CN100378207C - Preparation method of cleaning fuel additive - Google Patents
Preparation method of cleaning fuel additive Download PDFInfo
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- CN100378207C CN100378207C CNB2005100870689A CN200510087068A CN100378207C CN 100378207 C CN100378207 C CN 100378207C CN B2005100870689 A CNB2005100870689 A CN B2005100870689A CN 200510087068 A CN200510087068 A CN 200510087068A CN 100378207 C CN100378207 C CN 100378207C
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- polyethers
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- alkyl
- acetate
- polyisobutenyl
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Abstract
The present invention relates to a preparation method of detergency fuel additive. Said preparation method includes the step making polyisobutenyl succinimide and polyether acetic acid produce reaction at 20-100 deg.C to form salt. The polyisobutylene in polyisobutenyl sucinimide is the polyisobutylene whose terminal alkene content is greater than 70% and the number-average molecular weight of said polyisobutylene is 900-1300. The described polyether in polyether acetic acid is polyalkylene oxide polyether. Said invention also provides its structural formula. The additive prepared by said invention can reduce discharge of granular substances of diesel engine.
Description
Technical field
The invention belongs to fuel dope.
Background technology
The discharge of diesel engine mainly is particulate matter and oxynitride.Wherein particulate matter is the solid matter of discharging from engine, and its general size is less than 100 microns, and great majority are 10 microns or littler.From chemical aspect, these particulate matters are by the mixture of the carbon of partial oxidation and hydrocarbon materials, the sulphur that mainly exists with sulphate form and other non-volatile component for example metal, lubricating oil and the additive thereof etc. of engine scuffing.
Be used for aspect the agent of the diesel engine smoke of gunpowder a lot of trials having been arranged in searching, comprise some metallic compounds.Some of them nonmetallic compound class additive is prominent especially, and these additives mainly are the organism with certain dissemination.
WO 0042133 discloses a kind of compositions of additives of being made up of the acid amides or the ester of polyethers acetate can reduce the diesel particulate discharging.In the example formulations therein, except that containing above-mentioned additive, also contain lubricant, kilfoam, mixture and cetane number improver disappear.In the comparative example prescription, use the polyethers additive then not have the effect that reduces particulate matter.
CN1216977 discloses a kind of compositions of additives of being made up of the acid amides or the ester of polyethers acetate can reduce the intake valve settling.This piece patent and WO0042133 belong to same company, belong to same content and use in different fields.
CN1305520 discloses a kind of oil fuel with additive and fuel oil composition.This additive is made up of succimide or its boronation affixture and lubricant lipid acid, preferably also contains the third component low-temperature fluidity toughener.The combination of pointing out these three kinds of additives in the embodiment of patent has the effect that reduces diesel particulate.It is that carbon number is at least a in 4～22 unsaturated fatty acids or its dimeracid or their ester that patent spells out lubricant lipid acid.
CN1343764 discloses a kind of diesel oil multi-efficient additive.This additive is by allyl butyrate imide and phenol acids prepared in reaction.This additive has resistance of oxidation preferably, also has the detergent-dispersant performance energy, can significantly reduce the generation of oxidation sediment in the diesel oil.
EP0798364 discloses a kind of diesel-dope.With the aliphatic carboxylic acid salify or become acid amides, this additive is at 20～100 ℃ of salifies by aliphatic amide for this additive.
Summary of the invention
The invention provides a kind of preparation method that can reduce the fuel dope of diesel particulate discharging.
The preparation method of cleaning fuel additive provided by the invention comprises, makes polyisobutenyl succimide and polyethers acetic acidreaction, generates salt.
Said polyisobutenyl succimide and polyethers acetate can react under preferred 40～80 ℃ of temperature at 20～100 ℃, and the reaction times can be 0.5～4 hour, preferred 0.5～1.5 hour.The mol ratio of polyisobutenyl succimide and polyethers acetate is 1: 0.5～3, preferred 1: 0.5～1.5.
Reaction can be in or be not under the existence of organic solvent to be carried out.Said organic solvent can be polarity or non-polar organic solvent, and wherein non-polar organic solvent can be aliphatic hydrocarbon or aromatic hydrocarbons, as toluene, dimethylbenzene, BTX aromatics, petroleum solvent; Polar organic solvent can be ester class or alcohols, as carboxylicesters, isooctyl ester nitrate, hexanol, 2-Ethylhexyl Alcohol, decyl alcohol, different tridecanol or C7～C9 uncle alcohol mixture etc.
