CN114806650B

CN114806650B - Low-proportion methanol gasoline for vehicle

Info

Publication number: CN114806650B
Application number: CN202210392669.4A
Authority: CN
Inventors: 陈记; 路新龙
Original assignee: Individual
Current assignee: Individual
Priority date: 2022-04-15
Filing date: 2022-04-15
Publication date: 2023-07-14
Anticipated expiration: 2042-04-15
Also published as: CN114806650A

Abstract

The invention provides the low-proportion methanol gasoline for the vehicle, which has better power performance and fuel economy; when the methanol gasoline is used for the direct injection engine in the cylinder, the problems of carbon deposition, particulate matters generation and the like in the cylinder are obviously improved, the maintenance requirement and the maintenance cost of the engine are reduced, and the exhaust system is basically not blocked by the particle catcher which needs to perform special carbon burning regeneration due to the methanol gasoline when the particle catcher is assembled; the adopted atomized combustion control agent is easy to purchase, and the technical effects of reducing carbon deposition in a cylinder, reducing the generation amount of particulate matters and the like are achieved on the basis of lower addition amount. The low-proportion methanol gasoline for the vehicle is suitable for direct injection engines in cylinders and multipoint electronic injection engines with an air inlet manifold, comprises self-priming gasoline engines with exhaust gas turbocharging and/or gasoline engines with accurate valve control technology, particularly low-displacement gasoline engines with the displacement of less than 1.6L, and has better market prospect.

Description

Low-proportion methanol gasoline for vehicle

Technical Field

The invention belongs to the technical field of clean gasoline, and particularly relates to low-proportion methanol gasoline for vehicles.

Background

At present, the oil supply mode of the gasoline engine for the vehicle mainly comprises multipoint electric injection of an intake manifold and direct injection in a cylinder.

Compared with multi-point electronic injection, the in-cylinder direct injection technology mainly injects gasoline in a cylinder at a shorter time before and after ignition of a spark plug, and mixes the gasoline with air directly in the cylinder, so that the control and the matching of the injection time, the injection quantity and the ignition time are more accurate and flexible, the stratified combustion and the lean combustion with higher power efficiency and higher heat efficiency are realized under the conditions of high air-fuel ratio and high compression ratio, and the matching and the effect with complex air distribution conditions are easy to realize, thereby obviously improving the power performance of an engine such as power rise and maximum torque, especially low-speed torque, and reducing the oil consumption, and the application is gradually increased. The engine is effectively combined with an exhaust gas turbocharging technology and a valve control technology, so that high power performance and fuel economy of the engine are well realized, and the installed ratio of a low-displacement gasoline engine adopting an in-cylinder direct injection technology is higher and higher. However, the defects of easy carbon deposition, high particle generation and the like existing in the direct injection technology in a gasoline engine cylinder are still difficult to overcome, and are far more serious than the defects of the direct injection technology in a multi-point electronic injection technology, so that the engine maintenance requirements and the maintenance cost are high, the exhaust systems of many engines are also provided with particle traps, and the particle traps generally need to be regenerated by burning carbon; these problems cause a lot of inconvenience and trouble to the vehicle user.

The low-proportion methanol gasoline for vehicles, such as the formula and the M15 methanol gasoline prepared properly, can directly replace the conventional gasoline with the same grade, and has certain advantages in the aspects of fuel economy and tail gas emission. However, the low-proportion methanol gasoline for vehicles in the prior art, such as M15, is mostly developed based on the mainstream multi-point electronic injection technology and the engine exhaust emission standard at that time in ten years ago, and even if the blending component oil which accords with the national six-gasoline standard is changed, the improvement range of the defects of easy carbon deposition, high particle production and the like of the direct injection technology in a cylinder is limited, the engine maintenance requirement and the maintenance cost are still higher, and the exhaust system still always needs special carbon burning regeneration when being equipped with a particle catcher; that is, these low-ratio vehicular methanol gasoline are not well suited for the current mass-application in-cylinder direct injection technology engine, and are even less suited for the current mass-application exhaust gas turbocharging + in-cylinder direct injection low-displacement gasoline engines, such as 1.6L or less, which have insignificant advantages in terms of fuel economy and engine maintenance and some of the contained additives are disabled or are harder to purchase, thus not being easy to continue production and gaining market acceptance, compared with the conventional gasoline adopting the current national sixth standard.

Disclosure of Invention

In order to solve the technical problems, the invention provides the low-proportion methanol gasoline for the vehicle, which has better power performance and fuel economy; when the methanol gasoline is used for the direct injection engine in a cylinder, including the direct injection engine in the cylinder with exhaust gas turbocharging and/or accurate valve control technology, the problems of carbon deposition in the cylinder, particulate generation and the like are remarkably improved, the maintenance requirement and the maintenance cost of the engine are reduced, and the exhaust system is basically not blocked by the particle catcher which needs special carbon burning regeneration due to the methanol gasoline when the particle catcher is assembled; compared with the prior art low-proportion methanol gasoline for vehicles, which accords with the six standards of the current country and has the same standard as the conventional gasoline and similar methanol content, the methanol gasoline for vehicles has certain advantages; the adopted atomized combustion control agent is easy to purchase, and the technical effects of reducing carbon deposition in a cylinder, reducing the generation amount of particulate matters and the like are achieved on the basis of lower addition amount. The low-proportion methanol gasoline for the vehicle can be widely applied to direct injection engines in cylinders with different displacement, structures and control logics, is more applicable to multi-point electronic injection engines with inlet manifolds and low requirements on fuel quality and performance, is also applicable to double injection technology engines combining multi-point electronic injection and direct injection in cylinders of the inlet manifolds, comprises self-priming gasoline engines with exhaust gas turbocharging and/or gasoline engines with accurate valve control technology, particularly low-displacement gasoline engines with the displacement of less than 1.6L, and has good market prospect.

