CN1227866A - High-clean gasoline additive and its preparing process and application - Google Patents
High-clean gasoline additive and its preparing process and application Download PDFInfo
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Abstract
A high-cleanness additive for gasoline, especially for the gasoline on domestic market, whose principal component is catalytic cracked one, and which is prepared from disperser, polymerization inhibitor, light stabilizer, demulsifier, antirusting agent,cosolvent and base liquid, and serves to greatly reduce the generation of oil mud and carbon deposit, remove generated deposit, save fuel, improve the power performance of engine and decrease the harmful substances in tail gas.
Description
The present invention relates to gasoline dope, specifically relating to the catalytic cracking component is high-clean gasoline additive that gasoline was suitable for of main body composition and preparation method thereof.
With the catalytic cracking component is in the gasoline of main body composition, the olefin(e) centent height, at high temperature generate greasy filth and carbon deposit because of oxidation, polymerization easily, these settlings are carburettor, EFI mouth and the intake valve that causes motor car engine, the major reason of combustion chamber coking and blocking, can cause that thus engine oil is not smooth, incomplete combustion, not only waste fuel, and influence engine power performance, make the engine cisco unity malfunction, cause that objectionable impurities is that carbon monoxide, hydrocarbon polymer and content of nitrogen oxide increase significantly in the motor vehicle emission tail gas.
As everyone knows, developing of automobile industry is that development and national economy and the life that improves the people have brought very big benefit.The vehicle guaranteeding organic quantity of China is about 2,500 ten thousand, and wherein automobile is about 1,300 ten thousand, and annual speed increase about with 15～20%.Owing to reasons such as the basic industry technical equipment fall behind, the state of the art of automobile is low, China's bicycle pollutant discharge amount is several times even tens times of developed country, and the pollutant discharge amount of domestically-made vehicle is to five times of developed country.
21st century is environmental protection century, and discharge of harmful gases is a new problem that urgency is to be solved in the reduction vehicle exhaust.Principal pollutant in the exhaust emissions are hydrocarbon polymer, carbon monoxide and nitrogen oxide.Hydrocarbon polymer is to generate ozone easily in the sun and form photo-chemical smog with nitrogen oxide after hydrocarbon compound enters atmosphere, the ozone in high-altitude can cover ultraviolet ray, favourable to human body, the ozone in low latitude then can insulting respiratory system, also can influence the growth of farm crop.Carbon monoxide enters blood of human body and combines with oxyphorase, can reduce the blood transport function, causes when serious poisoning even the causing death.Nitrogen oxide not only influences human respiratory, causes the generation of trachitis, pneumonia and pulmonary disorder, also is the main component that generates acid rain.
Studies have shown that, the electronics direct injection fuel, the air/fuel ratio that computerizeds control can improve the specific power of engine, reduces fuel consumption, makes engine combustion complete, reduces exhaust pollution.The automobile major part of developed country all adopts this method to improve the performance of motor car engine, but must use the white gasoline that has been added with high-clean gasoline additive simultaneously, this is because under directly spray situation of electronics, chamber temperature raises, gasoline generates carbon deposit easily in nozzle, intake valve even combustion chamber, use the gasoline that is added with high-clean gasoline additive then can prevent the generation of carbon deposit.The gasoline of China is formed to compare with external gasoline very big difference, and most importantly catalytic cracking component proportion height be about 70～80%, and the catalytic cracking component has only 35.5% and 27% respectively in the gasoline in the U.S. and West Europe, each component relatively see Table 1.
The main composition of catalytic cracking component is an alkene, and gasoline very easily oxidation, the polymerization at high temperature that olefin(e) centent is high generates weakly acidic greasy filth and carbon deposit, so the problem of the gasoline of China generation greasy filth and carbon deposit is much more serious than external gasoline.This will cause engine oil path to stop up, the imbalance of air/fuel ratio, and incomplete combustion, engine power descends, and causes discharging obnoxious flavour amount increase in the tail gas.Adding high-clean gasoline additive in gasoline is one of effective way that addresses this problem.Therefore the United States Federal is made in the regulation that adds high-clean gasoline additive in the gasoline in nineteen ninety-five, and the content of restriction alkene is below 5～10% in reformulated gasoline, and states such as Europe, Japan also use in a large number.
