WO2013010309A1

WO2013010309A1 - High-efficiency and environmentally-friendly gasoline antiknock

Info

Publication number: WO2013010309A1
Application number: PCT/CN2011/077216
Authority: WO
Inventors: 熊靓
Original assignee: 深圳市泓耀环境科技发展股份有限公司
Priority date: 2011-07-15
Filing date: 2011-07-15
Publication date: 2013-01-24

Abstract

A high-efficiency and environmentally-friendly gasoline antiknock comprises an organometallic compound and an assistant antiknock, wherein the organometallic compound comprises methyl cyclopentadienylmanganese tricarbonyl and derivatives thereof, tetra-alkyl lead, ferrocene and derivates thereof, cerium (IV) organic chelate or a cyclic metallic compound containing manganese or iron, the assistant antiknock is β-diketones and is generally added as a single agent, with 2,4-pentanedione being preferred, and the assistant antiknock may be added as a composite agent of more than one diketone. The organometallic compound and the assistant antiknock may be added to gasoline respectively at an amount, and may also be formulated into a concentrated mixture by using a small amount of a solvent and then added to gasoline. By using β-diketones as the assistant antiknock, the amounts of the organometallic compound and the assistant antiknock can be reduced, thereby reducing emission of harmful environmental pollutants due to use of a metal-containing organic, and at the same time, maintaining a high antiknock effect.

Description

An efficient and environmentally friendly gasoline antiknock agent

The present invention relates to a gasoline antiknock agent for an internal combustion engine, and more particularly to a gasoline antiknock agent capable of increasing the octane number of gasoline and maintaining low harmful gas emissions.

A gasoline-fueled spark-piston internal combustion engine must have a high compression ratio (compression) in order to reduce fuel consumption. Run under ratio). However, the use of high compression ratio will bring about a drastic change in the pressure of the combustion chamber. When the fuel is not burned enough, the oil and gas mixture containing the remaining fuel will detonate spontaneously under high temperature and high pressure, causing interference to the normal ignition and combustion process of the cylinder and causing The pressure change in the cylinder is inconsistent with the stroke of the cylinder, resulting in knocking of the engine (ie, the engine vibrates and emits noise). One way to prevent knocking is to increase the octane of the gasoline (octane Number), gasoline octane number is a numerical indicator to measure the knocking resistance of gasoline in the cylinder. The high value indicates good antiknock performance, and the high octane gasoline produces higher temperature when burning. Thereby the fuel is burned more fully. A certain combustion promoter is usually added to ordinary gasoline to increase the octane number of the gasoline. Since these combustion additives are aimed at reducing engine knocking, they are often referred to as antiknocks (antiknock). Agent).

Gasoline antiknock agents can be divided into different types according to their chemical properties. At present, there are mainly alcohols, ethers, metals, amines, lipids and complexes, which can be divided into metal ash and according to application characteristics. Organic ashless type.

The earliest widely used antiknock agent was tetraalkyl lead (tetraalkyl). Lead), because it produces toxic lead-containing particles after burning, many governments have banned it from being added to gasoline. Similar organometallic compounds have been proposed to replace tetraalkyl lead, such as methylcyclopentadienyl Mangan Tricarbonyl (MMT), the Chinese name is methylcyclopentadienyl manganese tricarbonyl, however, the addition of MMT will increase hydrocarbon emissions and bring other side effects, such as spark plug blockage, valve combustion, exhaust gas denitrification catalyst blockage, etc. .