The low-proportion methanol gasoline for vehicles comprises, by weight, 10-30% of methanol, 0.1-0.5% of an atomized combustion control agent, 0.02-0.1% of a metal corrosion inhibitor, 0.02-0.2% of a rubber expansion inhibitor, and the balance of gasoline blending component oil; the control agent for atomized combustion comprises polymethylphenyl ethanol ((CH) ₃ ) _X -C ₆ H _6-X-1 )-CH ₂ -CH ₂ -OH, polymethylphenyl ethyl ether ((CH) ₃ ) _X -C ₆ H _6-X-1 )-O-CH ₂ -CH ₃ The weight ratio of diethyl malonate is 50-75:5-15:10-25, wherein the content of the polymethylphenylethanol, the polymethylphenylether and the diethyl malonate is more than or equal to 60wt%, and X=2 or 3; the polymethylphenyl group is an o-dimethylphenyl group, i.e., 1, 2-dimethylphenyl, or an m-dimethylphenyl group, i.e., 1, 3-dimethylphenyl, when x=2, and the-CH when the polymethylphenyl group is an o-dimethylphenyl group ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The linkage position to the benzene ring is 4-position, and when the polymethylphenyl group is m-dimethylphenyl, the-CH ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection position with the benzene ring is 5; the polymethylphenyl group is a mesityl group, i.e., 1,2, 3-mesityl group, or a meta-mesityl group, i.e., 1,2, 4-mesityl group, when x=3, in which case the-CH ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection positions with the benzene ring are all 5 positions.

In the atomized combustion control agent, the weight ratio of the polymethylphenyl ethanol, the polymethylphenyl ethyl ether and the diethyl malonate is preferably 55-70:8-10:12-15.

The atomized combustion control agent can be a mixture of the polymethylphenyl ethanol, the polymethylphenyl ethyl ether and the diethyl malonate, but the production amount of the two chemicals of the polymethylphenyl ethanol and the polymethylphenyl ethyl ether is low and the price is high at present, and no report of using the additive as a fuel additive for vehicles exists. Diethyl malonate is a common solvent, and has large production amount, moderate price and easy purchase.

The atomized combustion control agent comprises, for cost and purchase difficulty control, the polymethylphenyl ethanol and polymethylphenyl ethyl ether, which are prepared from one or more polymethylbenzene selected from o-xylene, m-xylene, hemimellitene and pseudocumene, or aromatic hydrocarbon oil containing more than 80wt% of the polymethylbenzene, as raw materials of the polymethylphenyl, and capable of forming the-CH at the connecting position of the phenyl ₂ -CH ₂ -OH、-O-CH ₂ -CH ₃ Is synthesized by direct reaction of a suitable starting material such as ethylene oxide. Components other than the polymethylbenzene in the hydrocarbon oil should not affect the reaction of the polymethylphenyl group with ethylene oxide to produce the polymethylphenyl ethanol and the polymethylphenyl ethyl ether.

The weight ratio of 50-75 is synthesized by reacting the polymethyl benzene or hydrocarbon oil containing more than 80wt% of the polymethyl benzene with ethylene oxide: 5-15 of polymethylphenyl ethanol and polymethylphenyl ethyl ether, and one preparation method thereof is as follows: mixing one or more of o-xylene, m-xylene, mesitylene and mesitylene or aromatic hydrocarbon oil containing more than 80wt% of the poly-toluene with ethylene oxide according to a required proportion, adding a powdery Pt/HZSM-5 molecular sieve catalyst, reacting at 30-40 ℃ under stirring for 8-20h under a liquid phase condition, separating the Pt/HZSM-5 molecular sieve catalyst after the reaction until the ethylene oxide is completely converted, and obtaining the catalyst containing 50-75:5-15 of polymethylphenyl ethanol, polymethylphenyl ethyl ether and the residual polymethylbenzene or the reaction generating solution of the aromatic hydrocarbon oil residual material; the dosage of the Pt/HZSM-5 molecular sieve catalyst in the reaction is 3 to 10 weight percent of the liquid dosage of the polymethylbenzene and the ethylene oxide. The Pt/HZSM-5 molecular sieve catalyst is provided by Shandong Xingxing new material science and technology Co-Ltd of the related company of the applicant, wherein the Pt content is 0.05-0.1wt%, is basically loaded into a pore canal in a crystal grain of the HZSM-5 molecular sieve by a cation exchange method, and is obtained by reducing and drying hydrazine hydrate; the HZSM-5 molecular sieve has a silicon-aluminum ratio of 60-120, is a crystal rather than a microcrystalline aggregate, has a relative crystallinity higher than 95%, has a grain number of 0.8-5 μm in an overall dimension of more than 95% and less than 1% of the total grain number, and has two main pore sizes of 0.53 x 0.56 and 0.51 x 0.55nm. The preparation method of the catalyst is shown in CN201910196183.1. The reaction is carried out to charge the polymethylbenzene, the ethylene oxide and the aromatic hydrocarbon oil containing more than 80 weight percent of the polymethylbenzene, and the aromatic hydrocarbon oil does not contain components which are toxic to the catalyst, especially the highly dispersed metal Pt, for example, the sulfur content is less than or equal to 1ppm.

The feeding ratio of the amount of the polymethylbenzene contained in the polymethylbenzene or the aromatic hydrocarbon oil to the amount of the ethylene oxide substance is 100: the reaction effect is better at 50-75, wherein 100:60-70, and the selectivity of the corresponding polymethylphenyl ethanol and polymethylphenyl ethyl ether in the reaction product is more than or equal to 99 percent based on the feeding of ethylene oxide, the selectivity of the polymerization product of ethylene oxide in the byproducts is less than or equal to 0.1 percent (the products are dimeric ether alcohol and tripholyether alcohol through ring-opening polymerization, and no more than four ether alcohol products are detected). The aromatic hydrocarbon oil can contain a small amount of toluene, ethylbenzene, propylbenzene, para-xylene, mesitylene and diethylbenzene, and the aromatic hydrocarbon is less reacted with ethylene oxide under the Pt/HZSM-5 molecular sieve catalyst and the reaction condition due to the limitation of the reactivity, steric hindrance or the pore size of molecular sieve particles. The 4-position hydrogen and the 5-position hydrogen of the phenyl in the polymethylbenzene have higher reactivity in the pore canal of the Pt/HZSM-5 molecular sieve catalyst, and react with ethylene oxide to generate polymethylphenyl ethanol and polymethylphenyl diethyl ether with the proportion.