Table 1 China, the U.S. and West Europe gasoline are formed %
| Gasoline component | The main composition | China | The U.S. 1993 | West Europe 1991 | |
| Nineteen ninety-five | 2000 | ||||
| The catalytic cracking component | Alkene | ?????73.1 | ????78.1 | ????35.5 | ????27 |
| The catalytic reforming component | Aromatic hydrocarbons | ?????6.5 | ????15.1 | ????33 | ????47 |
| The alkylation component | Isoparaffin | ?????0.2 | ????3.5 | ????12 | ?????4 |
| Iso-component | Isoparaffin | ?????- | ?????- | ????10 | ?????5 |
| The etherificate component | Contain oxygen ether | ?????- | ????3.3 | ????1.5 | ?????- |
| The straight run component | Alkane | ????16.1 | ?????- | ?????- | ?????8 |
| The coking component | Alkane | ?????1 | ?????- | ?????- | ?????- |
| The thermally splitting component | Alkane | ?????- | ?????- | ?????- | ?????- |
| The hydrocracking component | ??????- | ?????1 | ?????- | ?????2 | ?????- |
| Aromatic hydrocarbons | Aromatic hydrocarbons | ????0.6 | ?????- | ?????- | ?????- |
| Butane | Alkane | ?????- | ?????- | ?????6 | ?????6 |
| Other | ??????- | ????1.5 | ?????- | ?????- | ?????3 |
| Add up to | ????100 | ????100 | ????100 | ????100 | |
The high-clean gasoline additive that adds in the gasoline is a kind of tensio-active agent, it not only has the effect of cleaner engines oil piping system, and can be with the particles dispersed that washes down, take away burning by gasoline, thereby recover the normal fuel injection function of engine, improve the state of combustion of engine, reduce the exhaust emission that increases owing to incomplete combustion.The gasoline that is added with high-clean gasoline additive is used for that very strong cleaning carbon deposit effect is being arranged with car, and has more clean-keeping function when using in new car.
High-clean gasoline additive widespread use abroad at present, but it is as shown in table 1, because olefin(e) centent is very high in the gasoline of China, bigger difference is arranged with external gasoline forming, so that the gasolene cleaner of import is used for its effect of gasoline of China is not satisfactory; Chinese patent application Appl.No 94117669x, a kind of composition of gasoline composite additive is disclosed, used a kind of low-molecular-weight PIBA as dispersion agent, this additive has good dispersiveness and spatter property in the lower temperature region of carburettor and nozzle, but temperature is risen in about 240～250 ℃ intake valve, this low-molecular-weight dispersion agent then difficulty work.
Main purpose of the present invention provides a kind of high-clean gasoline additive, especially is applicable to the catalytic cracking component to be the composition of the high-clean gasoline additive of main body composition.
It is the preparation method of the high-clean gasoline additive of main body composition that another object of the present invention provides a kind of being applicable to the catalytic cracking component.
The present invention also aims to provide the application of this high-clean gasoline additive.
High-efficiency gasoline sanitising agent of the present invention is grouped into by following one-tenth: (weight %)
A, compound detergent-dispersant additive 8～40%
B, stopper 0.5～4%
C, photostabilizer 0.2～3%
D, emulsion splitter 0.3～3%
E, rust-preventive agent 0.5～3%
F, solubility promoter 2～10%
G, basal liquid surplus
Above-mentioned A, B, C, D, E, F, G component sum are 100%, wherein,
Compound detergent-dispersant additive is the mixture of the polyisobutene succinimide (I) of two kinds of different molecular weights:
In the last formula I, R is the polyisobutylene group of molecular weight 1100～1300, and R ' is the polyisobutylene group of molecular weight 1800～2200, and the ratio of two kinds of PIBA is 8～2: 2～8;
Stopper is the mixture of the 3-tertiary butyl-p-Methoxyphenol (II) and tert-butyl catechol (III), and the blending ratio of two kinds of compounds is 10～5: 1～5;
Photostabilizer is a kind of in two water oxygen acid esters (V) of 2-hydroxyl-4-methoxy benzophenone (IV), dihydroxyphenyl propane or the bis sebacate (VI);
Emulsion splitter is the block copolymer (VII) of Soxylat A 25-7 and polyethenoxy ether:
The composition of a item component is less than 15% of multipolymer total amount in this multipolymer, and the composition sum of b item and c item component is 20～90% of a multipolymer total amount, and surplus is water (this raw material is the commercial goods);
Rust-preventive agent is benzotriazole (VIII),
R is C
8～C
20Alkane:
Solubility promoter is Virahol (IX)
Basal liquid is the mixed solution of aviation kerosene and heavy aromatics, and ratio is 8～5: 2-5.
