阅读说明：本技术 一种汽油辛烷值促进剂 (Gasoline octane number promoter ) 是由 熊东路 杨轩 易松 龙绪俭 徐涛 肖增钧 鲁晓东 李斌仁 于 2020-05-08 设计创作，主要内容包括：本发明属于汽油添加剂技术领域,具体涉及一种汽油辛烷值促进剂。一种汽油辛烷值促进剂,包括至少一种衍生自醇类的化合物、酚类、添加剂,其中,所述至少一种衍生自醇类的化合物不包括衍生自乙醇的化合物,且所述至少一种衍生自醇类的化合物的干点大于或等于100℃,20℃下粘度小于或等于5.0×10<Sup>-3</Sup>Pa.s。该促进剂在汽油中添加量较少,不会降低汽油的燃烧速度,原料易得,不仅成本很低、而且高效节能环保,对汽油无任何不良影响,且最终使汽油质量显著提高,因此可被广泛应用汽油中以提高燃烧该类型汽油的车辆的燃料经济性。(The invention belongs to the technical field of gasoline additives, and particularly relates to a gasoline octane number accelerator which comprises at least one compound derived from alcohols, phenols and an additive, wherein the at least one compound derived from alcohols does not comprise a compound derived from ethanol, and the dry point of the at least one compound derived from alcohols is greater than or equal to 100 ℃, and the viscosity of the at least one compound derived from alcohols is less than or equal to 5.0 × 10 at 20 DEG C ‑3 Pa.s. The accelerator has the advantages of less addition amount in gasoline, no reduction of the combustion speed of the gasoline, easily obtained raw materials, low cost, high efficiency, energy conservation and environmental protection, no adverse effect on the gasoline, and finally obviously improved gasoline quality, so the accelerator can be widely applied to the gasoline to improve the fuel economy of vehicles burning the gasoline.)

1. A gasoline octane number booster comprising at least one compound derived from an alcohol, a phenol, and an additive, wherein the at least one compound derived from an alcohol does not include a compound derived from ethanol, and the at least one compound derived from an alcohol is converted to an alcoholThe compound has a dry point of 100 deg.C or higher and a viscosity of 5.0 × 10 or lower at 20 deg.C^-3Pa.s。

2. The gasoline octane booster of claim 1 wherein the at least one compound derived from an alcohol is at least one alcohol compound treated by a process selected from the group consisting of etherification, esterification, and amination.

3. The gasoline octane booster of claim 2, wherein the at least one compound derived from an alcohol is preferably at least one chain aliphatic diol which has been subjected to etherification treatment.

4. The gasoline octane number booster of claim 3, wherein the chain aliphatic diol is one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1, 2-butanediol, dipropylene glycol, 1, 3-propanediol, 1, 10-decanediol, 1, 4-butanediol, and 1, 6-hexanediol.

5. The gasoline octane booster of any one of claims 1-4 wherein the phenol is a hindered phenol.

6. The gasoline octane promoter of claim 5 wherein the hindered phenol is selected from the group consisting of 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 6-tert-butyl-o-cresol, 2, 6-diisopropylphenol, 2, 4-di-sec-butylphenol, and mixtures thereof consisting of one or more of 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 6-tert-butyl-o-cresol, 2, 6-diisopropylphenol, and 2, 6-di-tert-butyl-p-cresol.

7. The gasoline octane booster of any one of claims 1-6 wherein the additive is selected from one or more of organic peroxyesters, corrosion inhibitors, rust inhibitors, detergents and dispersants, lubricants, demulsifiers, dyes, cold flow improvers, inert diluents, biocides, antistatic additives, drag reducers, dehazers, anti-freeze additives, anti-knock additives, anti-seat shrinkage additives, lubricity additives, friction modifying additives, cold flow improvers, fuel economy additives, octane improvers, combustion improvers, manganese sources, and other metal-containing ignition improvers.

8. A gasoline comprising the gasoline octane booster of any one of claims 1-7, wherein the concentration of the gasoline octane booster in the gasoline is from 1 to 40 wt%.

9. The gasoline of claim 8 wherein the concentration of said phenols in the gasoline is 100-800 ppm; the concentration of the additive in the gasoline is 300-1000 ppm.

