CN1743435A - Anti-wear additive capable of improving diesel colour stability - Google Patents
Anti-wear additive capable of improving diesel colour stability Download PDFInfo
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- CN1743435A CN1743435A CN 200410073647 CN200410073647A CN1743435A CN 1743435 A CN1743435 A CN 1743435A CN 200410073647 CN200410073647 CN 200410073647 CN 200410073647 A CN200410073647 A CN 200410073647A CN 1743435 A CN1743435 A CN 1743435A
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Abstract
An antiwear additive for improving stability of diesel oil color is got under the reaction of C6-C40 fatty acid, C1-C6 methanal and C2-C20 organic amine under 50~200deg.c among which, the mole ratio of the fatty acid, methanal and organic amine is 1:0.1~10:0.1~10, the organic amine is a polyene poly-amine, alkamine or alkoxyl poly-amine or a mixture in the mole ratio of 1:0.01~10 with C3-C20 fatty amine, naphthene-base amine or heterocyclic amine.
Description
Technical field
The invention belongs to diesel-dope, definite saying so both can be used as diesel antiwear additive, also can be used as the multipurpose additive of diesel colour stablizer.
Technical background
Along with the pay attention to day by day of countries in the world to environmental issue, pollute in order to reduce diesel exhaust gas, produce high-quality clean diesel, become the developing direction of modern petroleum refining industry.This diesel oil has generally that sulphur content is low, and it is low to contain aromatic hydrocarbons, cetane value height, characteristics such as cut is light.Studies show that sulphur is the harmful element that increases CH, CO, particularly pellet (PM) in the diesel engine emissions, so it is particularly important to improving topsoil to reduce in the diesel oil sulphur content.Now the diesel oil specification of the U.S., Canada, every Western Europe country is all stipulated diesel oil S content less than 0.05%, some country even arrived less than 0.0015%.Aromaticity content is also lower.Because they have generally adopted harsh hydrogenation technique, the content that polarity in the diesel oil contains oxygen, nitrogenous compound is all very low, the content of many rings, double ring arene is also less, thereby reduced the natural lubricity of diesel oil, some oil injection pumps that rely on diesel oil itself to be lubricated have been caused, wearing and tearing occur as rotor pump (rotarypumps), proportioning pump (distributor pumps), reduced their work-ing life.
Simultaneously, the heterogeneous ring compound that also contains various unsaturated components and nitrogen, sulphur in the diesel oil.Deterioration by oxidation can take place and produce sediment, thereby the diesel engine filtering system is stopped up and the nozzle carbon distribution in these materials in the storage process of diesel oil.Be accompanied by the variation that this process usually has diesel colour.Though deepening of diesel colour might not mean that its oxidation sediment exceeds standard,, the user can not judge whether this diesel oil can be used safely this moment.The colourity of China's national Specification diesel oil is not more than 3.5 (ASTM-1500).
The problems referred to above can be alleviated by add additive in diesel oil.It is generally acknowledged that diesel antiwear additive can remedy because of diesel oil causes the loss that plays lubricated composition in the oil through hydrotreatment, improves diesel fuel lubricity; The diesel colour stablizer can stop, weakens or disturb above-mentioned various reaction, to suppress the diesel oil variable color.
The lipid acid anti-wear agent that rocket engine fuel is used, as the acid additives of dimerization acids, since bad with the composite performance of lubricating oil, can not be applied to diesel oil.Therefore diesel antiwear additive mostly is the derivative of fatty acid ester, acid amides or salt.EP773279 discloses and has used the carboxylicesters of dimeracid and hydramine prepared in reaction as diesel antiwear additive.EP798364 discloses with the salt of lipid acid and aliphatic amide prepared in reaction or acid amides as diesel antiwear additive.EP1209217 discloses C
6～C
50The reaction product of saturated fatty acid and dicarboxylic acid and short chain oils dissolubility primary, the second month in a season, tertiary amine is as diesel antiwear additive.WO9915607 discloses the reaction product of dimer (fatty acid) yl and epoxide as diesel antiwear additive.But these additives to the stability of diesel oil to no effect, and may also can make the oxidation stability variation of diesel oil in many cases.
GB 2,245, and the replacement triazine that 588 reports generate with primary amine, secondary amine and formaldehyde reaction, replacement methane compound are as diesel oil stabilizing agent.This class additive has certain stabilization to color, but its oil soluble is not so good.And diesel fuel lubricity there is not improvement yet.
Summary of the invention
The invention provides a kind of wear preventive additive that can improve diesel colour stability.
