring formylhydrazine of tetradecene base fourth two, the ring formylhydrazine of 15 allyl butyrate two, hexadecylene base fourth
Two ring formylhydrazines, the ring formylhydrazine of 17 allyl butyrate two, the ring formylhydrazine of octadecylene base fourth two etc..
The ring hydrazides of fourth two of described alkyl substitution is prepared by the succinic anhydride that alkyl substitutes and hydrazine reaction,
0~200 DEG C of reaction temperature, preferably 80~150 DEG C, preferably 1~36 hour reaction time, 5~10 hours.The fourth two of alkyl substitution
The mol ratio of acid anhydrides (being counted using maleic anhydride) and hydrazine is 1:0.5~10, preferably 1:0.8~1.5.
The reaction is carried out in non-pressure vessel, and reaction can both be not added with catalyst, and it is anti-to accelerate also to add appropriate catalyst
Should, the property of visual response can add acid or base catalyst.Acidic catalyst such as sulfuric acid, p-methyl benzenesulfonic acid, hydrochloric acid, acidity
Ion hands over exchanger resin, solid super-strong acid etc., base catalyst such as sodium hydroxide, sodium methoxide etc..Reaction can use solvent refluxing
Divide water, can also be removed water with purged with nitrogen flow.Solvent can be toluene, dimethylbenzene, ethylbenzene, n-hexane, hexamethylene, petroleum ether,
Industrial naptha, ethanol, isopropanol, n-butanol etc. or boiling range are 159~185 DEG C of aromatic diluent oil.
The general structure of the succinic anhydride of described alkyl substitution is：
It is at least one in R1, R2, R3, R4 therein to be alkyl containing 1-50 carbon or also contain other heteroatomic alkyl,
Remaining is hydrogen.The alkyl is preferably C8-C18 alkenyl, double bond number 1-3, can come from C2~C4Monoolefine is total to
Polymers or homopolymer, such as polyisobutene, random polypropylene or ethylene-propylene copolymer.
Described hydrazine is selected from hydrazine, hydrazine hydrate, the hydrazine hydrate aqueous solution or C1-C20 alkyl hydrazines, formula：
Wherein R5, R6 is the alkyl selected from hydrogen or containing 1~20 carbon or the alkyl containing other heteroatom groups, such as first
Base hydrazine, uns-dimethylhydrazine, ethyl hydrazine, pi-allyl hydrazine, phenyl hydrazine, benzyl hydrazine, tertiary butyl hydrazine, 1- (4- morpholinyls butyl) hydrazine, ring penta
Base hydrazine, cyclohexyl hydrazine, CAS：15888-12-7 etc..
Described component b is C8~C24 polyol esters of fatty acids.Described polyol esters of fatty acids can be natural oil with
The product of transesterification reaction or the esterification reaction product of C8~C24 aliphatic acid and polyalcohol of polyalcohol, can also be fat
The reaction product or product mixtures of fatty acid methyl esters (biodiesel) and polyalcohol.
Described polyalcohol is the alcohol at least containing two hydroxyls, preferably C2~C8 polyalcohols in molecule.Such as ethylene glycol,
Polyethylene glycol, glycerine, the propane diols of various isomers, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol,
Decanediol, and pentaerythrite, sorbierite, anhydrous sorbitol, trimethylolpropane etc..
Described natural oil is vegetable oil or animal oil, can be fresh grease or the waste oil of recovery.Its
Middle vegetable oil be selected from peanut oil, corn oil, cottonseed oil, rape seed oil, soybean oil, palm oil, safflower oil, linseed oil, coconut oil,
Oak Tree oil, apricot kernel oil, walnut oil, slight sesame oil, sesame oil, olive oil, sunflower oil etc., animal oil is selected from lard, chicken fat, duck
Oil, sheep oil, butter, haco oil, fish oil etc., wherein vegetable oil are preferable.
In the reaction product of natural oil and polyalcohol, a triglycerides molecule can be with one, two or three hydroxyl
Base reaction generation ester.