Polyisobutene in the said polyisobutenyl succimide is highly active polyisobutene, promptly holds alkene content greater than 70% polyisobutene.The number-average molecular weight of polyisobutene is 900～1300, preferred 950～1100.If the polyisobutene molecular weight is low then spatter property is relatively poor, the higher relative concentration that then reduces alkali nitrogen of molecular weight.
Said polyisobutenyl succimide prepares through the following steps: in the presence of nitrogen, polyamines polyene and polyisobutenyl succinic anhydride at 100～200 ℃, were reacted 1～8 hour, preferred 1～3 hour, decompression removes the water that reaction generates, and filters, and gets product polyisobutenyl succimide.Wherein the mol ratio of the add-on of polyisobutenyl succinic anhydride and polyamines polyene is 0.9～2: 1, preferred 1～2: 1.Said polyamines polyene is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines.
When preparation polyisobutenyl succimide, polyisobutenyl succinic anhydride can be connected on the primary amino, forms imide; Also can connect two primary aminos, form acid amides.The polyisobutenyl succimide of preparation is actual to be the mixture of an imide and acid amides.
Polyethers in the said polyethers acetate is that an end is an alkyl, and an end is the polyalkylene oxide polyethers of hydroxyl, and polyethers also can be the polyalkylene oxide polyethers that contains two hydroxyls, has following structure:
R
1-O-(CHR
2-CHR
3-O)
m-(CH
2-CH
2-O)
n-H
R wherein
1For hydrogen or carbon number are 1～30 alkyl or alkyl phenyl, preferred 4～20, more preferably 12～18.R
2And R
3Be independently selected from hydrogen or contain the replaced alkyl of 1～2 carbon atom, other R
2And R
3Be independently selected from the replaced alkyl that contains 1～2 carbon atom.M is 1～50 integer, and preferred 2～30 integer, n are 0～20 integer, preferred 0～6 integer, and condition is m＞n.
Polyethers acetate can form with chloroacetate reaction under the alkaline effect by polyethers.Said highly basic is sodium hydride, sodium hydroxide or potassium hydroxide etc.
Polyisobutene succinimide polyethers acetate of the present invention is dispersing additive, can reduce the diesel particulate discharging.
Embodiment
The invention will be further described below by example.
Embodiment 1
An Industrial products polyisobutenyl succimide (T151A, produce in Suzhou) alkali nitrogen content 1.3%, active principle 48%.Polyisobutene is a high-activity polyisobutene, its number-average molecular weight 1300.Thinning oil is the 150SN neutral mineral oil. in the time of 100 ℃, and kinematic viscosity 244mm
2/ s.
Embodiment 2
An Industrial products double focusing iso-butylene succimide (T152, produce in Suzhou) alkali nitrogen content 0.8%, active principle 25%.Polyisobutene is a high-activity polyisobutene, its number-average molecular weight 1000.Thinning oil is the 150SN neutral mineral oil.
Embodiment 3
Preparation polyisobutenyl succimide
In 1 liter of there-necked flask that agitator and thermometer be housed, add (0.227 mole of 250 gram, saponification value 86mgKOH/g, polyisobutene Mn=1000) polyisobutenyl succinic anhydride and 250 gram aromatic solvents, behind the nitrogen purging air, be warmed up to 130 ℃, drip 38.6 gram (0.204 mole) tetraethylene pentamine, be warmed up to 170 ℃ again, keep nitrogen flushing simultaneously in 2.5 hours, remove the water of generation, cool to 110 ℃, add 5 gram diatomite, stir the back filtered while hot, get the polyisobutenyl succimide, concentration is 44m%.