Wear preventive additive provided by the invention is by C
6～C
40Lipid acid and C
1～C
6Aldehyde and C
2～C
20Organic amine gets 50～200 ℃ of reactions 0.5～20 hour.The mol ratio of lipid acid and formaldehyde, organic amine reaction is 1: 0.1～10: 0.1～10, preferred 1: 0.2～5: 0.2～5.
Described C
6～C
40Lipid acid, preferred C
8～C
36Lipid acid.Can be monocarboxylic acid or polycarboxylic acid; Can be saturated acid or unsaturated acid.For example caproic acid, hexanodioic acid, sad, isocaprylic acid (2 ethyl hexanoic acid), capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, oleic acid, linolic acid, linolenic acid, stearic acid, Palmiticacid, ricinolic acid, 20 acid, dimerization oleic acid, linoleic acid dimer etc. is a kind of and multiple; Can also be mixing acid, as various vegetable fatty acids such as palmitinic acid etc., preferably normal temperature be down for liquid acid, as oleic acid, linolic acid, linolenic acid, dimerization oleic acid, linoleic acid dimer, ricinolic acid or its mixture.
Aldehyde wherein is meant C
1～C
6Aldehyde, as formaldehyde, acetaldehyde, propionic aldehyde, hexamethylene aldehyde etc., formaldehyde preferably, 36% formaldehyde solution or Paraformaldehyde 96 all can.
Described organic amine is polyamines polyene, amino alcohol or alkoxy polyamine, also can be at least a polyamines polyene, amino alcohol or alkoxy polyamine and C
3～C
20The mixture of aliphatic amide, Cycloalkyl amine or heterocyclic amine, the former and the latter's mol ratio is 1: 0.01～10, preferred 1: 0.1～5, be preferably 1: 0.2～2.
The structural formula of described 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 diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
Described amino alcohol is selected from 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, thanomin, diethanolamine or its mixture.
Described alkoxy polyamine is that polyamines polyene and epoxide are with 1: 0.5～10, the reaction product of preferred 1: 1～5 mol ratios, wherein polyamines polyene diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines, epoxide optimization ethylene oxide, 1,2-propylene oxide, 1, the 2-butylene oxide ring.
Described C
3～C
20Aliphatic amide can be primary amine, secondary amine; Can be connected primary carbon position, secondary carbon potential or tertiary carbon position, preferred C
6～C
20The primene JM-T and positive structure primary amine.Cycloalkyl amine can be cyclopentamine, hexahydroaniline etc.; Heterocyclic amine can be morpholine, piperazine etc.
This reaction both can also can be carried out in autoclave in non-pressure vessel, and reaction both can not add catalyzer, but the also character of visual response and add acidity or basic catalyst with accelerated reaction.Wherein an acidic catalyst such as sulfuric acid, tosic acid, acidic ion exchange resin, acidic white earth etc.; Basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, dimethylcyclohexylamine etc.Reaction can divide water with solvent refluxing, also can purge with nitrogen gas stream to dewater.Solvent can be toluene, dimethylbenzene, ethylbenzene, normal hexane, hexanaphthene, sherwood oil, industrial naptha etc., also can be that boiling range is 159～185 ℃ of aromatic hydrocarbons thinning oils.50～200 ℃ of temperature of reaction, preferred 70～160 ℃, 0.5～20 hour reaction times, preferred 1～10 hour.
Specifically, can be synthetic by following three kinds of modes:
1. described lipid acid and described organic amine carry out amination or esterification earlier, and reaction process divides water or nitrogen gas stream to purge with solvent refluxing to dewater, and then add formaldehyde and react, and the latter can once add, and also can add in batches.
2. described organic amine and Paraformaldehyde 96 or formalin carry out dehydration condensation earlier, and the latter can once add, and also can add in batches.And then add described lipid acid and react, reaction process divides water or nitrogen gas stream to purge with solvent refluxing to dewater.
3. described lipid acid, formaldehyde and described organic amine add simultaneously and react.Reaction process divides water or nitrogen gas stream purging to dewater with solvent refluxing.
The addition of multipurpose additive provided by the invention in diesel oil generally is 20～2000ppm, and preferred 40～1000ppm is preferably in 60～600ppm.
Additive provided by the invention also can slow down the generation of oxidation sediment in the diesel oil.
According to using needs, additive provided by the invention can also with other additive, use simultaneously as FLOW IMPROVERS, detergent-dispersant additive, cetane number improver, metal passivator, sanitas etc.
Embodiment.
The present invention is further illustrated below by embodiment.In these embodiments, the oilness of diesel oil according to CEC-F-06-A-96 or the described method of ISO/FDIS 12156-1 (American process is ASTM D-6079-97) at the reciprocal trier of high frequency (High-FrequencyReciprocating Rig, grinding defect diameter (Wear Scar Diameter when HFRR) upward (production of Britain PCS instrument company) measures 60 ℃, WSD), by the influence of temperature and humidity is proofreaied and correct the WS that reports the result
1.4Diesel colour is pressed the described method of ASTM D-1500 and is measured.