Many non-metallic compounds have also been found to be useful as antiknock agents. These non-metals are also referred to as ashless antiknock agents because they have no solid particles remaining after combustion. ). Typical ashless antiknock agents are 1,4 and 1.3 diamine butane (1,4 and 1,3 butane diamine), dimethylaminomethyltetrafluorophenol (2-dimethylamino). Methyl-4-fluorophenol), norbornadiene, and alkyl carbonates. A particularly ashless antiknock agent is aniline and its alkyl derivatives such as 2,6-dimethylaniline. N-methylaniline, n-alkyl toluidines and aromatic amino azides O-aminoazides). In addition, many derivatives of fulvene (methylene cyclopentadiene, fulvene) have also been proposed as antiknock agents, such as halogenated fulvenes, but the use of halogenated fulvenes causes emissions of organic compounds containing chlorine or fluorine. And these halogenated compounds are very powerful ozone depleting substances. US patent (U.S. Pat. No. 3,706,541) reveals some amino fulmene (such as dimethylamino fullate) Fulvene) can also be used as an antiknock agent, especially 6-dimethylamino fulvene is considered to be one of the most effective non-metallic antiknock agents. US patent (U.S. Pat. No. 5,118,325) further indicates 2-alkoxycarbonyl-6-(dimethylamino) –fulvene) and 2,3-dialkoxycarbonyl-6- (dimethylamino) Fulvene) or mixtures thereof are very effective antiknock agents with an optimum dose of 50-400 mg/L.

Also useful as ashless antiknock agents are alkyl substituents of aminopyridine derivatives such as 2-(methylamino)pyridine. a chemically similar compound, and a derivative obtained by substituting a low molecular alkyl group for a group on the aminopyridine ring; some benzylic Amines, such as dibenzylamine and n-methylbenzylamine And mixtures thereof; some alkoxy-substituted benzaldehydes And alkoxy-substituted benzoic esters; some 3-hydroxypyridines Amine substituted derivatives; some acetylenic amines such as N-methylpropargylamine and N-benzylpropargylamne (n-benzylpropargylamne), etc., these antiknock agents are usually not resistant to glue (gum Inhibitors, detergents, rust inhibitors, solvents, and emulsifiers.

US patent (U.S. Pat. No. 4,280,458) discloses ortho-azidophenol or its alkyl derivatives It can be used as an antiknock agent. Adding 4 g/gal of n-azidophenol can increase the research octane number of gasoline by 0.29 per gram gallon. Such compounds can also be used as co-antiknocks for metal antiknock agents (such as lead-containing or manganese-containing organometallic compounds) to minimize the use of metal antiknock agents, such as lead tetrachloride. The concentration can be as low as 0.05-2.5 grams (lead) per gallon, such as MMT at concentrations ranging from 0.01 to 0.9 grams (manganese) per gallon.

However, due to the high cost, relatively low antiknock quality, ability to be hydrolyzed, unstable by heat or oxygen, low solubility in gasoline, or too high solubility in water, the above ashless antiknock agent has never really been commercialized. application.

Since the addition concentration of organometallic compounds such as MMT is limited, in addition to the above-mentioned n-azidophenol can be used as an auxiliary antiknock agent, some auxiliary antiknock agents which have no anti-explosive effect themselves have also been proposed for improving organic metals. The antiknock activity of the compound. Some oxygenated organic compounds such as beta-diketone (beta) in the late 1950s Diketone), carboxylic acid Acids have been found to increase the octane rating of gasoline containing tetraethyllead (TEL) or MMT. Canadian Patent (Canadian Pat. No. 707,695) discloses that when a small amount of certain diketones are added to a high octane gasoline containing a base antiknock agent such as (TEL or MMT), the octane number of 2.5 can still be increased. The patent further discloses that when MMT is used as a base antiknock agent, the amount of diketone added is recommended to be 80-90 times the amount of MMT added (by weight, in terms of manganese). US patent (US Pat. No. 3,261,674) discloses that the diketone can also act to prevent photolysis of MMT, and that 1-3 moles of diketone is sufficient to prevent photolysis of 1 mole of MMT. However, not all diketones have the function of auxiliary antiknock agents, and many β-diketones, especially 2,4-pentanedione, which have a simple molecular structure and low production cost (2, 4) Pentanedione) (also known as acetyl acetone) can be wet rust present in gasoline delivery systems (wet Rust) reacts to lose the role of adjuvant antiknock agent. Many beta diketones also react with lead-tin alloys (90% lead, 10% tin) used as coatings in gasoline tanks. US patent (US Pat. No. 4,437,463) proposed to use benzoylacetone or methyl benzoylacetone (methyl) Bensoylacetone) As an auxiliary anti-explosive agent for MMT, these two diketones do not react with wet rust and lead-tin alloys. The molar ratio of the two auxiliary antiknock agents to the base antiknock agent MMT is from 5 to 60 at a dose of 0.005-0.1 g (manganese) per gallon of MMT. The patent also mentions that benzoylacetone can still react slowly with wet rust for a long time, but the reaction can be inhibited by some oil-soluble rust inhibitor (10-200 ppm). The recommended rust inhibitor is dicyclohexyl nitrite (dicyclohexyl) Ammonium nitrite) or diisopropanolamine. US patent (U.S. Pat. No. 4,211,535) proposes a β-diketone with a branched hydrocarbon group as a basic antiknock agent organic cerium (IV) complex (cerium (IV) Chelats) is an anti-knocking agent. The two hydrocarbon groups of the β-diketone each contain 1-8 carbon atoms and have a carbon number of not less than 5; the amount of the ruthenium complex additive is 0.01-5. G (铈) / gallon, auxiliary additives are added in an amount of 0.5-20 g / gallon. However, this patent does not mention the need to additionally add a rust inhibitor.