The reaction product liquid can be directly used for preparing the atomized combustion control agent; or removing more than 80% of residual polymethylbenzene or aromatic hydrocarbon oil residual material by normal pressure or reduced pressure distillation, collecting polymethylphenyl ethanol and polymethylphenyl ethyl ether at the bottom of the distillation tower, and then preparing the atomized combustion control agent.

The Pt/H beta molecular sieve catalyst similar to the preparation method (provided by Shandong Juxing New Material science and technology Co., ltd., see CN201910196183.1 specifically, the main pore size of H beta molecular sieve crystal grain is 0.56-0.75nm, the silicon-aluminum ratio is 40-100) has slightly poorer effect when being used for the reaction, the yield of the polymethyl phenyl ethyl ether is larger, the byproducts with larger molecular weight are obviously increased, the ratio of the polymethyl phenyl ethyl alcohol and the polymethyl phenyl ethyl ether is not easy to obtain, and the main reason is that the acid strength and the acid center number of the H beta molecular sieve are obviously higher than those of the HZSM-5 molecular sieve, the size of the pore canal in the crystal grain is larger, and the epoxy ethane is easier to react.

In the low-ratio methanol gasoline for vehicles, the content ratio of methanol to an atomized combustion control agent is preferably 100:1.0-2.0.

The gasoline blending component oil can comprise 20-30 parts by weight of naphtha, 20-30 parts by weight of raffinate oil, 10-20 parts by weight of No. 120 solvent oil, 8-15 parts by weight of alkylate and 5-20 parts by weight of aromatized oil; the oil can meet the requirements of various indexes of the ethanol gasoline blending component oil for vehicles such as GB 22030-2017, and the selection and blending proportion of the raw oil are determined according to the conditions of various oils and octane number requirements.

The naphtha comprises straight run naphtha and catalytic cracked naphtha; and naphtha produced by direct coal liquefaction and coal tar hydrogenation, such as light coal tar No. 2, refined wash oil No. 2, stable light hydrocarbon and the like.

The raffinate oil is the residue obtained by reforming the 60-130 ℃ fraction of straight-run gasoline after topping and extracting aromatic hydrocarbon, and the main components are C6-C8 alkane and naphthene.

The No. 120 solvent oil mainly comprises n-heptane, isoheptane and cycloheptane, and also contains a small amount of octane and hexane.

The alkyl oil is side chain alkane with isooctane as main component and is obtained through C4 alkylation after ether treatment.

The aromatized oil is C5-C10 separated from light hydrocarbon such as liquefied gas, condensate oil or aromatization product of C4 after ether.

The components of the metal corrosion inhibitor and the rubber expansion inhibitor meet the related technical requirements of the methanol gasoline additive for the GB/T34548-2017 vehicle, and the addition amount can enable the prepared methanol gasoline to meet the related local standard requirements of the operation area. One of the metal corrosion inhibitors is a mixture of benzotriazole and pyridone in a weight ratio of 3-6:1. The rubber expansion inhibitor can be JH4012 of Sean Jia macro technology Co.

The methanol comprises vehicle fuel methanol conforming to GB/T23510-2009, or qualified products, first-class products or superior products of GB/T338-2011 industrial methanol.

In the low-proportion methanol gasoline for vehicles, the polymethylphenyl ethanol polymethylphenyl ethyl ether and diethyl malonate of the atomization combustion control agent are not methylal, anilines, halogens, phosphorus-containing, iron-containing, silicon-containing and other harmful forbidden compounds specified in the current standards of the vehicle gasoline, the methanol gasoline and the ethanol gasoline; the specific addition amount is determined according to the components and performance conditions of the blended component gasoline and the requirements on carbon deposit resistance, particulate matter inhibition, grade, stability and the like of the blended methanol gasoline, wherein the stability comprises the layering temperature/cloud point of the methanol gasoline, the storage time under different temperature conditions and the tolerance to the water content of the methanol or the water absorption capacity of the methanol gasoline.

From the test results and specific application effects of the methanol gasoline of the following examples and comparative examples, and by combining the technical experience of the inventor, it is inferred that the principle of action of the atomized combustion control agent in the methanol gasoline for low-ratio vehicles of the present invention is as follows.

1. The polarity and the surface tension of the contained polymethylphenyl ethanol, polymethylphenyl ethyl ether and diethyl malonate are between those of stronger methanol and weaker gasoline components, so that the stability of the methanol gasoline is improved, the layering degree/cloud point of the methanol gasoline is very low, the storage time is long, the water content of the methanol is allowed to be less than 0.5wt%, and the water content of the methanol gasoline is not more than 0.3 wt%.

2. The atomization capability of the methanol gasoline is improved, the fineness of oil mist droplets obtained by direct injection in a cylinder is obviously increased, and the average outer diameter is obviously reduced, so that the oil mist droplets can volatilize more quickly, the surfaces of a spark plug, an oil nozzle and the inner wall and the piston surface at the upper part of the cylinder are not easy to wet, the combustion performance is obviously improved, and the generated carbon particles are obviously refined. Adverse effects between the atomized combustion control agent and the metal corrosion inhibitor and the rubber expansion inhibitor are not found in the examples and the application examples.

3. The polymethylphenyl ethanol has a certain antiknock effect, namely octane number increasing effect, can improve the octane number of the gasoline blending component oil on the premise of basically not changing the composition of the gasoline blending component oil and other technical indexes, reduces the peroxide concentration formed by the gasoline blending component oil in the combustion process, reduces the combustion speed of oil mist droplets, promotes the full combustion of the gasoline blending component oil, particularly ensures the full combustion of aromatic hydrocarbon components, has a certain synergy of the antiknock effect or the octane number increasing effect and the methanol antiknock effect or the octane number increasing effect, ensures that the combustion of the methanol gasoline in the operation process of the direct injection engine is more stable and more sufficient, obviously reduces the generation amount of carbon particles, is beneficial to removing the combustion carbon deposit in the cylinder, prolongs the maintenance period and the service life of the engine, and has lower emission amount of pollutants in tail gas; thus, the material selection range of the gasoline blending component oil can be widened to a certain extent.