Example 1
In a 500ml three-necked bottle, add 112.0g linolic acid (0.4mol) and 58.4g triethylene tetramine (0.4mol) and 160g toluene, about 4 hours of heated and stirred reflux water-dividing, add 12g (0.4mol) Paraformaldehyde 96, continue reflux water-dividing reaction 3 hours, toluene is removed in underpressure distillation, and adding the 168g boiling range again is that 159～185 ℃ of aromatic hydrocarbons thinning oils are made into about 50% diluent.
Example 2
In a 500ml three-necked bottle, the methanol solution (concentration 28 weight %) that adds 141.0g oleic acid (0.5mol), 52.5g diethanolamine (0.5mol), 6.9g sodium methylate, logical nitrogen, heated and stirred 140 ℃ of esterifications 3 hours, adds 12g (0.4mol) Paraformaldehyde 96, continue logical nitrogen 140 ℃ of reactions 4 hours, add the neutralization of 7.7g acidic white earth at last, filter and collection filtrate, adding boiling range again is that 159～185 ℃ of aromatic hydrocarbons thinning oils are made into about 50% diluent.
Example 3
In a 500ml three-necked bottle, add 56.7g tetraethylene pentamine (0.3mol) and 23.4g morpholine (0.3mol) and 90g toluene, heated and stirred refluxes, the formaldehyde solution (0.3mol) of 25.0g about 36% (weight) was added drop-wise in the three-necked bottle in 2 hours, about 2 hours of reflux water-dividing adds 178.8g ricinolic acid (0.6mol) again, continues reflux water-dividing reaction 3 hours, toluene is removed in underpressure distillation, and adding the 251g boiling range again is that 159～185 ℃ of aromatic hydrocarbons thinning oils are made into about 50% diluent.
Example 4
In a 500ml three-necked bottle, add 41.2g diethylenetriamine (0.4mol) and positive amino dodecane of 37.0g (0.2mol) and 80g120# industrial naptha, heated and stirred refluxes, the formaldehyde solution (0.5mol) of 41.7g36% was added drop-wise in the three-necked bottle in 2 hours, about 2 hours of reflux water-dividing, add 169.2g dimerization oleic acid (0.3mol) again, continue reflux water-dividing reaction 3 hours, industrial naptha is removed in underpressure distillation, and adding the 242g boiling range again is that 159～185 ℃ of aromatic hydrocarbons thinning oils are made into about 50% diluent.
Example 5
In a 500ml three-necked bottle, add 169.2g oleic acid (0.6mol), 46.4g five ethene hexamines (0.2mol), 6.0g (0.2mol) Paraformaldehyde 96 and 150g toluene, heated and stirred reflux water-dividing reaction 6 hours, toluene is removed in underpressure distillation, and adding the 242g boiling range again is that 159～185 ℃ of aromatic hydrocarbons thinning oils are made into about 50% diluent.
Example 6
This example is the result of use of multipurpose additive in diesel oil that example 14～20 makes.Select huge port 0 for use
#The mixed oil (a) and the Yanshan Mountain 0
#Processed oil (b).Its physicochemical property sees Table 1, adds HFRR method (ISO12156-1) the grinding defect diameter WS of agent front and back diesel oil
1.4, diesel oil at room temperature the lucifuge colour-change of storing 3 months see Table 2, when grinding defect diameter during less than 460um (60 ℃), then the oilness of diesel oil is qualified; Then the color of diesel oil was qualified when the colourity of diesel oil was not more than No. 3.5.