Add a small amount of 1,1,2-ethane tricarboxylic acid (1,1,2-ethane tricarboxylic acid) to MMT-containing gasoline The lipids of acid or their oil-soluble salts or derivatives can greatly alleviate the clogging problem of the off-gas catalyst caused by the use of MMT and improve the antiknock activity of MMT (U.S. Pat. No. 4, 052, 171). Other patents suggest the use of large amounts of low molecular oxygenated organics with a small amount of base organometallic antiknock to formulate high antiknock gasoline. Such as WIPO patents (WO 8905339) discloses the use of 5-25% of oxygenated hydrocarbons, such as less than 5 carbons of alcohol, and 75-95% of gasoline and 0.005-0.15 The gram (manganese) / gallon MMT can be composed of high antiknock gasoline. Russian patent (RU2161639) proposed by including organic metal oxides and oxygen agents (aromatic amines) Applicable to N-methy-laniline or toluidine mixture or xylidine mixture), crotonic Aldehide), acetaldehyde Aldehide)) and a small amount of water mixed anti-knocking agent, the dosage is 5-15%, the environmental impact of the combustion products after the addition does not increase, and the formation of CO and CH is reduced. British patent (GB802181) proposes an aliphatic oxygen agent (ethanol (ethyl) composed of non-aldehyde oxygen and non-acid oxygen Alcohol), isopropyl alcohol, oxo alcohol, ketone, acetal, Ester, ether, or cyclic ether such as furan Furan) and its derivatives are added to gasoline to form antiknock gasoline together with organometallic antiknock agents. Typical formulations such as ethanol, isopropanol, diisopropyl ether, dimethylfuran, alcohol obtained by oxidizing fresh petroleum brain Mixtures and tetraethyl lead.

