CN103146444A - Gasoline antiknock additive and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of petrochemical engineering and particularly relates to a gasoline antiknock additive and a preparation method thereof. The gasoline antiknock additive is prepared from toluene, a single alkyl substituted diphenylamine derivative and a dialky substituted diphenylamine derivative according to a certain proportion. According to the preparation method disclosed by the invention, diphenylamine and hydrocarbylation reagent are adopted to carry out reaction, and the material proportion meeting the requirement of the additive is synthesized by controlling the conditions of the reaction temperature, the molar ratio of a reactants and the like, thus greatly lowering the product cost; and substance molecules of the additive contain a conjugated system consisting of two benzene rings and a nitrogen atom, amino can be easily dissociated to produce hydrogen, and the concentration of peroxide is lowered through the reaction between free hydrogen and peroxide which is generated in the burning process of gasoline, thus improving the antiknock performance of the gasoline. The gasoline antiknock additive has the characteristics of little dosage, low cost, no side effects, high solubility in the gasoline, insolubility in water, stable property and the like.

Description

A kind of detonation suppressor and preparation method

(1) technical field under:

The invention belongs to petrochemical industry, particularly a kind of detonation suppressor and preparation method.

(2) background technology

The capability of antidetonance of gasoline is that the octane value by gasoline decides.The octane value of straight-chain paraffin is minimum; Hyperbranched isoparaffin and the octane value of aromatic hydrocarbons are the highest; The octane value of naphthenic hydrocarbon and alkene is between between them.The method that refinery improves gasoline octane rating has two kinds: a kind of is method by techniques such as catalytic reforming or alkylations; Another kind is to add octane enhancing additive.Under the present situation that China's oil refining apparatus technology consists of, adding octane promoter is to improve the comparatively cost-effective method of gasoline octane rating.

Gasoline antiknock totally can be divided into two large classes: a class is the metal octane promoter, is the compound of octane promoter (methyl cyclopentyl-dialkyl-tricarbon manganium MMT), iron-based octane promoter (ferrocene), rare earth metal as lead alkylide, manganese; Another kind of is nonmetal octane promoter, as alcohol, phenol, ether, aromatic amine, carboxylicesters and various polymkeric substance.

Just begin to make gasoline antiknock with tetraethyllead as far back as the nineteen twenty-one people, tetraethyllead can make the oxidizing reaction mitigation of hydro carbons carry out, and it can decompose at 200 ℃, and and the peroxidation that generates during hydrocarbon fuel, generation plumbous oxide precipitation stops fierce oxidizing reaction, reduces phenomenon of detonation.But the tetraethyllead environmental pollution is serious, and can make the three-way catalyst in exhaust pipe poisoning, and late nineteen eighties is forbidden very on a large scale in the world.Use again subsequently ferrocene, methyl cyclopentyl-dialkyl-tricarbon manganium, but ferrocene can increase the wearing and tearing of engine; Methyl cyclopentyl-dialkyl-tricarbon manganium can make oil nozzle stop up, and the exhaust pipe three-element catalytic is poisoning.

The most in the last few years, developing nonmetal ashless octane promoter had become focus, and methyl tertiary butyl ether is used in a large number.But methyl tertiary butyl ether is not octane promoter, just relies on self high-octane rating (RON:116) to improve the octane value of base gasoline.Therefore, its add-on is large, generally 10% one 15%, has affected some physical and chemical indexs of base oil.Simultaneously, due to methyl tertiary butyl ether have stronger water-soluble, produce and use procedure in inevitably have the part methyl tertbutyl ether and can dissolve in rainwater, or penetrate in underground water, pollute.Therefore, people have now begun to consider to abandon and forbid methyl tertiary butyl ether as gasoline dope.