4. The concentration of peroxide formed by the mixed gasoline component oil in the combustion process can be improved to a certain extent by the contained polymethylphenyl ethyl ether and diethyl malonate, so that the combustion speed of oil mist microdroplets is moderate, the reduction effect on the combustion speed of the oil mist microdroplets when the using amount of the polymethylphenyl ethyl alcohol is more is properly controlled, and the mixed gasoline component oil has a certain positive effect on ensuring the stable and full combustion of the mixed gasoline component oil in the stratified combustion and lean combustion processes, in particular the stable and full combustion of aromatic hydrocarbon components.

5. The combined action of the principles 2-4 obviously reduces the carbon deposition generation speed of the spark plug, the oil nozzle surface, the inner wall of the upper part of the cylinder and the top surface of the piston, obviously reduces the quantity of the generated particles, and reduces the size, namely refines the size, so that the generation weight of the particles is greatly reduced, and the particles are easy to burn off when the exhaust system is provided with the particle catcher, so that the blockage of the particle catcher which is required to be specially regenerated by the methanol gasoline is basically avoided; the surface of the spark plug, the surface of the oil nozzle and the inner wall of the upper part of the cylinder and the top surface of the piston are also cleaned and removed to a certain extent.

Detailed Description

The present invention is specifically described below by way of examples, which are not to be construed as limiting the invention.

Examples 1 to 7, comparative example 1.1, comparative example 1.2

Aromatic hydrocarbon solutions containing polymethylphenylethanol+polymethylphenylether of examples 1 to 7, comparative example 1.1, comparative example 1.2 were prepared according to the raw material ratios of table 1.

Examples 1-7 were operated as follows: in a fume hood, a 1000mL stainless steel small-sized reaction kettle with a jacket is filled with circulating ice water after nitrogen gas is tested and replaced, the temperature in the kettle is reduced to below 5 ℃, aromatic hydrocarbon or aromatic hydrocarbon oil and ethylene oxide with the temperature of 0-5 ℃ are added, stirring is started, 22g of Pt/HZSM-5 molecular sieve catalyst (about 5wt% of the feeding amount of aromatic hydrocarbon or aromatic hydrocarbon oil plus ethylene oxide) is added after 5min, the reaction kettle is sealed, the jacket is filled with circulating water with the temperature of 32 ℃, and the temperature in the kettle is controlled to be 30-32 ℃ for reaction; sampling 0.5mL for preservation every 1h in the reaction process, detecting by gas chromatography, stopping stirring for 5min before sampling, settling the catalyst, stopping stirring after detecting the residual of the ethylene oxide, pumping out all the feed liquid, separating the liquid and the catalyst by a sand core funnel, filling the obtained liquid product into a small-mouth reagent bottle, capping and numbering for storage, washing the catalyst with 200-220mL of o-xylene for three times, performing suction filtration, and sealing and storing by a bag or directly using the catalyst for the reaction of the next kettle.

Comparative example 1.1 the same raw material ratio, pt/HZSM-5 molecular sieve catalyst and operation procedure as in example 1 were adopted, except that the jacket was changed to 52 ℃ circulating water after the reaction vessel was closed, and the temperature in the vessel was controlled to 50-52 ℃ for reaction.

Comparative example 1.2 the same raw material ratio and operation procedure as in example 1 were adopted, except that 22g of Pt/H beta molecular sieve catalyst was used for the reaction, the temperature of circulating water passing through the jacket after the reaction vessel was closed was 32 ℃, and the reaction temperature in the vessel was controlled to be 30-32 ℃.

The powdered Pt/HZSM-5 molecular sieve catalyst used was prepared according to the recipe of CN201910196183.1 example 1, supplied by Shandong Juxing New Material technology Co., ltdThe Pt content of the catalyst is 0.062wt%, and the catalyst is prepared by basically loading the catalyst into pore channels in grains of an HZSM-5 molecular sieve by a cation exchange method, reducing the catalyst by hydrazine hydrate and drying the catalyst; the HZSM-5 molecular sieve has a Si/Al ratio of 60, which is crystal rather than microcrystal aggregate, and has relative crystallinity of 96%, crystal grain number of 0.8-5 μm and external dimension of 98.4% and less than 0.5 μm, and its two main pore sizes of 0.53 x 0.56 and 0.51 x 0.55nm, and specific surface area of 380m ² Per gram, the external surface area of the crystal grain is 0.85m ² /g。

The powdery Pt/H beta molecular sieve catalyst is prepared by a method provided by Shandong Juxing New Material science and technology Co., ltd, according to an example 5 of CN201910196183.1, wherein the Pt content is 0.063wt%, is basically loaded into a pore canal in a grain of the H beta molecular sieve by a cation exchange method, and is obtained by reducing and drying hydrazine hydrate; the H beta molecular sieve has Si/Al ratio 40, relative crystallinity of 95%, crystal grain size of 0.8-5 μm of 97.4% and specific surface area 563m below 0.5 μm ² Per gram, the external surface area of the crystal grain is 0.95m ² /g。

The o-xylene, m-xylene, mesitylene, pseudocumene and ethylene oxide are all analytically pure (sulfur content is less than or equal to 1 ppm); the aromatic hydrocarbon oil A, B, C is prepared from two additional analytically pure toluene and ethylbenzene (the sulfur content is less than or equal to 1 ppm) in analytically pure o-xylene, m-xylene, mesitylene and mesitylene according to the mass ratio of 45:45:5:5, wherein the aromatic hydrocarbon oil A is prepared from o-xylene, m-xylene, toluene and ethylbenzene, the aromatic hydrocarbon oil B is prepared from m-xylene, mesitylene, toluene and ethylbenzene, and the aromatic hydrocarbon oil C is prepared from o-xylene, mesitylene, toluene and ethylbenzene.

Table 1 reaction feed ratio, mol unit

。

In the preparation process of the above examples 1 to 7, the reaction time when the reaction liquid was examined to have no ethylene oxide remained was 10 to 13 hours.