The used detergent-dispersant additive of the present invention is the compound ashless dispersant that the rare succimide of poly-isobutyl by two kinds of different molecular weights mixes, its effect is that the oil-soluble group by the basic group of macromole one end and the other end is dissolved in the gasoline carbon deposit, reaches the purpose of peptization, solubilising and cleaning.Owing to clean the position difference, so temperature is also different, about 60 ℃ of the temperature of carburettor, the about 100-135 of nozzle temperature ℃, the about 240-250 of the temperature of intake valve ℃, reach the cleaning of whole process, just require additive that good dispersiveness and detergency are all arranged under different temperature, the present invention has selected for use the rare succinic diamide of poly-isobutyl of two kinds of different molecular weights to make mixed dispersant, to realize from low temperature to the pyritous cleaning action.The preferred proportion of above-mentioned dispersion agent is 14～27% (weight) of sanitising agent total amount.
Stopper of the present invention adopts the mixture of phenylmethylether compounds and tert-butyl o benzene xylenol compounds, and mainly acting on is to prevent olefinic polymerization and oxidation in the gasoline and generate slightly acidic greasy filth and carbon deposit under higher temperature.The preferred proportion of stopper is 0.5～2.5% (weight) of additive total amount.
Additive of the present invention has added photostabilizer in forming, because alkene can produce high-octane free radical under the high-temp combustion condition, it is to cause further polymerization, produce the major reason of carbon deposit, it also is the prerequisite that the reaction of airborne oxygen and nitrogen generates nitrogen oxide, the introducing of photostabilizer can absorb high-octane free radical, thereby prevents the generation of coking and minimizing and inhibited oxidation nitrogen under the high temperature.The preferred proportion of photostabilizer is the 0.3-1% (weight) of additive total amount.
The major function of emulsion splitter is to prevent gasoline and emulsifying water, brings water into combustion chamber and influences the combustion function of gasoline.The use of rust-preventive agent is for preventing that oil piping system from producing corrosion.Solubility promoter is a Virahol, is a kind of carrier oil, in order to guarantee the solvability of A～E component, makes it to form the solution of homogeneous, and in the multipolymer of use (VII), the composition sum of b item and c item component is 20～90% of a multipolymer total amount, preferably 50%.
High-clean gasoline additive of the present invention adopts heavy aromatics and aviation kerosene as basal liquid.These two kinds of composite basal liquids and other solvent phase ratio, greasy filth and coking there is better solubility property, and in the additive adding gasoline with high density, can not produce dissolving and expansion to the sebific duct in the pneumatic thickener kit, plastic component, purifier and oil pump, and can not produce secondary pollution behind the gasoline combustion.
The preparation method of high-clean gasoline additive of the present invention takes by weighing and makes earlier each component on request, under 35～50 ℃, be dissolved in dispersion agent in the basal liquid in advance then, stopper, photostabilizer, emulsion splitter and rust-preventive agent are dissolved in the solubility promoter, again with above-mentioned the two merging of having dissolved in each component, stir under the normal pressure, remove mechanical impurity in the feed liquid through ultrafiltration, the brown liquid that obtains is high-clean gasoline additive product of the present invention.
High-clean gasoline additive of the present invention can obtain high-clean gasoline in the interpolation concentration adding gasoline with 300～1000ppm when using, the detergency of this high-clean gasoline, the poly-property of resistance and sewage all are better than regular gasoline.
The most creative characteristics of the present invention are exactly at olefin(e) centent height in the gasoline of China, very easily oxidation and polymeric singularity under the high temperature, stopper and photostabilizer in the prescription of additive, have been used, and used the compound dispersion agent of two kinds of different molecular weights, this additive joins in the above-mentioned gasoline, form high-clean gasoline, test-results proves, not only can reduce greasy filth significantly, the generation of carbon deposit, the settling that has generated also capable of washing, reach fuel economy, effectively improve the dynamic performance of motor car engine, reduce the purpose of the harmful substance contents that produces owing to incomplete combustion in the exhaust emissions.
The used various raw materials of the present invention are the Chemicals that can buy, maybe can obtain by prior art for preparing.Additive product preparation method of the present invention is simple, easy to use, and effect is remarkable.
High-clean gasoline additive of the present invention is widely used in commodity doped fuel and white gasoline, also can be applicable to ordinary diesel oil.
In a word, the bright high-clean gasoline additive that provides of we can be described as that present Domestic Automotive Industry implementing with necessary product in the cross-centennial technology innovation that fuel oil directly sprays, an electrical ignition element type automobile is eliminated the carburetor type automobile that falls behind.
The physical and chemical index of high-clean gasoline additive of the present invention sees Table 2.