10. The gasoline of claim 8 or 9, wherein the gasoline is selected from any one of 85# gasoline, 87# gasoline, 90# gasoline and 92# gasoline.

Technical Field

The invention belongs to the technical field of gasoline additives, and particularly relates to a gasoline octane number promoter.

Background

The normal combustion of the automobile engine is that a flame center is formed from a spark plug, and the flame advances to all parts of a combustion chamber at a speed of 20-50m/s, so that the temperature is uniformly increased. Abnormal combustion is that a part of combustible gas is compressed and radiated with heat, under the condition of sharp rise of temperature and pressure, many unstable peroxides are generated, decomposition and self-ignition occur before normal flame is transmitted, and deflagration, that is, detonation, occurs.

Octane number is an important measure of gasoline antiknock performance, and generally speaking, the higher the octane number of gasoline, the better the antiknock performance. For gasoline with octane number not meeting the requirement, in order to reduce or eliminate knocking, a proper amount of octane number promoter can be artificially added into the gasoline.

The octane number accelerator comprises two main types of metal ash and organic ash-free. Metallic ashed octane promoters are the first octane promoter products used by humans, of which Tetraethyllead (TEL), ferrocene, Methylcyclopentadienyl Manganese Tricarbonyl (MMT), and the like are representative. The metal ashy octane number accelerator is the octane number accelerator with the most excellent antiknock efficiency, but the metal octane number accelerator generally has the residue problem after long-term use, and can cause the problems of engine spark plug blockage, cylinder body abrasion, poisoning of a three-way catalytic system of an automobile and the like, and the metal octane number accelerator also has larger toxicity (such as TEL, MMT and the like), so that serious health hidden troubles can be caused after a human body contacts the metal octane number accelerator. Organic ashless octane accelerators are primarily oxygen-containing and nitrogen-containing organic compounds, the primary representatives of which are methyl tert-butyl ether (MTBE), methanol, dimethyl carbonate (DMC), azomethylaniline, etc.

MTBE (methyl tert-butyl ether) is used as an octane number improver of gasoline, can increase the oxygen content of the gasoline, can promote clean combustion and reduce the emission pollution of harmful substances of automobiles. However, MTBE is very soluble in water. MTBE is found in drinking water bodies underground in the united states due to leakage from underground and above ground gasoline storage tanks. MTBE causes water malodor even at very low concentrations (Trends in Analytical Chemistry,2006, 25, 1016-1026). More seriously, MTBE has been found to be a possible carcinogen by various studies and has been classified as a possible carcinogen by the U.S. environmental protection agency (Toxicology Letters,2001,123, 89-113; Toxicology and Industrial Health,1995,11, 167-. Therefore, MTBE has been banned in countries such as europe and america. Therefore, the development of octane number accelerators for gasoline is urgently needed to meet the actual domestic demand.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a gasoline octane number enhancer comprising at least one compound derived from an alcohol, a phenol, and an additive, wherein the at least one compound derived from an alcohol does not include a compound derived from ethanol, and the at least one compound derived from an alcohol has a dry point of 100 ℃ or more and a viscosity of 5.0 × 10 or less at 20 ℃ or less^-3Pa.s。

The Dry Point (DP) is a term of petrochemical industry and refers to the temperature, expressed in degrees celsius, at which the last drop of liquid evaporates from the lowest point in the distillation flask when the oil is subjected to a distillation range measurement under specified conditions.

The viscosity refers to the resistance presented by the fluid to flow. When a fluid (gas or liquid) flows, one part flows over the other part, and is subjected to resistance, which is the internal friction of the fluid. To enable fluid flow, tangential forces are applied in the direction of fluid flow to counter the resistance.

As a preferred technical scheme, the at least one compound derived from the alcohols is at least one alcohol compound subjected to a treatment selected from etherification, esterification and amination.

As a preferable embodiment, the at least one compound derived from an alcohol is preferably at least one chain aliphatic diol subjected to etherification treatment.

As a preferable technical scheme, the chain aliphatic diol is one or more selected from ethylene glycol, diethylene glycol, propylene glycol, 1, 2-butanediol, dipropylene glycol, 1, 3-propanediol, 1, 10-decanediol, 1, 4-butanediol and 1, 6-hexanediol.