, can be by its molecule for convenience of rate of charge is calculated because natural oil is all the mixed glyceride based on 18 carbon
Amount is considered as (molecular weight 890) identical with glycerol stearate roughly.Reaction can with acid catalysis for example sulfuric acid, p-methyl benzenesulfonic acid,
Acid-exchange resin, Lewis acid etc., base catalysis such as sodium hydroxide, potassium hydroxide, dimethyl cyclohexyl amine etc. can also be used.
Reaction time is 1~20 hour, preferably 2~10 hours.Reaction temperature is 50~300 DEG C, preferably 80~260 DEG C.
When aliphatic acid carries out esterification with polyalcohol, aliphatic acid can be selected from C8~C24 aliphatic acid, such as octanoic acid, the last of the ten Heavenly stems
Acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, arachidic acid, wych-elm acid, erucic acid etc., preferably
Oleic acid and linoleic acid.Can also be various sour mixtures, such as animal oleic acid or vegetable oil acid, such as lard, chicken fat, duck oil,
Goose oil, sheep oil, house oil, butter, rabbit oil, haco oil, shark fatty acid oil；Peanut oil, corn oil, cottonseed oil, rape seed oil, soybean
Oil, palm oil, safflower oil, linseed oil, coconut oil, Oak Tree oil, apricot kernel oil, walnut oil, castor oil, sesame oil, olive oil, to
Day certain herbaceous plants with big flowers oil, curcas oil, tung oil, shinyleaf yellowhorn oil, the aliphatic acid of the halophytes such as grease such as kostelezkya virginica, cyperue esculentus, can be with
It is the ready denier oil acid extracted in papermaking waste material, preferably through the refined ready denier oil acid for being stripped of rosin acid, such as U.S.
The trade mark of Arizonal companies of state is 2LT ready denier oil acid.The reaction mol ratio of aliphatic acid and fatty alcohol is 1：0.1~
10, preferably 1：0.5~5, reaction temperature is 50~300 DEG C, preferably 80~260 DEG C.Reaction can not have to catalyst, can also use
Acid catalysis such as sulfuric acid, p-methyl benzenesulfonic acid, acid-exchange resin, Lewis acid etc., can also with base catalysis such as sodium hydroxide,
Potassium hydroxide, dimethyl cyclohexyl amine etc..Reaction time is 1~20 hour, preferably 2~10 hours.Reaction can be lazy with nitrogen etc.
Property gas, which blows water, to take water with solvent.
Described fatty acid methyl ester is the fatty acid methyl ester admixture based on C16~C20, such as methyl hexadecanoate, hard
Resin acid methyl esters, methyl oleate, methyl linoleate, methyl linolenate, methyl arachidate, methyl erucate etc..Fatty acid methyl ester with it is more
The reaction mol ratio of first alcohol is 1：0.1~10, preferably 1：0.5~5, reaction temperature is 50~300 DEG C, preferably 80~260 DEG C.Instead
It should not can have to catalyst, acid catalysis such as sulfuric acid, p-methyl benzenesulfonic acid, acid-exchange resin, Lewis acid etc. can also be used,
Base catalysis such as sodium hydroxide, sodium methoxide, potassium hydroxide, dimethyl cyclohexyl amine etc. can also be used.Reaction time is 1~20 hour,
It is preferred that 2~10 hours.Reaction can also carry the methanol of reaction generation with the inert blowing gas such as nitrogen methanol with solvent.
According to using needs, solvent, institute can also be contained in low sulphur diesel oil multi-efficient additive composition provided by the invention
Toluene, dimethylbenzene, ethylbenzene, n-hexane, hexamethylene, petroleum ether, industrial naptha, methanol, ethanol, isopropyl can be selected from by stating solvent
Alcohol, n-butanol etc. or boiling range are 159~185 DEG C of aromatic diluent oil.
In low sulphur diesel oil multi-efficient additive composition provided by the invention, other additives, such as hexadecane can also be contained
It is worth modifier, flow improving agent, metal deactivator, preservative etc..