By association with analytically pure substancesPeak time contrast, judgment considers: the reaction products of examples 1 to 7 fully illustrate the reaction and effect of the polymethylbenzene with ethylene oxide described in the summary of the invention. Example 1-CH in the target reaction product of o-xylene with ethylene oxide ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection position with the 1, 2-dimethylphenyl is the 4-position of the benzene ring, and the chemical names are respectively 4- (1, 2-dimethylphenyl) -2-ethanol and 4- (1, 2-dimethylphenyl) -diethyl ether; EXAMPLE 3-CH in the target reaction product of mesitylene and ethylene oxide ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection position with the 1,2, 3-trimethylphenyl is the 5-position of benzene ring, and the chemical names are respectively 5- (1, 2, 3-triphenyl) -2-ethanol and 5- (1, 2, 3-trimethylphenyl) -diethyl ether; each of the liquid products obtained in examples 5 to 7 contained 4 kinds of polymethylphenyl ethanol and polymethylphenyl ethyl ether, which were respectively contained in the same manner as the target reaction products obtained in examples 1 to 4, but different from each other in terms of aromatic hydrocarbon composition.

The liquid products obtained in examples 1-7 were clear and transparent, and the weight ratio of the target products of the detection of the mixture of the polymethylphenyl ethanol and the polymethylphenyl ethyl ether was 58.5-61.3:8, calculating the ethylene oxide feeding, wherein the selectivity of the corresponding polymethylphenyl ethanol and polymethylphenyl ethyl ether is more than or equal to 99.2 percent, and the selectivity of the polymerization product of the ethylene oxide is less than or equal to 0.1 percent (the polymerization product is the di-polyether alcohol and the tri-polyether alcohol, and no more than four polyether alcohol products are detected); the liquid products obtained in examples 5-7 had selectivity to methyl phenyl ethanol, methyl phenyl ethyl ether, ethyl phenyl ethanol, ethyl phenyl ethyl ether of less than or equal to 0.2% based on the ethylene oxide feed.

In each liquid product prepared in the examples 1-4, the content of the polymethylphenyl ethanol and the polymethylphenyl ethyl ether is 72.6-73.5wt%, and the rest components are mainly xylene and trimethylbenzene which are not reacted, and no new aromatic hydrocarbon is detected to be generated outside the feeding; the content of the polymethylphenyl ethyl alcohol and the polymethylphenyl ethyl ether in each of the liquid products prepared in examples 5 to 7 is 66.1 to 66.9wt%; the rest components mainly comprise unreacted dimethylbenzene, trimethylbenzene, toluene and ethylbenzene, and no new aromatic hydrocarbon is detected to be generated outside the feeding.

In the preparation process of comparative example 1.1, the reaction time of the reaction liquid for detecting the residual of the ethylene oxide is 5 hours; the liquid product obtained contained o-dimethylphenylethanol, i.e. 4- (1, 2-dimethylphenyl) -2-ethanol, and o-dimethylphenylether, i.e. 4- (1, 2-dimethylphenyl) -diethyl ether, in a weight ratio of 60:22, calculated by ethylene oxide feeding, the selectivity of the o-dimethylphenylethanol and the o-dimethylphenylether is 90.5 percent, and the selectivity of the polymerization product of the ethylene oxide is 8.9 percent (the polymerization product is di-polyether alcohol, trimeric ether alcohol, tetra-polyether alcohol, pentapolyether alcohol and hexapolyether alcohol, wherein the selectivity of the tetra-polyether alcohol, the pentapolyether alcohol and the hexapolyether alcohol is 4.6 percent).

In the preparation process of comparative example 1.2, the reaction time of the reaction liquid for detecting the residual of the ethylene oxide is 6 hours; the liquid product obtained contained o-dimethylphenylethanol, i.e. 4- (1, 2-dimethylphenyl) -2-ethanol, and o-dimethylphenylether, i.e. 4- (1, 2-dimethylphenyl) -diethyl ether, in a weight ratio of 60:30, calculated by ethylene oxide feeding, the selectivity of the o-dimethylphenylethanol and the o-dimethylphenylether is 96.1 percent, and the selectivity of a polymerization product of the ethylene oxide is 3.7 percent (the polymerization product is the polyether alcohol, the trimeric ether alcohol, the polyether alcohol and the polyether alcohol, wherein the selectivity of the polyether alcohol and the polyether alcohol is 1.4 percent).

Examples 8 to 22, comparative examples 2 to 11

The two gasoline blending component oils M, N used in the preparation of the low-ratio methanol gasoline of examples 8-22 and comparative examples 2-11 were prepared as shown in Table 2 by mixing the raw materials in the proportions by weight. The octane number (RON) of the resulting gasoline blend component M, N is 89-90.

Table 2 formulation of gasoline blending component oil M, N, parts by weight

。

40kg of low-proportion methanol gasoline of examples 8-22 and comparative examples 2-10 is prepared according to the proportion of the table 3; wherein the methanol is qualified product of industrial methanol meeting GB/T338-2011, and the water content is less than or equal to 0.20wt%; the metal corrosion inhibitor is benzotriazole and pyridone mixture powder with the weight ratio of 4.5:1, and is ground to 600 meshes after being uniformly mixed; the rubber expansion inhibitor adopts JH4012 of the Western An Jiahong technology Co. The preparation process comprises the following steps: and after nitrogen replacement in a stirring tank, sequentially adding required amount of methanol, an atomization combustion control agent, a metal corrosion inhibitor and a rubber expansion inhibitor, stirring for 30min until powder is completely dissolved and uniformly mixed, adding gasoline blending component oil, and stirring for 30min until the mixture is uniformly mixed, thus obtaining the low-proportion methanol gasoline.

The octane numbers (RON) of the methanol gasoline obtained in examples 8, 19, 21, 22 and comparative example 11 were 92.1, 95.0, 92.3, 95.5 and 93.8, respectively, and according to the practical experience of the applicant, the octane numbers (RON) of the low-ratio methanol gasoline obtained in examples 9 to 18 and comparative examples 2 to 8 were higher than 92, and the octane numbers (RON) of the low-ratio methanol gasoline obtained in examples 20 and comparative examples 9 to 10 were higher than 95.