Table 2
| Project | Physical and chemical index | Test method |
| Outward appearance | Brown liquid | Range estimation |
| Density, 20 ℃ of g/cm 3 | ????0.77～0.85 | ????GB/T?1881 |
| 50 ℃ of copper strip tests, 3h | Qualified | ????GB/T?5096 |
| Nitrogen content % | ????≥0.2 | Coulometry |
| Flash-point (remaining silent) ℃ | ????≥28 | ????GB/T?261 |
Embodiment 1
Prepare 100 kilograms of high-clean gasoline additive products, the amount of taking of various raw materials is as follows:
A, dispersion agent: 14 kilograms
(wherein molecular weight 1100～1300 and 1800～2200 polyisobutene succinimide are each 7 kilograms)
B, stopper: 0.5 kilogram of the 3-tertiary butyl-p-Methoxyphenol (II)
0.5 kilogram of tert-butyl catechol (III)
C, photostabilizer: 0.5 kilogram of 2-hydroxyl-4-methoxy benzophenone (IV)
D, emulsion splitter: 0.5 kilogram
E, rust-preventive agent: 1.2 kilograms
F, solubility promoter: 6 kilograms
G, basal liquid: (aviation kerosene wherein: heavy aromatics=1: 1) 76.8 kilograms
Under 35～50 ℃ of conditions, to dissolve in the basal liquid after two kinds of polyisobutene succinimides mixing, the 3-tertiary butyl-p-Methoxyphenol, tert-butyl catechol, 2-hydroxyl-4-methoxy benzophenone, emulsion splitter and rust-preventive agent are dissolved in the solubility promoter, the two merging, stir under the normal pressure, remove mechanical impurity in the feed liquid through ultrafiltration, the brown liquid that obtains is high-clean gasoline additive product of the present invention.
Embodiment 2
Prepare 100 kilograms of high-clean gasoline additive products, the amount of taking of various raw materials is as follows:
A, dispersion agent: 20 kilograms
(molecular weight 1100～1300 and 1800～2200 polyisobutene succinimide are respectively 8 and 12 kilograms)
B, stopper: 0.7 kilogram of the 3-tertiary butyl-p-Methoxyphenol (II)
0.3 kilogram of tert-butyl catechol (III)
C, photostabilizer: 0.5 kilogram of the two water oxygen acid esters (V) of dihydroxyphenyl propane
D, emulsion splitter: 0.8 kilogram
E, rust-preventive agent: 1.5 kilograms
F, solubility promoter: 8 kilograms
G, basal liquid: (aviation kerosene: heavy aromatics=1: 1) 68.2 kilograms
The preparation method is with embodiment 1.
Embodiment 3
Prepare 100 kilograms of high-clean gasoline additive products, the amount of taking of various raw materials is as follows:
A, dispersion agent: 25 kilograms
(molecular weight 1100～1300 and 1800～2200 polyisobutene succinimide are respectively 7.5 and 17.5 kilograms)
B, stopper: 0.8 kilogram of the 3-tertiary butyl-p-Methoxyphenol (II)
0.4 kilogram of tert-butyl catechol (III)
C, photostabilizer: 0.5 kilogram of bis sebacate (VI)
D, emulsion splitter: 1.0 kilograms
E, rust-preventive agent: 2.0 kilograms
F, solubility promoter: 10 kilograms
G, basal liquid: (aviation kerosene: heavy aromatics=1: 1) 60.3 kilograms
The preparation method is with embodiment 1.
Effect test 1
The high-clean gasoline additive of formulated among the embodiment 1 is pressed in No. 93 white gasolinees of 1000ppm adding, 58455 kilometers Santana one carburettor car uses for travelling, drive a vehicle 2764 kilometers, under the idling condition, measure the change value of carbon monoxide (CO) and hydrocarbon polymer (HC) in the discharging tail gas, the results are shown in Table 3.
Table 3
| The CO quantity discharged is measured ppm in the tail gas | The HC quantity discharged is measured ppm in the tail gas | |||
| High idle speed | Low idling | High idle speed | Low idling | |
| Travel 58455 kilometers, do not added sanitising agent | ????7.30 | ??9.50 | ????292 | ????741 |
| Drive a vehicle 2764 kilometers after adding sanitising agent | ????5.95 | ??7.30 | ????255 | ????383 |
| The reduction of nuisance (%) in the tail gas | ???18.49 | ??23.18 | ????12.7 | ????48.3 |
Effect test 2
The high-clean gasoline additive of formulated among the embodiment 3 is pressed in No. 93 white gasolinees of 8000ppm adding, 61219 kilometers Santana one carburettor car uses for travelling, drive a vehicle 993 kilometers, under the idling condition, measure the change value of carbon monoxide (CO) and hydrocarbon polymer (HC) in the discharging tail gas, the results are shown in Table 4.