As a preferred technical scheme, the phenols are hindered phenols.

As a preferable technical scheme, the hindered phenol is selected from one or more of 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 6-tert-butyl-o-cresol, 2, 6-diisopropyl phenol, 2, 4-di-sec-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 6-tert-butyl-o-cresol, 2, 6-diisopropyl phenol or 2, 6-di-tert-butyl-p-cresol.

As a preferred embodiment, the additive is selected from one or more of organic peroxyesters, corrosion inhibitors, rust inhibitors, detergents and dispersants, lubricants, demulsifiers, dyes, cold flow improvers, inert diluents, biocides, antistatic additives, drag reducing agents, dehazers, antifreeze additives, antiknock additives, anti-valve seat shrinkage additives, lubricity additives, friction modifying additives, pour point depressants, cold flow improvers, fuel economy additives, octane improvers, cetane improvers, combustion improvers, manganese sources, and other metal-containing ignition improvers.

In a second aspect the invention provides a gasoline comprising a gasoline octane number booster, the concentration of the gasoline octane number booster in the gasoline being in the range 1 to 40 wt%.

As a preferable technical proposal, the concentration of the phenols in the gasoline is 100-800 ppm; the concentration of the additive in the gasoline is 300-1000 ppm.

As a preferable technical scheme, the gasoline is selected from any one of 85# gasoline, 87# gasoline, 90# gasoline and 92# gasoline.

Has the advantages that: the invention provides a gasoline octane number promoter, which has the advantages of low addition amount in gasoline, no reduction of the combustion speed of the gasoline, easily available raw materials, low cost, high efficiency, energy conservation and environmental protection, no adverse effect on the gasoline, and finally obviously improved gasoline quality, thereby being widely applied to the gasoline to improve the fuel economy of vehicles combusting the gasoline.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.

The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

Unless otherwise explicitly stated, the following abbreviations in this specification have the following meanings: min is minutes; ms is millisecond; μ m to μm; ppm is one part per million; ppb to parts per billion, micrograms per liter; ppm-parts per million, milligrams per liter; DEG C is centigrade; g/L is gram/liter; dm is decimeter; wt% ═ weight percent; all numerical ranges are inclusive and combinable with each other in any order so long as the sum of the numerical ranges is limited, logically, to 100%.

In order to solve the above problems, a first aspect of the present invention provides a gasoline octane number enhancer comprising at least one compound derived from an alcohol, a phenol, and an additive, wherein the at least one compound derived from an alcohol does not include a compound derived from ethanol, and the at least one compound derived from an alcohol has a dry point of 100 ℃ or more and a viscosity of 5.0 × 10 or less at 20 ℃ or less^-3Pa.s。

In a preferred embodiment, the at least one compound derived from alcohols is at least one alcohol compound subjected to a treatment selected from the group consisting of etherification, esterification and amination.

In a preferred embodiment, the at least one compound derived from an alcohol is preferably at least one chain aliphatic diol which has been subjected to an etherification treatment.

In a preferred embodiment, the chain aliphatic diol is selected from one or more of ethylene glycol, diethylene glycol, propylene glycol, 1, 2-butanediol, dipropylene glycol, 1, 3-propanediol, 1, 10-decanediol, 1, 4-butanediol, 1, 6-hexanediol.

In a more preferred embodiment, the chain aliphatic diol is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol.

In a more preferred embodiment, the above preferred at least one compound derived from an alcohol includes, but is not limited to: ethylene glycol tert-butyl ether, ethylene glycol di-tert-butyl ether, 1, 2-butanediol tert-butyl ether, 1, 4-butanediol tert-butyl ether.

In a more preferred embodiment, said at least one compound derived from alcohols has a dry point greater than or equal to 130 ℃ and a viscosity at 20 ℃ of 4.0 × 10^-3-5.0×10^-3Pa.s; examples of this class include, but are not limited to: ethylene glycol tert-butyl ether, ethylene glycol di-tert-butyl ether, 1, 2-butanediol tert-butyl ether, 1, 4-butanediol tert-butyl ether. Wherein the ethylene glycol tert-butyl ether and the ethylene glycol are ethylene glycolThe t-butyl ether, 1, 2-butanediol t-butyl ether, can be obtained commercially or prepared by a method commonly used by those skilled in the art.