A kind of low-sulfur diesel-oil composition, combined including low-sulfur diesel-oil and multi-effect additive of low-surface diesel of the present invention
Thing, on the basis of low-sulfur diesel-oil weight, content of the additive in diesel oil is usually 10~500mg/kg, preferably 50~
300mg/kg。
Sulfur content in the low-sulfur diesel-oil is 0~100mg/kg, particularly 0~50mg/kg.
According to using needs, other additives can also be contained in low-sulfur diesel-oil composition provided by the invention, such as 16
Alkane value modifier, flow improving agent, metal deactivator, preservative etc..
Low-sulfur diesel-oil is wear-resistant and the method for resistant to rust ability for a kind of improvement, it is characterised in that by low-sulfur provided by the invention
Diesel oil multi-efficient additive composition is added in low-sulfur diesel-oil, and on the basis of low-sulfur diesel-oil gross weight, the additive is in diesel oil
In content be usually 10~500mg/kg, preferably 50~300mg/kg.
Sulfur content in the low-sulfur diesel-oil is 0~100mg/kg, particularly 0~50mg/kg.
Low sulphur diesel oil multi-efficient additive composition provided by the invention can not only improve the wear resistence (lubrication of low stream diesel oil
Property), the corrosion of diesel oil can also be suppressed, while influence very little of the compound additive of the present invention to diesel oil acidity is added, it will not make
Add agent diesel oil acidity be above standard requirement " be not more than 7mgKOH/100mL " limit value.
Brief description of the drawings
Fig. 1 be embodiment it is 2-in-1 into hydrazides mass spectrogram.
It is alkenyl there was only one in R1, R2, R3, R4 therein, and remaining is hydrogen.R5, R6 are hydrogen.In mass spectrogram：M/z=
The molecular ion peak of 266,280,294 hydrazides substituted for affiliated hendecene base, laurylene base, tridecylene base, m/z=267,
268,281,282,295,296 correspond to the isotopic peak of three kinds of hydrazides respectively.
Embodiment
Below by embodiment, the present invention is further illustrated.
In these embodiments, the rust-preventing characteristic of diesel oil according to GB/T 11143-2008 methods describeds by 300mL samples and
30mL distilled water or synthetic seawater mixing, are totally submerged in the experiment rod iron of cylinder wherein, are stirred at 60 DEG C.Experiment
Cycle is 24h, and the test period terminates the vestige of rear viewing test copper rod corrosion and the degree of corrosion.
In these embodiments, the lubricity of diesel oil is according to side described in CEC-F-06-A-96 or ISO/FDIS 12156-1
Method (American process is ASTM D-6079) high-frequency reciprocating tester (High-Frequency Reciprocating Rig,
HFRR on) (production of PCS instrument companies of Britain) determine 60 DEG C when grinding defect diameter (Wear Scar Diameter, WSD), pass through
Influence to temperature and humidity, which is corrected, must report result WS1.4.The measure of acid number uses the methods of GB/T 7304, acidity
Measure uses the methods of GB/T 258.
Other materials are as solvent outside described in not adding during following examples reaction.
Part commodity (unconventional commodity) producer's trade mark in embodiment：
Castor oil is the industrial castor oil of Xing He bio tech ltd of Tongliao, Inner Mongolia city production；Soybean oil is Jin Long
The edible soybean oil of fish company production；Cottonseed oil is the industrial products that cotton purple light Mian Ye Co., Ltds produce in Xingtai；Dish
Seed oil is Hunan Vchen Industry Co., Ltd's production " double low " rapeseed oil；Biodiesel is the outstanding gloomy biodiesel stock in Ningbo
The refining biodiesel that saturated fatty acid is stripped of by distillation of part Co., Ltd production；D-sorbite is Aladdin reagent public affairs
The AR of department；Glycerine is the AR of Chinese medicines group.
Example 1
This example is the preparation of the ring hydrazides of fourth two of alkyl substitution.
By 50g (0.19mol) dodecenylsuccinic acids acid anhydride, 6.0g (0.19mol) hydrazine be placed in one equipped with electric mixer,
In the three-necked flask reactor of thermometer, reflux water-dividing device and nitrogen ingress pipe, nitrogen heating stirring temperature control is passed through 30
DEG C, with nitrogen purging reaction 1 hour, that is, product is generated as, measures acid number 20.6mgKOH/g.