Example 8, comparative example 11, made a significant difference in the octane number (RON) of methanol gasoline, demonstrating that the antiknock effect, i.e., octane number boosting effect, of 4- (1, 2-dimethylphenyl) -2-ethanol in these two methanol gasolines was much lower than that of the prior art (CN 109929622B, an ethanol gasoline dispersant and ethanol gasoline containing the dispersant), 2- (p-methylphenyl) -2-butanol; the obvious differences of the methanol gasoline prepared in the example 8 and the comparative example 11 in the application example 1 below in terms of engine oil consumption, noise level and idle speed also show that the atomization and combustion effects, namely the power effects, of 4- (1, 2-dimethylphenyl) -2-ethanol in the direct injection engine in the cylinder are obviously higher than those of 2- (p-methylphenyl) -2-butanol.

Table 3 low ratio methanol gasoline blend ratio

。

The methanol gasoline prepared in examples 8-22 was subjected to stability tests, respectively, the test methods and results included: (1) Each 500mL glass bottle is sealed under shading, and is placed for 30 days at the temperature of minus 20 ℃ and 30 ℃ respectively, and no visible change exists; (2) Each 500mL glass bottle is filled with 2mL water, and the glass bottles are uniformly mixed, shaded and sealed, and are respectively placed for 30 days at the temperature of minus 20 ℃ and 30 ℃ without visible change.

Application example 1

The low-proportion methanol gasoline of examples 8-22 and comparative examples 2-11 is applied and tested on a representative national six-vehicle in sequence (the engine is a four-cylinder 1.5L turbo-charging and direct injection in a cylinder, a 7-speed wet double-clutch automatic gearbox is provided with a particle catcher and an oil tank volume of 55L), and each methanol gasoline is prepared 15-17 days before test and use; and (5) examining the performance of each methanol gasoline in the aspects of engine power performance, oil consumption and noise. The vehicle age of the vehicle before the test is 15 months, the six gasoline of China No. 92 is added to drive 31000km, the SP grade total synthetic engine oil with proper viscosity is adopted, the oil-gas separator is normal in effect, the engine state is good, the engine oil is not burned, and carbon deposition in a checking cylinder, an air inlet manifold and the back surface carbon deposition of an air inlet valve are very slight. The test takes 5 months, and runs for 24000km altogether, wherein the former 6000km is firstly added with Chinese hexapetrol of No. 92 for running 3800km, then added with Chinese hexapetrol of No. 95 for running 2200km, and then added with low-proportion methanol petrol of examples 8-22 and comparative examples 2-11 for running 18000km, wherein the methanol petrol of example 8 and comparative example 4 is respectively replaced by more than 4 holes after the first test to reach more efficient fuel injection nozzles, and the fuel injection nozzles are replaced by the original fuel injection nozzles after the first test; the air temperature is 20-25 ℃ and the air speed is less than or equal to 6m/s during the test; the air quality of the driving route is high for most of time, and is good for less part of time, and slight or more haze does not occur and sand dust does not meet; the intake filter is replaced once every 4000km, the same engine oil is replaced once every 6000km, and the test effect of 100km after the intake filter and the engine oil are replaced is not included in statistical calculation. In the test process, the driving mileage of the vehicle at the constant speed of 60km/h, 80 km/h and 100 km/h and the wind speed of less than or equal to 3.3m/s is ensured to be more than 18000 km. The purpose of using SP grade total synthetic engine oil is to avoid the effect of carbon dust on the particle catcher that might be produced by slightly burning the engine oil.

The test items include: (1) Engine power consumption and noise comparison at the constant speed of 60km/h, 80 km/h and 100 km/h of the basically horizontal newly built asphalt pavement highway; (2) The engine oil consumption and noise comparison are carried out when the speed of a newly built asphalt pavement long slope highway with the gradient of about 3% is fixed by 60km/h, 80 km/h and 100 km/h; (3) comparing the idle speed of the engine after 50km of running; (4) comparing the burnt carbon regeneration conditions of the particle catcher; (5) carbon deposition in the cylinder after the test.

The test results include the following.

(1) When the constant speed of the newly built asphalt pavement road is 60km/h, 80 km/h and 100 km/h, the average value of each oil consumption of the engine is reduced by more than 5% when 92 # methanol gasoline of examples 8-18 and 21 is added, and the noise level of the engine is equal to or slightly lower than that when 92 # gasoline is added at the initial stage; when the 92 # methanol gasoline of the comparative examples 2-3, 5-7 and 11 is added, the average value of the oil consumption of the engine is reduced by 0-2% compared with that of the 92 # gasoline added in the initial stage, and the noise level of the engine is equivalent or slightly higher; when 92 # methanol gasoline of comparative examples 4 and 8 is added, the average value of each oil consumption of the engine is improved by 1-2% compared with that of the initial 92 # gasoline, and the noise level of the engine is obviously higher. When the 95 # methanol gasoline of the examples 19-20 and 22 is added, the average value of each oil consumption of the engine is lower than that when the 95 # methanol gasoline is added in the initial stage, the increase amplitude is lower than that when the 95 # methanol gasoline is added in the initial stage, and the noise level of the engine is equal to or slightly lower than that; when 95 # methanol gasoline of comparative examples 9-10 was added, the average value of each fuel consumption of the engine was increased by 10-15% compared with the initial addition of 95 # gasoline, and the noise level of the engine was comparable or slightly higher. Wherein the fuel consumption of the methanol gasoline of example 8 when the high-efficiency fuel injection nozzles are replaced respectively after the first test is reduced by less than 1% compared with the fuel consumption of the original fuel injection nozzles, and the fuel consumption of the methanol gasoline of comparative example 4 when the high-efficiency fuel injection nozzles are replaced respectively after the first test is reduced by about 2%.