Chinese patent CN1138846C uses pyromellitic dianhydride, and the many kinds of substances such as isobutylamine have prepared a kind of detonation suppressor, though can change more significantly the anti-knocking property of some gasoline, but additive component is complicated, and cost is high, and the gasoline difference of dissimilar component is larger.Chinese patent CN1389546A and CN1394940A, used the main component of methylphenylamine as detonation suppressor, but existed following point: 1. in the few gasoline component of alkene, aromaticity content, easy crystallization; 2. methylphenylamine has immersional wetting to some plastics, rubber parts; 3. the gasoline that is in harmonious proportion is unstable, easily produces colloid; 4. the toxicity of methylphenylamine is large, and is seriously polluted.

(3) summary of the invention:

The object of the invention is to overcome the deficiencies in the prior art, a kind of ashless detonation suppressor and cheap preparation method are provided, it had both had the characteristic of metal octane promoter, had overcome again simultaneously metal octane promoter (tetraethyllead, ferrocene, manganese tricarbonyl) and can make that three-way catalyst in vapor pipe is poisoning, the drawback of wearing and tearing petrol jets.

Technical scheme of the present invention is as follows: a kind of main component of detonation suppressor is: the derivative (alkyl is iso-octyl or 1 one styroyls) of the derivative of toluene, single alkyl substituted diphenylamine (alkyl is iso-octyl or 1 one styroyls), dialkyl substituted diphenylamine.Its mass percent is

The derivative 60-90% of single alkyl substituted diphenylamine

The derivative 5-20% of dialkyl substituted diphenylamine

Toluene 0-15%

A kind of detonation suppressor that satisfies said ratio need not by mixing according to a certain ratio realization with pure single replacement and the derivative of two substituted diphenylamines, adopt the reaction of pentanoic and hydrocarbylation reagent (diisobutylene, vinylbenzene), realize by controlling the substitution reaction condition, concrete steps are:

1. take a certain amount of pentanoic and join in reactor, 60 ℃ of lower heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 130 ℃～150 ℃;

3. slowly add hydrocarbylation reagent, the mol ratio of add-on and pentanoic is 1.3～1.5: 1;

4. 130 ℃～150 ℃ lower isothermal reactions, with gas chromatograph monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer less than 0.5% the time, cools to room temperature;

The viscosity of 6. looking product adds toluene, quantitative filling.

Beneficial effect of the present invention: the per-cent that 1. satisfies additive desired substance quality, need not to mix with pure single replacement and the derivative of two substituted diphenylamines, but realize by the hydrocarbyl reaction condition of controlling pentanoic, this has greatly reduced the cost of additive; 2. efficient is high, and addition can make the octane value of gasoline improve 3～5 units 0.5～1%, greatly is better than MTBE; 3. burn ashless, do not produce precipitation or residue; 4. the indexs such as the boiling range of base oil, saturated vapor pressure are had no adverse effects; 5. be soluble in gasoline, water insoluble, therefore be difficult for polluted source; 6. stable in properties, be easy to store, use.

Antiknock mechanism: gasoline is in cylinder in combustion processes, and along with the rising of cylinder temperature and gaseous tension can produce a large amount of organo-peroxides, before normal flame passed to, these superoxide can violent the decomposition and spontaneous combustion, thereby causes pinking.That is to say that unsettled superoxide is the root that gasoline produces pinking, inhibition and the superoxide of eliminating in cylinder are the keys that alleviates pinking.Contain the conjugated system that two phenyl ring and nitrogen-atoms form in the structure of the compound molecule of additive of the present invention, easily dissociate hydrogen, the free radical generation oxidizing reaction that the superoxide that free hydrogen and hydrocarbon oxidization generate and fission thereof produce, make free radical be combined to stable compound, thereby change the path of reaction, extend the inductive phase of unburned mixture spontaneous combustion, the speed limit of fuel combustion in normal combustion range.

(4) embodiment:

Following specific embodiment explanation technical scheme of the present invention, but protection of the present invention is not limited to this.

Embodiment 1:

A kind of detonation suppressor, its main component is by mass percentage:

Single di-iso-octyldiphenylamine 85-90%

Di-iso-octyldiphenylamine 10-15%

A kind of preparation method of detonation suppressor comprises the following steps:

1. the pentanoic that takes 85Kg joins in reactor, 60 ℃ of heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 130 ℃;

3. slowly add the 73Kg diisobutylene;

4. 130 ℃ of lower isothermal reactions, with gas-chromatography monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer, cool to room temperature less than 0.5% the time;

6. quantitative filling.