Table 4
| The CO quantity discharged is measured ppm in the tail gas | The HC quantity discharged is measured ppm in the tail gas | |||
| High idle speed | Low idling | High idle speed | Low idling | |
| Travel 61219 kilometers, do not added sanitising agent | ?????5.95 | ???7.30 | ????255 | ????383 |
| Drive a vehicle 993 kilometers after adding sanitising agent | ?????2.00 | ???0.85 | ????205 | ????129 |
| The reduction of nuisance (%) in the tail gas | ?????66.4 | ???88.4 | ????19.61 | ????66.3 |
Above test-results can illustrate, use has added the gasoline of high-clean gasoline additive, can make nuisance content minimizing in the motor vehicle emission tail gas, automobile recovers good operating mode, also has oil-saving effect simultaneously, through above-mentioned test is measured with car, not adding the preceding oil consumption of high-clean gasoline additive is 9.96 liters/hundred kilometers, and driving is 3757 kilometers behind the adding high-clean gasoline additive, 320 liters of oil consumptions, oil consumption is 8.52 liters/hundred kilometers, fuel-economizing 14.5%.
Claims (7)
1, a kind of high-clean gasoline additive, it is characterized in that this additive is grouped into by following one-tenth: (weight %) A, compound detergent-dispersant additive 8～40%B, stopper 0.5～4%C, photostabilizer 0.2～3%D, emulsion splitter 0.3～3%E, rust-preventive agent 0.5～3%F, solubility promoter 2～10%G, the above-mentioned A of basal liquid surplus, B, C, D, E, F, G component sum is 100%, wherein, compound detergent-dispersant additive is the mixture of the polyisobutene succinimide (I) of two kinds of different molecular weights:
In the last formula I, R is the polyisobutylene group of molecular weight 1100～1300, and R ' is the polyisobutylene group of molecular weight 1800～2200, and the ratio of two kinds of PIBA is 8～2: 2～8
Stopper is the mixture of the 3-tertiary butyl-p-Methoxyphenol (II) and tert-butyl catechol (III), and the blending ratio of two kinds of compounds is 10～5: 1～5;
Photostabilizer is a kind of in two water oxygen acid esters (V) of 2-hydroxyl-4-methoxy benzophenone (IV), dihydroxyphenyl propane or the bis sebacate (VI);
Emulsion splitter is the block copolymer (VII) of Soxylat A 25-7 and polyethenoxy ether:
The composition of a item component is less than 15% of multipolymer total amount in this multipolymer, and the composition sum of b item and c item component is 20～90% of a multipolymer total amount, and surplus is a water;
Rust-preventive agent is benzotriazole (VIII),
R is C
8～C
20Alkane; Solubility promoter is Virahol (IX)
Basal liquid is the mixed solution of aviation kerosene and heavy aromatics, and ratio is 8～5: 2～5.
2, high-clean gasoline additive according to claim 1 is characterised in that, the additional proportion of compound detergent-dispersant additive is 14～27% (weight) of additive total amount.
3, high-clean gasoline additive according to claim 1 is characterised in that, the additional proportion of stopper is 0.5～2.5% (weight) of additive total amount.
4, high-clean gasoline additive according to claim 1 is characterised in that, the additional proportion of photostabilizer is 0.3～1% (weight) of additive total amount.
5, a kind of preparation method of high-clean gasoline additive as claimed in claim 1, be characterised in that, earlier take by weighing and make each component on request, under 35～50 ℃, be dissolved in dispersion agent in the basal liquid in advance then, stopper, photostabilizer, emulsion splitter and rust-preventive agent are dissolved in the solubility promoter, with above-mentioned basal liquid and the two merging of solubility promoter that is dissolved with each component, stir under the normal pressure again, remove mechanical impurity in the feed liquid through ultrafiltration.
6, a kind of application of high-clean gasoline additive as claimed in claim 1 is characterised in that, this additive can be added on and make high-clean gasoline in the gasoline.
7, the application of high-clean gasoline additive according to claim 6 is characterised in that, this additive in gasoline interpolation concentration be 300～1000ppm.
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| CN98100880A CN1054626C (en) | 1998-03-04 | 1998-03-04 | High-clean gasoline additive and its preparing process and application |
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|---|---|---|---|
| CN98100880A CN1054626C (en) | 1998-03-04 | 1998-03-04 | High-clean gasoline additive and its preparing process and application |
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| CN1054626C CN1054626C (en) | 2000-07-19 |
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| CN1035115C (en) * | 1994-11-01 | 1997-06-11 | 中国石化销售公司 | Compound additive for gasoline |
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