(2) When the new asphalt pavement long-slope highway with the gradient of about 3% is subjected to constant speed of 60km/h, 80 km/h and 100 km/h, the average fuel consumption of the engine is reduced by more than 6% when 92 # methanol gasoline of examples 8-18 and 21 is added, and the noise level of the engine is equivalent or slightly lower than that when 92 # gasoline is added at the initial stage; when the 92 # methanol gasoline of the comparative examples 2-3, 5-7 and 11 is added, the average value of the oil consumption of the engine is reduced by 1-3% compared with that of the 92 # gasoline added in the initial stage, and the noise level of the engine is equivalent or slightly higher; when the 92 # methanol gasoline of the comparative examples 4 and 8 is added, the average value of each oil consumption of the engine is improved by 2-4% compared with the initial 92 # gasoline, and the noise level of the engine is obviously higher. When the 95 # methanol gasoline of the examples 19-20 and 22 is added, the average value of each oil consumption of the engine is lower than 7% when the 95 # methanol gasoline is added in the initial stage, and the noise level of the engine is equivalent; when 95 # methanol gasoline of comparative examples 9-10 is added, the average value of each oil consumption of the engine is improved by 16-20% compared with that of the initial 95 # gasoline, and the noise level of the engine is slightly higher. Wherein the fuel consumption of the methanol gasoline of example 8 when the high-efficiency fuel injection nozzles are replaced respectively after the first test is reduced by less than 1% compared with the fuel consumption of the original fuel injection nozzles, and the fuel consumption of the methanol gasoline of comparative example 4 when the high-efficiency fuel injection nozzles are replaced respectively after the first test is reduced by about 3%.

(3) The idling speed of the engine after 50km running is reduced by 30-50rpm when the No. 92 methanol gasoline of examples 8-18 and 21 is added compared with the No. 92 gasoline at the initial stage of the test; the addition of 92 # methanol gasoline of comparative examples 2-3, 5-7, 11 decreased by 10-25rpm; the addition of 92 methanol gasoline of comparative examples 4 and 8 increased 20-40rpm. The increase in the speed of the methanol gasoline of examples 19 to 20 and 22 was 20 to 40rpm compared to the initial addition of the gasoline of 95; the addition of the methanol gasoline No. 95 of comparative examples 9 to 10 increased the speed by 60 to 80rpm.

(4) During the test of adding methanol gasoline, no prompt of carbon burning regeneration of the particle catcher is found; during the period of adding No. 92 and No. 95 gasoline in the initial stage, the particle catcher is found to be prompted for 3 times in the carbon burning regeneration, and the particle catcher runs until the carbon burning regeneration is finished every time, wherein the power output of an engine is seriously influenced for 1 time.

(5) After the test of adding methanol gasoline is finished, the carbon deposition condition in each cylinder is checked through a spark plug hole inner peeping head, and the slight carbon deposition on the surfaces of the spark plug and the oil nozzle, the inner wall of the upper part of the cylinder and the top surface of the piston is basically removed.

Application example 2

The methanol gasoline of the examples 8 and 22 is respectively prepared into 200kg each time, and the continuous adding effect of the methanol gasoline under the normal use condition is inspected on 6 representative vehicles respectively; the engine of the 6 vehicles is not burned engine oil, wherein the 1 st vehicle is a vehicle with four cylinders of 1.5L turbocharging, direct injection in the cylinders and particle catcher configured in application example 1, the 2 nd vehicle is a vehicle with four cylinders of 2.0L turbocharging, direct injection in the cylinders and particle catcher configured in the cylinders, the 3 rd vehicle is a vehicle with four cylinders of 1.5L turbocharging, direct injection in the cylinders configured in the cylinders, the 4 th vehicle is a vehicle with four cylinders of 1.5L turbocharging, multi-point electric injection in an air inlet manifold configured in the cylinders of 2.0L natural air suction and multi-point electric injection in the air inlet manifold configured in the cylinders of 5 th vehicle, the 6 th vehicle is a vehicle with four cylinders of 1.6L natural air suction and multi-point electric injection in the air inlet manifold configured in the cylinders of 1.0L, 2 and 5 vehicles have a constant-speed cruising function, and the 1,2 and 5 vehicles have accurate valve control technologies.

The ages of the 2 nd to 6 th vehicles before the test are respectively 10, 13, 45, 16 and 51 months, the driving mileage is 16000, 20000, 72000, 24000 and 118000km, the engine state is good, the carbon deposition in the checking cylinder, the carbon deposition on the back of the air inlet manifold and the air inlet valve are light, the effect of the oil-gas separator is normal, and the SP-grade total synthetic engine oil with proper viscosity is respectively replaced before the test. The test is finished when the 6 vehicles all run for 26000km, and the time is 5-8 months; wherein the first 6000km is firstly driven by adding the Chinese hexapetrol of 92 # and then by adding the Chinese hexapetrol of 95 # to drive 3000km, then by adding the methanol petrol of 92 # of example 8 to drive 10000km, and then by adding the methanol petrol of 95 # of example 22 to drive 10000km; the temperature is 20-35 ℃ during driving, the wind speed is less than or equal to 10m/s, but only the test effect condition is recorded when the wind speed is less than or equal to 3.3 m/s; the air quality of the driving route is high for most of time, and is good for less part of time, and severe or more haze and sand dust are not generated; the intake filter is replaced once every 5000km, the same engine oil is required to be replaced once every 6000km, and the test effect of 100km after the intake filter and the engine oil are replaced is not included in statistical calculation. The test items include: (1) Engine power consumption and noise comparison at the constant speed of 60km/h, 80 km/h and 100 km/h of the basically horizontal newly built asphalt pavement highway; (2) The engine oil consumption and noise comparison are carried out when the speed of a newly built asphalt pavement long slope highway with the gradient of about 3% is fixed by 60km/h, 80 km/h and 100 km/h; (3) comparing the idle speed of the engine after 50km of running; (4) Comparing the special carbon burning regeneration conditions when the particle catcher exists; (5) And comparing the carbon accumulation condition in the cylinder after the test with that of the previous 6000km plus the running of the national six-gasoline. In the test process, the driving mileage of each vehicle at the constant speed of 60km/h, 80 km/h and 100 km/h and the wind speed of less than or equal to 3.3m/s is ensured to be more than 20000 km.

The test results include the following.

(1) When the constant speed of the newly built asphalt pavement road is 60km/h, 80 km/h and 100 km/h, the average value of each oil consumption of the engine is reduced by more than 4% when the 92 # methanol gasoline of the example 8 is added, and the noise level of the engine is equal to or slightly lower than that when the 92 # gasoline is added at the initial stage; when the 95 # methanol gasoline of example 22 was added, the average value of each fuel consumption of the engine was lower than 8% when the 95 # gasoline was added at the initial stage, and the noise level of the engine was equal to or slightly lower.

