CN103740419B

CN103740419B - A kind of ashless organic anti-knock agent

Info

Publication number: CN103740419B
Application number: CN201310710181.2A
Authority: CN
Inventors: 申志明; 常永龙; 李翔; 吴跃曲; 郭芬
Original assignee: SHANXI HUADUN INDUSTRY Co Ltd
Current assignee: SHANXI HUADUN INDUSTRY Co Ltd
Priority date: 2013-12-22
Filing date: 2013-12-22
Publication date: 2015-09-30
Anticipated expiration: 2033-12-22
Also published as: CN103740419A

Abstract

The invention discloses a kind of ashless organic anti-knock agent, be a kind ofly allocated ether, the combined compound octane promoter of phenol made by propylene glycol monobutyl ether and 2-methylphenol, wherein the add-on of 2-methylphenol meets in often liter of propylene glycol monobutyl ether and adds 0.1kg 2-methylphenol.Knock test result shows, adds the ashless organic anti-knock agent of 0.1% ~ 0.5% the present invention in the oil, can significantly improve the octane value of gasoline, and the capability of antidetonance strengthens, and seldom can improve the additive use of its gasoline octane rating as a kind of novel consumption.

Description

A kind of ashless organic anti-knock agent

Technical field

The present invention relates to a kind of fuel gasoline additive, particularly relate to a kind of gasoline antiknock.

Background technology

The anti-knocking property of gasoline are the important indicators of quality of gasoline, and it is evaluated with octane value, and octane value is higher, and better, automobile compression ratio just can improve the anti-knocking property of gasoline, and then energy-conservation.The knocking combustion of gasoline is very harmful to engine, the infringement of each device of meeting boost engine, makes the increase of its power drop, combustion-chamber deposit, deterioration of emission.

It is adjustment gasoline component that the method for raising gasoline octane rating mainly contains two kinds: one, reduces straight run and thermally splitting component ratio, improves cracking, reformation alkylation components.This approach relates to the improvement of refining process, complex process, invest huge; Two is add octane promoter, and this improves the effective and the most most economical method of motor spirit anti-knocking property, is widely adopted.

Alkyl lead-type octane promoter is efficient, but meets with because of environmental pollution eliminating.Manganese metal, iron class octane promoter, due to metal quantitative limitation in gasoline, use and also will be limited.Representative non-metal kind octane promoter MTBE is now widely used in gasoline upgradnig field, but relative to traditional metallic anti-knock agent, exist consumption large, to problems such as different gasoline sensitivity difference are large.In addition, MTBE is not easy degraded, easily to environment.Due to pollution problem, the U.S. forbids MTBE.Therefore exploitation is efficient, and oligosaprobic ashless octane promoter remains the problem needing solution badly.

Produce Particulate Pollution due to metal species octane promoter and to problems such as ternary catalyzing unit infringements, be in its research the stage of a relative standstill.The research emphasis of various countries to octane promoter has been placed on non-metal kind octane promoter, mainly comprises ether, alcohol, ester class etc.

A, ethers.Ethers octane promoter with methyl tertiary butyl ether (MTBE), Ethyl Tertisry Butyl Ether (ETBE), tert amyl methyl ether(TAME) (TAME), Di Iso Propyl Ether (DIPE) for representative, such material has higher octane because of himself, is admixed to the octane value that can be improved oil product in oil product by blending effect.In ethers octane promoter, what once replaced tetraethyllead and MMT to be used widely is methyl tertiary butyl ether, 1979 by Italy first industrialization synthesized MTBE.Because MTBE and gasoline can dissolve each other and layering does not occur by arbitrary proportion, good blending effect is had with gasoline component, blending octane value, higher than its clear octane number, can reduce the discharge of the objectionable impuritiess such as carbon monoxide, is able to generally use in the whole world between subsequently more than 20 year.

In the later stage nineties 20th century, first the U.S. found MTBE in the underground water of California.Research shows, MTBE easily infiltrate soil and with the mode diffuse pollution water body of radiation and be difficult to degraded.In addition, MTBE has hormesis to human body mucous membrane and respiratory tract, also has injury effect to kidney and liver.Within 2002, California, USA forbids fusion MTBE in the oil, within 2010, forbids MTBE comprehensively.ETBE and MTBE compares, except oxygen level is slightly low, have blending octane value high, easily mix with gasoline, the advantage such as boiling point is high, can lower gasoline volatility, environmental pollution is little.ETBE not yet find at present similar MTBE environmental protection and to problems such as human injuries, and large by the change the line of production possibility of ETBE of MTBE, the market application potential of ETBE is larger.The TAME having a similar quality with ETBE both can improve the octane value of gasoline, also efficiently utilize C5 alkene simultaneously, TAME can reduce the pollution to air such as photo-chemical smog, and vapour pressure, the benzene content of restriction gasoline, also will progressively limit aromatic hydrocarbons and olefin(e) centent.But China's TAME synthetic technology is in the industrial implementation stage.DIPE and MTBE compares has many advantages, although its octane value (105) is slightly lower than MTBE, the Reid Vapour Pressure of DIPE is only the half of MTBE.The market potential of ETBE, TAME and DIPE is very large, all will become the substitute of MTBE.