Embodiment 4
Preparation polyethers acetate
In being installed, 1000 ml flasks that mechanical stirrer and nitrogen drying cross add 100 milliliters of sodium hydride (21 grams, 0.44 mole, 50% oil suspension) and tetrahydrofuran (THF)s.In about 3 hour time, in stirring the mixture, gained adds polyethers (12 poly alkyl alcohol propylene oxide, its molecular weight 1200 gradually; 264 grams, 0.22 mole) tetrahydrofuran (THF) (250 milliliters) solution, mixture reflux 3 hours under agitation condition is cooled to 40～50 ℃ then, adds Mono Chloro Acetic Acid (23.76 grams, 0.22 mole) tetrahydrofuran (THF) (20 milliliters) solution in about 2 hours.Then, mixture reflux 3 hours under agitation condition is cooled to envrionment temperature (20 ℃), uses hydrochloric acid (2N, the aqueous solution) acidifying again, up to solution becomes acidity.Utilize ether (300 milliliters three times) extraction organism, the organic phase that water (300 milliliters three times) washing merges.The organic phase anhydrous magnesium sulfate drying filters and evaporation obtains 279 gram products.Be light yellow oil.
Embodiment 5
Preparation polyethers acetate
In 1000 ml flasks that mechanical stirrer and nitrogen drying cross are installed, add polyethers (m=19, n=5) (137 grams, 0.09mol), (3.6 restrain water 0.1mol) (20ml) solution for toluene (250ml) and sodium hydroxide.Mixture heating up arrives reflux temperature, and all water in reaction mixture are separated by water separator, and (10.4 grams, 0.09mol), mixture heating up arrives reflux temperature 14 hours to cooling mixture to enough allowing to add the Mono Chloro Acetic Acid sodium salt.Cooling mixture utilizes hydrochloric acid (the 2N aqueous solution) acidifying, separates phase.Utilize saturated sodium-chloride water solution (50 milliliters of secondaries) washing organic phase, organic phase is used anhydrous magnesium sulfate drying, filters evaporating solvent and gets 140 gram products, is light yellow oil.
Embodiment 6
Remove and use polyethers (nonyl phenol poly(propylene oxide), its molecular weight 1500; 330 grams, 0.22 mole) change outside, all the other are with embodiment 4.
Embodiment 7
Remove and use polyethers (poly(propylene oxide), its molecular weight 1000; 220 grams, 0.22 mole) change outside, all the other are with embodiment 4.
Embodiment 8
Under the molar conditions such as polyethers acetate among succimide among the embodiment 1 and the embodiment 4, add 30% xylene solvent, 50 ℃ of Heating temperatures, heat 1 hour must product.
Embodiment 9
Polyethers acetate among succimide among the embodiment 1 and the embodiment 7 is waiting under the molar conditions, adds 30% xylene solvent, 50 ℃ of Heating temperatures, heat 1 hour must product.
Embodiment 10
Polyethers acetate among succimide among the embodiment 2 and the embodiment 6 adds 30% heavy aromatic solvent under the condition of aromatic hydrocarbons solution, 50 ℃ of Heating temperatures, heat 1 hour must product.
Embodiment 11
Polyethers acetate among succimide among the embodiment 3 and the embodiment 5 is waiting under the molar conditions, 50 ℃ of Heating temperatures, heat 1 hour product.
Comparative Examples 1
Prepare acid amides by patent WO0042133 disclosed method by polyethers acetate.Polyethers acetate and triethylene tetramine reacted in benzole soln 8 hours, remove to anhydrate, through super-dry, distill product.
Embodiment 13
This example explanation additive of the present invention is to the influence of diesel emission smoke intensity.
The additive that adds embodiment and Comparative Examples preparation in No. 0 commercially available diesel oil uses Huanghai Sea board motor bus to test, by about 4000 kilometers test run.Measure the exhaust emissions smoke intensity before and after the test.Press the GB/T3846 method and measure the motor vehicle exhaust smoke intensity, measurement result sees Table 1.
Table 1
| Sequence number | Additive | Additive dosage, ppm | Smoke intensity change value before and after the test, % |
| 1 | Do not have | ?-3.5 | |
| ?2 | Example 1 | ?500 | ?15 |
| ?4 | Example 4 | ?500 | ?11 |
| ?5 | Example 8 | ?500 | ?25 |
| ?6 | Example 11 | ?500 | ?23 |
| ?7 | Comparative Examples 1 | ?500 | ?20 |
As can be seen from Table 1, the salt pair diesel emission smoke intensity of succimide and polyethers acetate formation has clear improvement.