As mentioned above, the organometallic antiknock agent has good antiknock effect, relatively low additive amount and added cost, and is still the most commonly used antiknock agent. However, their use is limited because they cause the emission of harmful particulate matter. In many countries, the addition of TEL to certain gasolines has been banned, and the concentration of MMT added is also strictly regulated. The ashless antiknock agent cannot be realized because of its low antiknock quality, high additive amount and high cost of addition, hydrolysis, heat or oxygen instability, low solubility in gasoline, or too high solubility in water. Commercial applications. High-dose addition of low molecular oxygenated hydrocarbons or alcohols (5-25%) or other mixed oxygenates containing aromatic amines and aldehydes (5-15%) or other non-acidic non-aldehyde mixed oxygenators (Alcohol, ether, fat, ketone, furan and petroleum brain) combined with a small amount of organometallic antiknock agent, although it can reduce the amount of organometallic antiknock additive, reduce cost, and improve the antiknock performance of fuel, but fuel The nature of the product is bound to be greatly affected, such as the heat value of the fuel may decline. Appropriate addition of an anti-knocking agent such as β-diketone can greatly reduce the dosage of the organometallic antiknock agent while maintaining high antiknock performance, which is a good choice, however, the diketone compound It reacts with wet rust or lead-tin metal alloys in gasoline, causing such auxiliary anti-explosives to fail, and may cause deposits and turbidity of the gasoline, greatly affecting their use. US patent (U.S. Pat. No. 4, 437, 436) proposed the use of benzoylacetone And p-methylbenzoylacetone (p-methylbenzoylacetone) as an auxiliary antiknock agent, but these two compounds are complex in structure and high in production cost, and there is a need to use more diketones or other auxiliary antiknock agents in actual production. And exclude the disadvantages in use.

The application of the present invention is directed to the above-mentioned deficiencies existing in the field of gasoline antiknock agents, especially the diketones encountered in the use of β-diketone-assisted antiknock agents and the wet rust in gasoline and A new type of mixed antiknock agent is provided by the reaction of lead-tin alloys, which causes the failure of such auxiliary antiknock agents.

The application of the present invention is achieved by the following technical solutions:

The invention relates to a high-efficiency and environmentally-friendly gasoline antiknock agent, which comprises an organometallic compound antiknock agent, an auxiliary antiknock agent and a rust preventive agent.

Specifically, the invention relates to an efficient environmentally friendly gasoline antiknock agent, characterized in that the antiknock agent comprises an organometallic compound antiknock agent and an auxiliary antiknock agent.

Wherein the organometallic antiknock agent comprises methylcyclopentadienyl manganese tricarbonyl (MMT) and its derivatives, tetraalkyl lead, ferrocene and its derivatives or cerium (IV) (Ce (IV)) an organic chelate (cerium chelate).

Adding dose: MMT: 0.005-0.05 g (Mn) / gallon (Gal), ferrocene: 0.005-0.05 g (Fe) / gallon, the amount of other organometallic antiknock additives is also calculated according to the amount of metal, Roughly in the same range, such as tetraalkyl lead is added in an amount of 0.005-0.05 grams (Pb) per gallon based on metal lead.

The metal antiknock agent also includes a ring metal compound containing manganese or iron (cyclomatic Compound). The molecular structures of typical ring manganese compounds and ring iron compounds have the following general formulas: AMn(CO)3 and AFeA', respectively. In the above formula of the ring manganese and the ring iron compound, A and A' are any cyclopentadienyl group having 5 to 13 carbon atoms or more, and these groups are composed of carbon atoms and have The monocyclic, bicyclic, or tricyclic structure is also added in an amount of 0.005 to 0.05 g (Mn) per gallon or 0.005 to 0.05 g (Fe) per gallon, based on the metal contained.

The cerium (IV) organic chelate is made of a β-diketone having the following formula R1-CO-CH2-CO-R2, and R1 and R2 are alkyl groups each having 1 to 12 carbon atoms (alkyl ), Aralkyl, The cycloalkyl group together has 5-20 carbon atoms, wherein the highly branched aliphatic β-diketone is the most preferred, and the structure and preparation method of the cerium (IV) organic chelate has been In the prior art, the amount added is from 0.005 to 0.05 g/gal in terms of the amount of metal cerium IV.

Hey, the atomic number is 58 and the atomic weight is 140.115. The element name is derived from the English name of the asteroid Vale. In 1803, the German chemist Klaprot and the Swedish chemist Becherius discovered the oxides of bismuth. There are four kinds of natural stable isotopes of strontium: 铈136, 138, 140, 142. The content of strontium in the earth's crust is about 0.0046%, which is the highest abundance among rare earth elements.