(2) When the new asphalt pavement long-slope highway with the gradient of about 3% is subjected to constant speed of 60km/h, 80 km/h and 100 km/h, the average fuel consumption of the engine is reduced by more than 5% when 92 # methanol gasoline of the example 8 is added, and the noise level of the engine is equal to or slightly lower than that when 92 # gasoline is added at the initial stage; when the 95 # methanol gasoline of example 22 was added, the average value of fuel consumption of the engine was lower than 9% when the 95 # gasoline was added at the initial stage, and the noise level of the engine was equivalent.

(3) The idle speed of the engine after running for 50km was reduced by 30 to 50rpm when No. 92 or No. 95 of the methanol gasoline of example 8 was added, and increased by 20 to 40rpm when No. 95 of the methanol gasoline of example 22 was added, as compared with the case when No. 92 or No. 95 of the gasoline was added at the initial stage of the test.

(4) During the test of adding methanol gasoline to the 1 st and 2 nd vehicles, no prompt of carbon burning regeneration of the particle catcher is found; during the initial addition of No. 92 and No. 95 gasoline, the particle catcher is found to be prompted 5 times in the carbon burning regeneration, and the particle catcher runs until the carbon burning regeneration is finished, wherein the power output of the engine is seriously affected 3 times.

(5) After the test is finished, the spark plug in each cylinder, the surface of the oil nozzle, the inner wall of the upper part of the cylinder and the carbon deposit on the top surface of the piston are inspected by a spark plug hole inner probe, and the 1 st vehicle is found to be completely removed, the 2 nd to 6 th vehicles are obviously reduced compared with the vehicle before methanol gasoline is used, and the carbon deposit in each cylinder is basically removed.

Claims

1. A low-proportion methanol gasoline for car contains methanol (10-30 wt.%), atomized combustion controller (0.1-0.5), metal corrosion inhibitor (0.02-0.1), rubber expansion inhibitor (0.02-0.2) and gasoline as additiveAn oil; the control agent for atomized combustion comprises polymethylphenyl ethanol ((CH) ₃ ) _X -C ₆ H _6-X-1 )-CH ₂ -CH ₂ -OH, polymethylphenyl ethyl ether ((CH) ₃ ) _X -C ₆ H _6-X-1 )-O-CH ₂ -CH ₃ The weight ratio of diethyl malonate is 50-75:5-15:10-25, and the total content of the polymethylphenyl ethanol, the polymethylphenyl ethyl ether and the diethyl malonate is more than or equal to 60wt%, wherein X=2 or 3; the polymethylphenyl group is an o-dimethylphenyl or m-dimethylphenyl group when x=2, and the-CH when o-dimethylphenyl ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection position with benzene ring is 4-position, and is-CH when being m-dimethylphenyl ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection position with the benzene ring is 5; when x=3, the polymethylphenyl group is a mesityl group or a trimethiyl group, the-CH ₂ -CH ₂ -OH or-O-CH ₂ -CH ₃ The connection positions of the benzene ring and the benzene ring are all 5 positions;

the preparation method of the polymethylphenyl ethanol and polymethylphenyl ethyl ether in the atomized combustion control agent comprises the following steps: mixing one or more of o-xylene, m-xylene, mesitylene and mesitylene or aromatic hydrocarbon oil containing more than 80wt% of the poly-methyl benzene with ethylene oxide according to a required proportion, adding a powdery Pt/HZSM-5 molecular sieve catalyst, reacting at a temperature of 30-40 ℃ under a liquid phase condition for 8-20h under stirring, separating the Pt/HZSM-5 molecular sieve catalyst after the reaction until the ethylene oxide is completely converted, and obtaining a reaction generating solution containing poly-methyl phenyl ethanol, poly-methyl phenyl ether and the rest poly-methyl benzene or the aromatic hydrocarbon oil rest material in a weight ratio of 50-75:5-15; the dosage of the Pt/HZSM-5 molecular sieve catalyst in the reaction is 3-10wt% of the total dosage of the polymethylbenzene and the ethylene oxide liquid; the Pt content of the Pt/HZSM-5 molecular sieve catalyst is 0.05-0.1wt%, and the catalyst is loaded into a pore canal in a crystal grain of the HZSM-5 molecular sieve by a cation exchange method, and is obtained by reducing and drying hydrazine hydrate; the HZSM-5 molecular sieve has a silicon-aluminum ratio of 60-120, is a crystal rather than a microcrystalline aggregate, has a relative crystallinity higher than 95%, has a grain number of 0.8-5 μm in an overall dimension of more than 95% and less than 1% of the total grain number, and has two main pore sizes of 0.53×0.56nm and 0.51×0.55nm respectively;

in the preparation process of the polymethylphenyl ethanol and the polymethylphenyl diethyl ether, the feeding ratio of the polymethylbenzene or the polymethylbenzene contained in the aromatic hydrocarbon oil to the mass of the ethylene oxide is 100:50-75.

2. The low-ratio methanol gasoline for vehicles according to claim 1, wherein the weight ratio of the polymethylphenyl ethanol, the polymethylphenyl ethyl ether, and the diethyl malonate in the atomized combustion control agent is 55-70:8-10:12-15.

3. The low-ratio vehicular methanol gasoline as in claim 1 wherein the weight ratio of methanol to atomized combustion control agent is 100:1.0-2.0.

4. The low-ratio vehicular methanol gasoline as in claim 1 wherein the gasoline blend component oil comprises, in parts by weight, 20-30 parts naphtha, 20-30 parts raffinate, 10-20 parts 120 # solvent oil, 8-15 parts alkylate, 5-20 parts aromatized oil.

5. The low-proportion methanol gasoline for vehicles according to claim 1, wherein the metal corrosion inhibitor is a mixture of benzotriazole and pyridone in a weight ratio of 3-6:1; the rubber expansion inhibitor is JH4012 of the Western An Jiahong technology Co.

6. The low-ratio vehicular methanol gasoline as in claim 1, wherein the methanol comprises vehicular fuel methanol conforming to GB/T23510-2009, and qualified, first-grade or superior methanol for GB/T338-2011 industry.