The physicochemical property of table 1 diesel oil
| Diesel oil | ||
| (a) | (b) | |
| Density (20 ℃)/gcm -3Viscosity (40 ℃)/mm 2·s -1S content/ppm N content/ppm basic nitrogen/total the double ring arene of the total mononuclear aromatics/m% of the total cycloalkane/m% of ppm alkane/m%/m% thrcylic aromatic hydrocarbon/m% initial boiling point/℃ 20% heats up in a steamer a little/℃ 50% heat up in a steamer a little/℃ 90% heat up in a steamer a little/℃ do/℃ | 0.8576 2.548 238 120 10 38.5 18.4 29.6 11.9 1.6 188 230 252 343 353 | 0.8360 2.510 197 163 36 47.2 22.3 21.6 7.9 1.0 190 214 260 324 350 |
Table 2 multipurpose additive is to the effect of improving of diesel fuel lubricity and color stability
| Addition/mgkg -1 | Oilness WS 1.4/um | Colour stability (colourity/number) | |||||
| Diesel oil | Additive | 0 day | 30 days | 60 days | 90 days | ||
| a a a a a a | / example 1 example 2 examples 3 examples 4 examples 5 | / 300 400 350 400 250 | 535 297 328 336 317 309 | 1.0 1.0 1.0 1.0 1.0 1.0 | 1.5 1.0 1.0 1.0 1.0 1.0 | 2.0 1.0 1.5 1.0 1.0 1.0 | 2.5 1.5 1.5 1.0 1.5 1.0 |
| b b b b b b | / example 1 example 2 examples 3 examples 4 examples 5 | / 300 400 350 400 350 | 475 244 276 303 229 256 | 1.5 1.5 1.5 1.5 1.5 1.5 | 2.0 1.5 1.5 1.5 1.5 1.5 | 2.5 1.5 1.5 2.0 1.5 1.5 | 3.0 2.0 2.0 2.0 2.0 1.5 |
By table 2 as can be seen, diesel oil multi-efficient additive provided by the invention can improve Lubricity of Low-Sulfur Diesel Fuels, can improve the colour stability of diesel oil again.
Claims (10)
1. wear preventive additive that can improve diesel colour stability is by C
6～C
40Lipid acid and C
1～C
6Aldehyde and C
2～C
20Organic amine obtains 50～200 ℃ of reactions, and the mol ratio of lipid acid, aldehyde, organic amine is 1: 0.1～10: 0.1～10, and wherein organic amine is at least a polyamines polyene, amino alcohol or alkoxy polyamine, or itself and C
3～C
20The mol ratio of aliphatic amide, Cycloalkyl amine or heterocyclic amine is 1: 0.01～10 mixture.
2. according to the described additive of claim 1, it is characterized in that the mol ratio of lipid acid, aldehyde, organic amine is 1: 0.2～5: 0.2～5.
3. according to the described additive of claim 1, it is characterized in that described lipid acid is C
8～C
36Lipid acid.
4. according to the described additive of claim 1, it is characterized in that described lipid acid is oleic acid, linolic acid, linolenic acid, dimerization oleic acid, linoleic acid dimer or ricinolic acid.
5. according to the described additive of claim 1, it is characterized in that the structural formula of polyamines polyene is H
2N[(CH
2)
nNH]
mH, n are 2～4 integer, and m is 1～5 integer.
6. according to the described additive of claim 1, it is characterized in that amino alcohol is selected from 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, thanomin, diethanolamine, or its mixture.
7. according to the described additive of claim 1, it is characterized in that alkoxy polyamine is polyamines polyene and the epoxide reaction product with 1: 0.5～10 mol ratios.
8. according to the described additive of claim 1, it is characterized in that aliphatic amide is C
6～C
20Aliphatic amide; Cycloalkyl amine is cyclopentamine, hexahydroaniline; Heterocyclic amine is morpholine, piperazine.
9. according to the described additive of claim 1, it is characterized in that polyamines polyene, amino alcohol or alkoxy polyamine and C
3～C
20The mol ratio of aliphatic amide, Cycloalkyl amine or heterocyclic amine is 1: 0.1～5.
10. according to the described additive of claim 1, it is characterized in that temperature of reaction is 70～160 ℃, 0.5～20 hour reaction times.
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|---|---|---|---|
| CNB2004100736473A CN100497555C (en) | 2004-08-31 | 2004-08-31 | Anti-wear additive capable of improving diesel colour stability |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100736473A CN100497555C (en) | 2004-08-31 | 2004-08-31 | Anti-wear additive capable of improving diesel colour stability |
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|---|---|
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| CN100497555C CN100497555C (en) | 2009-06-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031178A (en) * | 2010-12-24 | 2011-04-27 | 淄博德丰化工有限公司 | Low sulfur diesel lubricity additive and preparation method thereof |
| CN102277212A (en) * | 2011-07-22 | 2011-12-14 | 中国石油化工股份有限公司 | Diesel fuel additive |
-
2004
- 2004-08-31 CN CNB2004100736473A patent/CN100497555C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031178A (en) * | 2010-12-24 | 2011-04-27 | 淄博德丰化工有限公司 | Low sulfur diesel lubricity additive and preparation method thereof |
| CN102277212A (en) * | 2011-07-22 | 2011-12-14 | 中国石油化工股份有限公司 | Diesel fuel additive |
| CN102277212B (en) * | 2011-07-22 | 2013-08-14 | 中国石油化工股份有限公司 | Diesel fuel additive |
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| Publication number | Publication date |
|---|---|
| CN100497555C (en) | 2009-06-10 |
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