Example 2
This example is the preparation of the ring hydrazides of allyl butyrate two.
50g (0.19mol) dodecenylsuccinic acids acid anhydride (is contained into a small amount of hendecene base succinic anhydride and tridecylene base succinic acid
Acid anhydride), 11.2g (0.19mol) hydrazine hydrate (85%, wt) is placed in one and electric mixer, thermometer, reflux water-dividing device and nitrogen is housed
In the three-necked flask reactor of ingress pipe, it is passed through nitrogen heating stirring and is warming up to 150~160 DEG C, it is small with nitrogen purging reaction 3
When, that is, it is generated as product, acid number 19.9mgKOH/g.
Example 3
This example is the preparation of the ring hydrazides of fourth two of alkyl substitution.
100g (0.31mol) hexadecylene base succinic anhydride, 18.6g (0.31mol) ethyl hydrazine are placed in one electric mixing is housed
In the three-necked flask reactor for mixing device, thermometer, reflux water-dividing device and nitrogen ingress pipe, nitrogen heating stirring temperature control is passed through
At 80 DEG C, with nitrogen purging reaction 5 hours, that is, product, acid number 22.5mgKOH/g are generated as.
Embodiment 4~9 is the preparation of polyol esters of fatty acids
Example 4
By 100g castor oil, 17g 1,2- propane diols, (mol ratio of castor oil and l, 2- propane diols is about 1:2) and
L.2g p-methyl benzenesulfonic acid is placed in a reactor equipped with electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe, is led to
Entering nitrogen 5~10 minutes, and keep faint nitrogen stream during the course of the reaction, heating stirring is warming up to 150 DEG C, reacts 5 hours,
Then 0.5gCa (OH) is added2P-methyl benzenesulfonic acid is neutralized, cooling, which filters, produces product, acid number 0.4mgKOH/g.
Example 5
By 100g soybean oils, 30g D-sorbites, (mol ratio of soybean oil and D-sorbite is about 1:And 2.8g methanol 1.5)
Receive/catalyst for methanol be placed in one equipped with electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe reactor in, lead to
Entering nitrogen 5~10 minutes, and keep faint nitrogen stream during the course of the reaction, heating stirring is warming up to 160 DEG C, reacts 6 hours,
It is cooled to 90 DEG C and adds 3.2g Emathlites and neutralizes and filter and produce product, acid number 0.3mgKOH/g.
Example 6
By 100g cottonseed oils, 10.5g 1,2- butanediols, (mol ratio of cottonseed oil and 1,2- butanediols is about 1:2) and
L.5g dimethyl cyclohexyl amine is placed in a reactor equipped with electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe,
It is passed through nitrogen 5~10 minutes, and keeps faint nitrogen stream during the course of the reaction, heating stirring is warming up to 150 DEG C, and reaction 7 is small
When, cool down and produce product, acid number 0.8mgKOH/g.
Example 7
By 100g rapeseed oils, 51g glycerine, (mol ratio of rapeseed oil and glycerine is about 1:5) it is placed in one with 1.0gKOH and is equipped with
Electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe reactor in, be passed through nitrogen 5~10 minutes, and reacting
During keep faint nitrogen stream, heating stirring is warming up to 200 DEG C, reacts 6 hours, stands and separated in separatory funnel
The glycerine of amount, adds 5g Emathlites and 1g suction filtered through kieselguhr, and filtrate is product, acid number 0.3mgKOH/g.