The ethylene glycol tert-butyl ether ETB is prepared by taking ethylene glycol and isobutene (or MTBE) as raw materials and generating under the action of acid catalysis. Ethylene glycol, isobutylene and MTBE are derived primarily from coal or petroleum. Currently, there is a large worldwide excess of MTBE. On the one hand, ETB as an octane number promoter belongs to the coal-to-liquid industry, and on the other hand, ETB is beneficial to consuming excessive MTBE. Moreover, the quality analysis of the ETB related oil shows that the ETB can be completely used as a gasoline additive to be added into gasoline.

In a more preferred embodiment, the at least one compound derived from an alcohol comprises (a) ethylene glycol tert-butyl ether and (b) ethylene glycol di-tert-butyl ether and/or 1, 2-butanediol tert-butyl ether; and the mass ratio of (a) to (b) is (1.5-3): 1; preferably (2-3): 1; most preferably (2.5-3): 1.

the inventors have found that the combustion speed of gasoline is easily decreased when any one of the above-mentioned preferred at least one alcohol-derived compound is added alone, and the combustion speed of gasoline is significantly improved when it is added after being mixed with toluene and xylene-based compounds, and surprisingly, the inventors have found that not only the combustion speed of gasoline is not decreased but also the octane number is significantly increased by using the above-mentioned (a) and (b) components as compared with the addition of toluene-based compounds.

In actual use, compared with methanol gasoline, the methanol gasoline does not contain alcohol additives per se, so the oxygen content of the methanol gasoline is lower than that of the methanol gasoline, the gasoline can be commonly used 85# gasoline, 87# gasoline, 90# gasoline, 92# gasoline and the like during production, and the inventors found that the unsaturated hydrocarbon can be promoted to be an epoxy compound in a flash combustion period under the specific proportion of (a) and (b), and the generation probability of a plurality of flame centers is reduced, so that the final octane number of the gasoline with lower oxygen content is excellent.

And the non-metallic antiknock agent reduces the probability of generating a plurality of flame centers by converting unsaturated hydrocarbons into epoxy compounds in a flash-off period.

In a preferred embodiment, the phenol is a hindered phenol.

In a preferred embodiment, the hindered phenol is selected from the group consisting of 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 6-tert-butyl-o-cresol, 2, 6-diisopropylphenol, 2, 4-di-sec-butylphenol, and one or more of 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 6-tert-butyl-o-cresol, 2, 6-diisopropylphenol, or 2, 6-di-tert-butyl-p-cresol.

As the above preferred hindered phenols, the most effective embodiments include, for example, 2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 2, 4-dimethyl-6-tert-butylphenol, 4' -methylenebis (2, 6-di-tert-butylphenol), and mixed methylene bridged polyalkyl phenols, with combinations of tert-butylphenols such as 2, 6-di-tert-butyl-p-methylphenol being particularly preferred for use in the practice of the present invention.

In a preferred embodiment, the additive is selected from one or more of organic peroxyesters, corrosion inhibitors, rust inhibitors, detergents and dispersants, lubricants, demulsifiers, dyes, cold flow improvers, inert diluents, biocides, antistatic additives, drag reducing agents, dehazers, antifreeze additives, antiknock additives, anti-valve seat shrinkage additives, lubricity additives, friction modifying additives, cold flow improvers, fuel economy additives, octane improvers, combustion improvers, manganese sources, and other metal-containing ignition improvers.

For example, in some embodiments, suitable amounts of demulsifiers, antiknock agents, corrosion inhibitors, metal deactivators may be added to improve gasoline performance.

Examples of demulsifiers include, but are not limited to: organic sulfonate, polyoxyalkylene glycol, alkoxylated phenol resin, and the like. Particularly preferred are mixtures of alkylaryl sulfonates, polyoxyalkylene glycols and alkoxylated alkylphenol resins.

Examples of antiknock agents include, but are not limited to, alkali metal-containing organics, alcohols, nitrogen-containing compounds.