Embodiment 2:

A kind of detonation suppressor, its main component is by mass percentage:

Single di-iso-octyldiphenylamine 80-85%

Di-iso-octyldiphenylamine 15-20%

A kind of preparation method of detonation suppressor comprises the following steps:

1. the pentanoic that takes 85Kg joins in reactor, 60 ℃ of heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 140 ℃;

3. slowly add the 78Kg diisobutylene;

4. 140 ℃ of lower isothermal reactions, with gas-chromatography monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer, cool to room temperature less than 0.5% the time;

6. quantitative filling.

Embodiment 3:

A kind of detonation suppressor, its main component is by mass percentage:

List-1-styroyl pentanoic 85-90%

Two-1-styroyl pentanoic 10-15%

A kind of preparation method of detonation suppressor comprises the following steps:

1. the pentanoic that takes 85Kg joins in reactor, 60 ℃ of heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 130 ℃;

3. slowly add 68Kg vinylbenzene;

4. 130 ℃ of lower isothermal reactions, with gas-chromatography monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer, cool to room temperature less than 0.5% the time;

6. quantitative filling.

Embodiment 4:

A kind of detonation suppressor, its main component is by mass percentage:

List-1-styroyl pentanoic 75-85%

Two-1-styroyl pentanoic 15-20%

Toluene 10-15%

A kind of preparation method of detonation suppressor comprises the following steps:

1. the pentanoic that takes 85Kg joins in reactor, 60 ℃ of heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 145 ℃;

3. slowly add 73Kg vinylbenzene;

4. 145 ℃ of lower isothermal reactions, with gas-chromatography monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer, cool to room temperature less than 0.5% the time;

6. add 18Kg toluene to stir, quantitative filling.

Embodiment 5:

A kind of detonation suppressor, its main component is by mass percentage:

Single di-iso-octyldiphenylamine, list-1-styroyl pentanoic 75-85%

Di-iso-octyldiphenylamine, two-1-styroyl pentanoic 15-20%

Toluene 10-15%

A kind of preparation method of detonation suppressor comprises the following steps:

1. the pentanoic that takes 85Kg joins in reactor, 60 ℃ of heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 130 ℃;

3. slowly first add the 37Kg diisobutylene, then add 40Kg vinylbenzene;

4. 130 ℃ of isothermal reactions, with gas-chromatography monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer, cool to room temperature less than 0.5% the time;

6. add 20Kg toluene to stir, quantitative filling.

Claims (3)

1. a detonation suppressor and preparation method, is characterized in that, it is comprised of toluene, single alkyl substituted diphenylamine sulfonamide derivatives, dialkyl substituted diphenylamine sulfonamide derivatives, and its mass percent is:

The derivative 60-90% of single alkyl substituted diphenylamine

The derivative 5-20% of dialkyl substituted diphenylamine

Toluene 0-15%.

2. a kind of detonation suppressor and preparation method according to claim 1, is characterized in that, the step of preparation is:

1. take a certain amount of pentanoic and join in reactor, 60 ℃ of heat fused;

2. start agitator and stir, add catalyzer, be warmed up to 130 ℃～150 ℃;

3. slowly add hydrocarbylation reagent, the mol ratio of add-on and pentanoic is 1.3～1.5: 1;

4. 130 ℃～150 ℃ lower isothermal reactions, with gas chromatograph monitoring reaction process;

5. the content of analyzing pentanoic filters out catalyzer less than 0.5% the time, cools to room temperature;

The viscosity of 6. looking product adds toluene, quantitative filling.

3. according to claim 1,2 described a kind of detonation suppressor and preparation methods, it is characterized in that, the alkyl in described alkyl substituted diphenylamine sulfonamide derivatives is iso-octyl, 1-styroyl; Described hydrocarbylation reagent is diisobutylene, vinylbenzene.