Example 8
By 100g ready denier oil acids (Arizonal companies of the U.S. produce, trade mark 2LT) and 40g glycerine (tall oil fat
The mol ratio of fat acid and glycerine is about 1:1.2) one is placed in import equipped with electric mixer, thermometer, reflux condensing tube and nitrogen
In the reactor of pipe, nitrogen being passed through 5~10 minutes, and keeping faint nitrogen stream during the course of the reaction, heating stirring is warming up to
200 DEG C, reaction is got product for 10 hours, acid number 0.9mgKOH/g.
Example 9
By 100g biodiesel and 35g glycerine, (biodiesel and the mol ratio of glycerine are about 1:1.2) it is placed in 1.0gKOH
In one reactor equipped with electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe, nitrogen is passed through 5~10 minutes, and
Faint nitrogen stream is kept during the course of the reaction, and heating stirring is warming up to 200 DEG C, reacts and adds within 6 hours the friendship of 2.2g acid ions
Change in resin and base catalyst is got product, acid number 0.1mgKOH/g.
Example 10~17 is the preparation of composition of additive for diesel oil provided by the invention.
The ring hydrazides of fourth two that alkyl selected from one of example 1~3 is substituted is as component a, selected from one of example 4~9
Polyol ester component b, mixed according to the part by weight shown in table 1, obtain different compositions.
The preparation of the multi-effect composite additive of table 1
Comparative example
(trade mark of Run Yinglian companies production is InfiniumR655 fatty acid ester type diesel oil to the ester type antiwear additive 1 of comparative example 1
Antiwear additive, acid number 0.54mgKOH/g)
Comparative example 2 is ester type antiwear additive 2 (the fatty acid ester type diesel antiwear additive of Jiangsu Creative Company production, acid number
0.3mgKOH/g)
Comparative example 3 is T746 antirust agent.(the dodecenylsuccinic acid type antirust agent of Dalian Lvshun chemical plant production,
Acid number 359.6mgKOH/g)
Example 18
This example is the lubricity effect that additive made from example 10,11,12,13,14,15,16,17 uses in diesel oil
Fruit.DF-06 ready-mixed oils, its physicochemical property are shown in Table 2, add HFRR methods (ISO12156-1) the grinding defect diameter WS1.4 of diesel oil after agent to see
Table 3, when grinding defect diameter is less than 460um (60 DEG C), then the lubricity of diesel oil is qualified.WS1.4 data are smaller, sample anti-wear effect
Better.
Example 19
This example uses anti-for compositions of additives made from example 10,11,12,13,14,15,16,17 in diesel oil
Tarnish resistance effect, DF-06 ready-mixed oils, its physicochemical property are shown in Table 2, and resistant to rust effect is shown in Table 4.Experimental method GB/T 11143-
2008.The smaller explanation corrosion of 24h corrosion percentages is smaller, and data are 0 explanation non-corroding, and the resistant to rust effect of additive is best.
The physicochemical property of the diesel oil of table 2
The increase of improvement and acidity of the additive of table 3 to diesel fuel lubricity
As can be seen from Table 3, the hydrazides of allyl butyrate two described in component a is individually added into, is had to Lubricity of Low-Sulfur Diesel Fuels necessarily
The improvement of degree, being individually added into the polyol esters of fatty acids described in component b also has improvement, but addition group to Lubricity of Low-Sulfur Diesel Fuels
Divide a and component b with 1:After 1~6 compound additive, Lubricity of Low-Sulfur Diesel Fuels is greatly improved, and effect is than each individually adding
Entering to have significantly strengthens.Anti-wear effect also fatty acid ester type antiwear additive (comparative example 1 He more conventional than industrially after compound
2) to get well, anti-wear effect is far better than conventional antirust agent T 746.Component a and component b is with 1:9 compound rear anti-wear effect
Synergistic effect is deteriorated.Influence very little of the component a and component b compound additive to diesel oil acidity is added, and adds industrial antirust
The acidity increase of diesel oil is very big after agent T746, causes the acidity of diesel oil more than 7mgKOH/100mL, diesel oil after adding 200mg/kg
Acidity exceed standard requirement limit value.
Improvement of the additive of table 4 to diesel oil rust-preventing characteristic
It can be seen from Table 4 that additive (example 10-17) provided by the invention can substantially improve the rust-preventing characteristic of diesel oil,
Effect is good when being used alone than component a or component b, is also better than the conventional commercial fatty acids ester type diesel antiwear additive (He of comparative example 1
2).Component a and component b is with 1:1~6 compound rear rust-proof effect of ratio is better than component a and component b with 1:9 ratios are compound (to be implemented
Example 17).