A chelate is a complex having a cyclic structure formed by a combination of a central ion and a multidentate ligand. The chelate is a kind of a complex, and in the structure of the chelate, there must be one or more multidentate The ligand provides a plurality of pairs of electrons to form a coordinate bond with the centrosome.

The auxiliary antiknock agent mainly comprises a β-diketone auxiliary antiknock agent, and has a molecular formula:

R1-CO-CH2-CO-R2.

Wherein R1, R2 are various hydrocarbon groups, may be linear or branched, and may contain an aromatic hydrocarbon group having 1-8 carbon atoms.

Preferably, the β-diketone auxiliary antiknock agent comprises: 2,4-pentanedione, 2,4-hexanedione, 2,4-heptane 2,4-heptanedione, 3,5-heptanedione, 6-methyl-2,4-heptanedione, 2, 2,6,6-tetramethyl-3,5-heptanedione (2,2,6,6-tetra-methyl-3,5-heptanedione), 2,4-nonanedione, 2,4-nonanedione, 2,2-dimethyl-3,5-hexanedione, 5,5-dimethyl-2,4-hexanedione, 2,4-octanedione, 3,3-dimethyl-4,6-octanedione (3,3-dimethyl-4,6-octanedione), 2,2,6-trimethyl-6-ethyl-3,5-octanedione (2,2,6-trimethyl-6-ethyl-3,5-octanedione), 7-methyl-2,4-octanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, dibenzoylmethane.

The auxiliary anti-knocking agent is generally added in a single dose, and 2,4-pentanedione is preferred, but it may also be added in more than one compounding agent, and the amount of the additive and the corresponding organometallic compound antiknock agent (calculated as metal). The molar ratio is 5-90:1.

The corrosion inhibitor comprises dicyclohexylamine nitric acid (dicyclohexyl) Ammonia nitrite) (DICAM), diisopropanolamine, imidazolines, Hexamine, benzotriazole, phenylenediamine, Dimethylethanolamine, polyaniline, cinnamaldehyde, Aldehydes, amines and amines, hydrazine, ascorbic acid, Nitric acid and nitrites (nitrites/nitrates), Phosphates and their derivatives. The amount of the rust inhibitor is between 5 and 50 ppm, and the ppm concentration is the concentration expressed by the mass of the solute in parts per million of the mass of the solution, also referred to as the parts per million.

The rust inhibitor further includes a dimer of an unsaturated fatty acid having 8-20 carbon atoms (dimerized unsaturated) Fatty acids such as linoleic acid (Empol 1022) and containing 3-4 alkylene Oxide-alkylated phenol (such as ethoxylated p-octyl, P-nonyl, p-dodecyl Phenol, ethoxy-octyl-phenol, ethoxy-decyl-phenol, ethoxy-dodecyl-phenol) are added in a ratio of 2-5:1 by weight, and the amount of the additive is 3-12ppm.

The above three additives - the metal compound antiknock agent, the auxiliary antiknock agent and the rust preventive agent, may be separately added to the gasoline according to the amount of the additive, or may be formulated into a concentrated mixture and then added to the gasoline with a small amount of solvent.

The above three additives are added to the gasoline without the addition of the rust inhibitor. For the gasoline which has been mixed with the rust inhibitor, the rust inhibitor of the above three components may not be used.

The high-efficiency environmentally-friendly gasoline antiknock agent of the invention has the following advantages:

1. By using a β-diketone auxiliary antiknock agent, the amount of organometallic compound or organometallic chelate antiknock agent can be greatly reduced, thereby reducing the emission of harmful environmental pollutants caused by the use of metal-containing organic substances. At the same time maintain a high level of anti-explosion effect;

2. Compared with other ashless antiknock agents, β-diketone production cost is lower, which can greatly reduce the use cost of antiknock agent, and auxiliary antiknock agent does not cause serious environmental pollution after complete combustion because it does not contain metal elements. ;

3. The low-dose rust inhibitor can block the reaction of wet rust and lead-tin alloy in the β-diketone gasoline storage and transportation system, and also can prevent the corrosion of the metal surface.

detailed description

The high-efficiency environmentally friendly gasoline antiknock agent described in the present application is described below in conjunction with a specific embodiment, in order to better understand the technical content of the present application, and not to limit the technical content. The formulation of the gasoline antiknock agent and the content of each component are improved by the same or similar principle as the application of the present invention, including the use of an organometallic compound antiknock agent having similar physical and chemical properties, an auxiliary antiknock agent and an anti-explosive agent. The rusting agent to replace the components described in the present application is generally available to those skilled in the art without the need for inventive labor, and is therefore within the technical solutions claimed in the present application.