B, alcohols.Since 21 century, the research and development of new type gasoline octane promoter are very active.USS alcohol company has developed a kind of biological degradation water soluble cleaning fuel dope, and it is straight chain C 1-C8 fuel-grade alcohol mixture, and octane value 128 can replace MTBE to be used for gasoline octane rating improving agent.Alcohols additive starting material are extensive, have larger market potential.At present existing several low-carbon alcohol, as methyl alcohol, ethanol and the trimethyl carbinol use as gasoline octane rating improving agent, in these three kinds of gasoline improving agents, methyl alcohol and the trimethyl carbinol self have very large toxicity, limit their development in the oil and application.Ethanol self toxicity is little, is renewable resources, has quite high mediation value, adds the gasoline after ethanol and has the good capability of antidetonance.The external a large amount of mainly U.S., Brazil, European Union etc. of country using ethanol petrol at present.

C, ester class.Of greatest concern at present in octane promoter is methylcarbonate (DMC).RON and MON of DMC is respectively 110 and 97, slightly lower than MTBE.DMC is oxygenatedchemicals, and soon, post-combustion pollution degree is comparatively light to add ignition speed in gasoline to, and wherein contained Sauerstoffatom also can participate in burning, improves combustion processes, reduces unburn HC quantity discharged.Research finds, adds DMC and the combustion heat value of gasoline can be made to decrease, and freezing point and oxygen level raise, on gasoline boiling range, saturated vapor pressure and water-solublely there is no impact; DMC is more suitable for the gasoline concoction that basic octane value is greater than 80.The current evaluation to DMC result of use is only for laboratory.Separately there is patent report malonic ester additive can improve the octane value of gasoline.

Summary of the invention

The object of this invention is to provide a kind of ashless organic anti-knock agent, to significantly improve the octane value of gasoline, strengthen gasoline antiknock performance.

Ashless organic anti-knock agent provided by the invention is a kind ofly allocated ether, the combined compound octane promoter of phenol made by propylene glycol monobutyl ether and 2-methylphenol, and wherein the add-on of 2-methylphenol meets in often liter of propylene glycol monobutyl ether and adds 0.1kg 2-methylphenol.

The propylene glycol monobutyl ether of satisfied metering and 2-methylphenol add in reactor by the concrete preparation method of the present invention is ashless organic anti-knock agent, and at 60 ~ 120 DEG C, hybrid reaction 24h obtains.

Knock test result shows, adds the ashless organic anti-knock agent of 0.1% ~ 0.5% the present invention in the oil, can significantly improve the octane value of gasoline, and the capability of antidetonance strengthens.

Research in recent years shows, by the impact of hydrocarbon structure, a more active part is only had to be the root of fuel generation pinking in the superoxide that hydro carbons produces in combustion and free radical, these free radicals are called as active nucleus, and the power of pinking in reaction is decided by the concentration of gas mixture active nucleus.The present invention, according to this principle, provides the compound octane promoter of a kind of ethers, phenols organic assembling, only needs to add on a small quantity in the oil, effectively can eliminate the peroxide actives in cylinder, alleviate pinking root, improve the octane value of gasoline.

Compared with prior art, ashless organic anti-knock agent of the present invention has unique character and utilization, seldom can improve the additive use of its gasoline octane rating as a kind of novel consumption.

Embodiment

Embodiment 1

In the four-hole bottle with mechanical stirring, thermometer, feed hopper, prolong, add propylene glycol monobutyl ether 85.5mL, 2-methylphenol 8.5g, is warming up to 60 DEG C, and stirring reaction 24h is cooled to room temperature and namely obtains octane promoter.

In 100mL gasoline, add 0.5mL octane promoter, the RON octane value of gasoline is increased to 94.3 from 90.5.

Embodiment 2

In with the 50L reactor of mechanical stirring, thermometer, feed hopper, condenser, add propylene glycol monobutyl ether 30L, 2-methylphenol 3.0Kg, is warming up to 120 DEG C, and stirring reaction 24h is cooled to room temperature and namely obtains octane promoter.

By the octane promoter of the present embodiment with 0.1%, 0.3%, 0.5% ratio (V/V) add in different base oil, as can be seen from table 1, table 2, in catalytic gasoline, blended gasoline, add the octane promoter of 0.5%, organon, motor-method octane number all can improve more than 4 units.

Table 3 gives the changing conditions adding each index of gasoline before and after 0.5% octane promoter in blended gasoline, therefrom can find out, octane promoter adds the indexs such as front and back colloid, sulphur, manganese, iron, lead, mechanical impurity, moisture all without obviously increasing, simultaneously also little on the impact of the indexs such as density, vapour pressure, inductive phase, the requirement of gasoline dope can be met completely.

Joined in 5000L 93# gasoline by the 29.4Kg octane promoter obtained and carry out pilot plant test, vehicle uses normal, does not occur the problem such as engine abnormity, component corrosion, damage oil pump.

Claims

1. an ashless organic anti-knock agent, is allocated by propylene glycol monobutyl ether and 2-methylphenol and makes, and wherein adds 0.1kg 2-methylphenol in the satisfied often liter of propylene glycol monobutyl ether of the add-on of 2-methylphenol.

2. the preparation method of the ashless organic anti-knock agent of claim 1, be add in reactor by propylene glycol monobutyl ether and 2-methylphenol, at 60 ~ 120 DEG C, hybrid reaction 24h obtains.

3. the using method of the ashless organic anti-knock agent of claim 1, be according to 0.1% ~ 0.5% volume ratio add in the oil.