Claims (12)
1. a kind of low acid type diesel oil multi-efficient additive composition, including：A) the ring hydrazides of fourth two of alkyl substitution；B) C8~C24 fat
The weight ratio of fat acid polyol ester, wherein a and b is 1:0.1~20.
2. according to the composition described in claim 1, wherein, a and b weight ratio are 1:1~6.
3. according to the composition described in claim 1, wherein, the alkyl of the ring hydrazides of fourth two of alkyl substitution is C8-C18 alkene
Base.
4. according to the composition described in claim 1, wherein, the ring hydrazides of fourth two of described alkyl substitution is selected from hendecene base base
The ring hydrazides of fourth two, the ring hydrazides of laurylene base fourth two, the ring hydrazides of tridecylene base fourth two, the ring hydrazides of tetradecene base fourth two, 15 alkenyls
The ring hydrazides of fourth two, the ring hydrazides of hexadecylene base fourth two, the ring hydrazides of 17 allyl butyrate two, the ring hydrazides of octadecylene base fourth two, hendecene base
The ring formylhydrazine of base fourth two, the ring formylhydrazine of laurylene base fourth two, the ring formylhydrazine of tridecylene base fourth two, the ring formyl of tetradecene base fourth two
Hydrazine, the ring formylhydrazine of 15 allyl butyrate two, the ring formylhydrazine of hexadecylene base fourth two, the ring formylhydrazine of 17 allyl butyrate two, octadecylene base fourth
At least one of two ring formylhydrazines.
5. according to the composition described in one of claim 1-4, wherein, the ring hydrazides of fourth two of described alkyl substitution is to pass through hydrocarbon
What the succinic anhydride of base substitution was prepared with hydrazine reaction.
6. according to the composition described in claim 5, wherein, reaction condition is 0~200 DEG C of reaction temperature, and/or the reaction time
1~36 hour, and/or the succinic anhydride of alkyl substitution and the mol ratio of hydrazine are 1:0.5~10.
7. according to the composition described in claim 5, wherein, described hydrazine is selected from hydrazine, hydrazine hydrate, the hydrazine hydrate aqueous solution
Or C1-C20 alkyl hydrazines.
8. according to the composition described in claim 1, wherein, described C8~C24 polyol esters of fatty acids, selected from natural oil
With the product of transesterification reaction of polyalcohol, the esterification reaction product of aliphatic acid and polyalcohol, and fatty acid methyl ester and polyalcohol
Reaction product or product mixtures.
9. according to the composition described in claim 8, wherein described polyalcohol is C2~C8 polyalcohols.
10. according to the composition described in claim 8, wherein described natural oil is vegetable oil or animal oil, and/or it is described
Aliphatic acid be the refined ready denier oil acid for being stripped of rosin acid, and/or described fatty acid methyl ester be using C16~C18 as
Main fatty acid methyl ester admixture.
11. a kind of low-sulfur diesel-oil composition, more including one of low-sulfur diesel-oil and claim 1~10 low acid type diesel oil
Compositions of additives is imitated, on the basis of low-sulfur diesel-oil weight, content of the additive in diesel oil is 10~500mg/kg.
12. low-sulfur diesel-oil is wear-resistant and the method for resistant to rust ability for a kind of improvement, it is characterised in that by one of claim 1~10
Described low sulphur diesel oil multi-efficient additive composition is added in low-sulfur diesel-oil, described to add on the basis of low-sulfur diesel-oil gross weight
Add content of the agent in diesel oil to be 10~500mg/kg.
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| CN1272415C (en) * | 2002-09-26 | 2006-08-30 | 尤尼罗亚尔化学公司 | Alkyl succinite hydrazide additive for lubricant |
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| CN1272415C (en) * | 2002-09-26 | 2006-08-30 | 尤尼罗亚尔化学公司 | Alkyl succinite hydrazide additive for lubricant |
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