Among them, the organic matter containing alkali metals has its outstanding advantages as gasoline antiknock. Although alkali metal-containing organic antiknock agents have a number of advantages, they also have disadvantages: most of the additives belong to ionic bond type compounds and are not easy to volatilize, so the additives are more suitable for internal combustion engines with injection systems, and for carburetor type internal combustion engines with air suction pipes, the additives can generate deposits at the air suction pipes after long-term use to cause oil circuit blockage; after some carboxylates are added into gasoline, the induction characteristic of the gasoline is deteriorated, namely the induction period is shortened; when some metal carboxylates are used as gasoline antiknock agent, it is necessary to add methanol, ethanol, isopropanol, ethylene glycol monomethyl ether and other assistants, but this results in an increase in the total dosage.

For alcohol antiknock, lower alcohols such as methanol, ethanol, propanol and tert-butanol, or mixtures thereof have been used as gasoline additives. The mixture used as gasoline additive has similar function to MTBE and also has price advantage.

In addition, the nitrogen-containing compounds which can be used as the antiknock agent are mainly amines, wherein the most important is aromatic amine, including aniline, monomethyl aniline, dimethyl aniline, ethyl aniline, polyaromatic amine, diphenylamine, o-azidoaniline, benzidine, trinonyl benzidine and the like. But the use of the N-methylaniline antiknock agent reduces the combustion rate of gasoline. In fact, the special antiknock agent adopted in the invention is FT20-11 type gasoline antiknock agent which is prepared by carrying out chemical reaction on different organic amides and organic phenols and can be purchased from Shanxi flying science and technology company Limited. When the anti-knock agent and the two substances (a) and (b) of the invention act together, dry point, viscosity and solubility parameters of the substances (a) and (b) are controlled, so that no oil product stratification exists when the substances (a) and (b) are added into gasoline, high gasification latent heat is ensured to maintain stable combustion speed, a small amount of the anti-knock agent can promote the active groups in the substances (a) and (b) to react with peroxide, OH & lt- & gt and other groups generated by the oxidation of the gasoline due to the active groups with the action of mobile bonds, so that the fuel is subjected to dissimilatory reaction in a branch ignition wire, the concentration of oxides before flame is greatly reduced, the branch of the chain is reduced, the length is reduced, and finally the quality of the gasoline is improved.

Examples of corrosion inhibitors include, but are not limited to: dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, linoleic acid, and the like. Further suitable types of corrosion inhibitors for the practice of the present invention are alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenyl succinic acid, tetrapropenyl succinic anhydride, tetradecenyl succinic acid, tetradecenyl succinic anhydride, hexadecenyl succinic acid, hexadecenyl succinic anhydride, and the like. Furthermore, half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as polyethylene glycols can also be used.

Examples of metal deactivators include, but are not limited to: n, N '-disalicylidene-1, 2-alkanediamine, or N, N' -disalicylidene-1, 2-cycloalkanediamine, or mixtures thereof. Examples include N, N ' -disalicylidene-1, 2-ethylenediamine, N ' -disalicylidene-1, 2-propylenediamine, N ' -disalicylidene-1, 2-cyclohexanediamine and N, N ' -disalicylidene-N ' -methyldipropylenetriamine.

In a second aspect the invention provides a gasoline comprising a gasoline octane number booster, the concentration of the gasoline octane number booster in the gasoline being from 1 to 40 wt%; more preferably 5-15 wt%; most preferably 10-15 wt%.

In a preferred embodiment, the concentration of the phenols in the gasoline is 100-800 ppm; more preferably 100-300 ppm; most preferably 200 ppm; the concentration of the additive in the gasoline is 300-1000 ppm; more preferably 400-600 ppm; most preferably 500 ppm.

In a preferred embodiment, the gasoline is selected from any one of 85# gasoline, 87# gasoline, 90# gasoline and 92# gasoline.

It will be appreciated that in addition to the above-mentioned inclusion of a gasoline octane number booster, the gasoline of the present invention may be supplemented with any of the conventional additives which do not affect the quality of the gasoline of the present invention, all in the conventional amounts used for such additives included in the gasoline of the present invention. Thus, the amount of these optional additives added is not critical to the practice of the present invention. The amount used in each particular case is sufficient to impart the desired functional properties to the fuel composition, and such amounts are well known to those skilled in the art.

The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.