Embodiment 1

Add 0.01 g of MMT in manganese to 1 gallon of gasoline without any antiknock agent, then add 0.4 g 2,4-pentanedione, and 20 ppm Dicyclohexylamine ammonia nitrate. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Embodiment 2

Add 14 mg (Mn) / L of antiknocks MMT and 900 to 16% reforming gasoline and 84% hydrogenated gasoline blended gasoline Peptide auxiliary antiknock agent, study octane value comparison: the situation without the auxiliary anti-explosive agent increased from 92.516 to 92.9, without the anti-explosive agent and without the auxiliary anti-explosive agent, the research octane number is only 91.76.

Embodiment 3

Add 10 mg (Mn) / L of MMT and 900 ppm to 100% catalytic gasoline With the aid of antiknock agents, the octane number increased from 90.2 to 92.3.

Embodiment 4

Add 0.005 g of MMT in manganese to 1 gallon of gasoline without any antiknock agent, then add 0.6 g 2,4-hexanedione, and 5 ppm dimethylethanolamine. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Embodiment 5

Add 0.05 g of MMT in manganese to 1 gallon of gasoline without any antiknock agent, then add 0.4 g 2,4-nonanedione, and 50 ppm of phenylenediamine. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Embodiment 6

Add 0.005 g (Fe) of ferrocene to 1 gallon of gasoline without any antiknock agent, then add 0.5 g 2,2,6-trimethyl-6-ethyl-3,5-octanedione, and 30 ppm Phenyltriazole. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Example 7

Add 0.03 g (Fe) of ferrocene to 1 gallon of gasoline without any antiknock agent, then add 0.4 g 3,3-dimethyl-4,6-octanedione, and 40 ppm Nitrous acid. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Example eight

Add 0.02 g (Pb) of tetraalkyl lead to 1 gallon of gasoline without any antiknock agent, then add 0.5 g Dibenzoylmethane, and 40 ppm of hexamine. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Example nine

Add 0.02 g of cerium (IV) organic chelate to 1 gallon of gasoline without any antiknock agent, then add 0.5 g 3,5-heptanedione, and 9 ppm Linoleic acid and ethoxy-octyl-phenol, wherein the ratio of linoleic acid to ethoxy-octyl-phenol is 3:1. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

Example ten

Add 0.05 g of cerium (IV) organic chelate to 1 gallon of gasoline without any antiknock agent, then add 0.6 g Dibenzoylmethane, and 9 ppm Linoleic acid and ethoxy-dodecyl-phenol, wherein the ratio of linoleic acid to ethoxy-dodecyl-phenol is 4:1. The octane number of its gasoline can be increased by 2-3, and there is no obvious wet rust problem in the fuel supply pipeline during long-term use, and the antiknock performance of gasoline is not significantly reduced.

The gasoline antiknock agent described in the application of the invention can increase the octane number of gasoline by 2-3 by adding an organometallic compound antiknock agent, an auxiliary antiknock agent and a rust preventive agent to gasoline, and when used for a long time, There is no obvious wet rust problem in the refueling pipeline, and the antiknock performance of gasoline has no significant decline, which has broad application prospects.