Claims (11)
1. the preparation method of a cleaning fuel additive comprises, in the presence of organic solvent, makes polyisobutenyl succimide and polyethers acetate 20～100 ℃ of reactions down, generates salt.
2. according to the described preparation method of claim 1, it is characterized in that temperature of reaction is 40～80 ℃.
3. according to the described preparation method of claim 1, it is characterized in that the mol ratio of polyisobutenyl succimide and polyethers acetate is 1: 0.5～3.
4. according to the described preparation method of claim 3, it is characterized in that the mol ratio of polyisobutenyl succimide and polyethers acetate is 1: 0.5～1.5.
5. according to the described preparation method of claim 1, it is characterized in that said organic solvent is aliphatic hydrocarbon, aromatic hydrocarbons, ester class or alcohols.
6. according to the described preparation method of claim 5, it is characterized in that said organic solvent is toluene, dimethylbenzene, BTX aromatics, petroleum solvent, carboxylicesters, isooctyl ester nitrate, hexanol, 2-Ethylhexyl Alcohol, decyl alcohol, different tridecanol or C7～C9 mixing primary alconol.
7. according to the described preparation method of claim 1, it is characterized in that, the polyisobutene in the said polyisobutenyl succimide for end alkene content greater than 70% polyisobutene, the number-average molecular weight of polyisobutene is 900～1300.
8. according to the described preparation method of claim 1, it is characterized in that, said polyisobutenyl succimide is formed by polyamines polyene and polyisobutenyl succinic anhydride reaction, and said polyamines polyene is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines.
9. according to the described preparation method of claim 1, it is characterized in that the polyethers in the said polyethers acetate is the polyalkylene oxide polyethers, has following structure: R
1-O-(CHR
2-CHR
3-O)
m-(CH
2-CH
2-O)
n-H, wherein R
1Be the alkyl or the alkyl phenyl of hydrogen or carbon number 1～30, R
2And R
3Be hydrogen or the alkyl that contains 1～2 carbon atom, R
2And R
3Be selected from the alkyl that contains 1～2 carbon atom, m is 1～50 integer, and n is 0～20 integer, m＞n.
10. according to the described preparation method of claim 9, it is characterized in that R
1Alkyl or alkyl phenyl for carbon number 4～20; M is 2～30 integer, and n is 0～6 integer.
11., it is characterized in that R according to the described preparation method of claim 10
1Alkyl or alkyl phenyl for carbon number 12～18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100870689A CN100378207C (en) | 2005-07-26 | 2005-07-26 | Preparation method of cleaning fuel additive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100870689A CN100378207C (en) | 2005-07-26 | 2005-07-26 | Preparation method of cleaning fuel additive |
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| Publication Number | Publication Date |
|---|---|
| CN1904000A CN1904000A (en) | 2007-01-31 |
| CN100378207C true CN100378207C (en) | 2008-04-02 |
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ID=37673367
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|---|---|---|---|
| CNB2005100870689A Active CN100378207C (en) | 2005-07-26 | 2005-07-26 | Preparation method of cleaning fuel additive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2481278A (en) * | 2010-06-14 | 2011-12-21 | Afton Chemical Corp | Diesel fuel additive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000042133A1 (en) * | 1999-01-15 | 2000-07-20 | Infineum International Ltd | Improved fuel compositions |
| CN1343764A (en) * | 2000-09-15 | 2002-04-10 | 中国石油化工股份有限公司 | Multi-effect additive for diesel oil |
-
2005
- 2005-07-26 CN CNB2005100870689A patent/CN100378207C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000042133A1 (en) * | 1999-01-15 | 2000-07-20 | Infineum International Ltd | Improved fuel compositions |
| CN1343764A (en) * | 2000-09-15 | 2002-04-10 | 中国石油化工股份有限公司 | Multi-effect additive for diesel oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2481278A (en) * | 2010-06-14 | 2011-12-21 | Afton Chemical Corp | Diesel fuel additive |
| GB2481278B (en) * | 2010-06-14 | 2012-05-30 | Afton Chemical Corp | Diesel fuel additive |
| US8475541B2 (en) | 2010-06-14 | 2013-07-02 | Afton Chemical Corporation | Diesel fuel additive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1904000A (en) | 2007-01-31 |
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