Claims

The invention relates to an efficient and environmentally friendly gasoline antiknock agent, characterized in that the antiknock agent comprises an organometallic compound antiknock agent and an auxiliary antiknock agent.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 1, wherein the organometallic antiknock agent comprises methylcyclopentadienyl manganese tricarbonyl and a derivative thereof, tetraalkyl lead, ferrocene and Its derivative, an organic chelate of cerium IV or a cyclic metal compound containing manganese or iron.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 2, wherein the molecular structure of the manganese or iron-containing metal compound has the following general formula: AMn(CO)3 and AFeA', in the above In the formula of the ring manganese and the ring iron compound, A and A' are any cyclopentadienyl group having 5 to 13 carbon atoms or more, and these groups are composed of a hydrocarbon atom and have a single ring. Double or triple ring structure.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 2, wherein the methylcyclopentadienyl manganese tricarbonyl and a derivative thereof are added in an amount of 0.005 to 0.05 g/gallon based on the metal manganese.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 2, wherein the ferrocene and its derivative are added in an amount of 0.005 to 0.05 g/gallon based on metallic iron.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 2, wherein the tetraalkyl lead is added in an amount of 0.005 to 0.05 g/gallon based on metal lead.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 2, wherein the manganese or iron-containing ring metal compound is added in an amount of 0.005 to 0.05 g/gallon of metal manganese or iron.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 2, wherein the organic chelate compound of cerium IV is made of β-diketone having the following formula: R1-CO-CH2-CO-R2, R1 and R2 are an alkyl group, an aralkyl group or a cycloalkyl group each having 1 to 12 carbon atoms, which together have 5 to 20 carbon atoms, and the addition amount is 0.005 to 0.05 g/gal in terms of the amount of metal cerium IV. .
The high-efficiency eco-friendly gasoline antiknock agent according to claim 1, wherein the auxiliary antiknock agent comprises a β-diketone auxiliary antiknock agent having a molecular formula: R1-CO-CH2-CO-R2, Where R1, R2 is a hydrocarbon group of various types, and may be a straight chain or a branched chain, and may have an aromatic hydrocarbon group having 1 to 8 carbon atoms.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 1, wherein the β-diketone auxiliary antiknock agent comprises: 2,4-pentanedione, 2,4-hexanedione, 2, 4-heptanedione, 3,5-heptanedione, 6-methyl-2,4-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 2,4-indanedion, 2,4-indanedion, 2,2-dimethyl-3,5-hexanedione, 5,5-dimethyl-2,4-hexanedione, 2, 4-octanedione, 3,3-dimethyl-4,6-octanedione, 2,2,6-trimethyl-6-ethyl-3,5-octanedione, 7-methyl-2,4-octanedione, 2,2,6,6-tetramethyl-3,5-heptanedione or dibenzoylmethane, the molar ratio of the additive to the corresponding organometallic compound antiknock agent in terms of metal is from 5 to 90:1.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 1, wherein the high-efficiency eco-friendly gasoline antiknock agent further comprises a rust preventive agent.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 11, wherein the rust inhibitor comprises dicyclohexylamine ammonia, diisopropanolamine, imidazoline, hexamine, Phenyltriazole, phenylenediamine, dimethylethanolamine, polyaniline, cinnamaldehyde, aldehydes, amines and imines, hydrazine, ascorbic acid, nitric acid and nitrous acid, phosphoric acid, and derivatives thereof.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 12, wherein the rust inhibitor has an additive amount of between 5 and 50 ppm.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 11, wherein the rust inhibitor further comprises a dimer of an unsaturated fatty acid having 8 to 20 carbon atoms and a 3-4 alkylene oxide group. The ethoxy-alkyl-phenol of the group, the former is added to the latter in a weight ratio of 2-5:1, and the additive amount is 3-12 ppm.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 14, wherein the dimer of the unsaturated fatty acid having 8 to 20 carbon atoms includes linoleic acid.
The high-efficiency eco-friendly gasoline antiknock agent according to claim 14, wherein said ethoxylated alkyl-phenol having 3-4 alkylene oxide groups comprises ethoxy-octyl-phenol , ethoxy-decyl-phenol or ethoxy-dodecyl-phenol.