Alcohol-based vehicle clean fuel and preparation method thereof

Abstract

The invention provides an alcohol-based automotive clean fuel and a preparation method thereof. The alcohol-based fuel comprises the following components in parts by weight: 60-90 parts of methanol, 2-10 parts of ethanol, 1-5 parts of multi-carbon alcohol, 5-15 parts of aliphatic ether, 0.2-2 parts of a catalyst, 2-6 parts of peroxide and 1-3 parts of a corrosion inhibitor. The alcohol-based fuel prepared by the invention has a relatively high octane number, which shows that the anti-knock property is good, and knock is not easy to occur when the alcohol-based fuel is used in an engine; the sulfur content is relatively low, so that the corrosion to engine parts can be reduced, the emission of sulfur dioxide is reduced, and the environmental pollution is reduced; the density is relatively high, so that the combustion heat value can be improved, and the stability in the storage and transportation processes is higher; the copper sheet corrosion grade is low, which shows that the corrosion to metal is low; compared with the prior art, the alcohol-based fuel has low emission of HC, CO and NOx, which indicates that the alcohol-based fuel is greener and cleaner, and the raw materials such as methanol and ethanol can be prepared from renewable resources such as wood chips, corncobs, cereals and straws, so that the requirement of sustainable development is met.

Description

Technical Field

[0001] The invention belongs to the technical field of alcohol-based fuels, and in particular relates to an alcohol-based clean fuel for vehicles and a preparation method thereof. Background Art

[0002] Energy is a key factor supporting human production and life, and is also an important material basis for national economic development. At present, global energy consumption mainly relies on fossil fuels such as coal, oil and natural gas, and these primary energy sources constitute the main body of global energy supply. my country is a typical country that is poor in oil, poor in gas and rich in coal. Moreover, as the world's most populous country, the per capita reserves of various major resources are far lower than the world's per capita level. In the energy consumption structure, the demand for oil in the transportation sector, especially automobiles, continues to grow, which makes the supply and demand of oil particularly prominent in my country. In the face of the challenges of the 21st century, my country must gradually adjust the energy structure of vehicle use according to its own resource conditions and energy characteristics, and actively develop and promote clean alternative fuels to meet the energy needs of the post-oil era.

[0003] Alcohol is a flammable liquid oxygen-containing fuel and is considered a promising alternative "clean fuel" for vehicles. In particular, alcohol fuel made from biomass is a renewable "green energy" that can reduce the emission of harmful substances such as carbon oxides and nitrogen oxides, and reduce air pollution.

[0004] The main alcohol fuels currently used are methanol and ethanol. When pure methanol or pure ethanol is used as engine fuel, the engine needs to be modified. In addition, alcohol fuels themselves contain oxygen and are prone to produce unconventional emissions such as formic acid and formaldehyde during combustion. These substances are corrosive to the engine. Therefore, the conventional method in the prior art is to mix alcohols in different proportions with other substances for use as fuel. However, there are still problems such as poor anti-knock performance, high corrosiveness, and emissions that are more harmful to the environment and human health.

[0005] In view of the problems existing in the prior art, how to provide an alcohol-based fuel with good anti-knock performance, low corrosiveness, high combustion heat, and green and cleanness is a problem to be solved urgently in the present invention. Summary of the invention

[0006] The object of the present invention is to provide an alcohol-based clean fuel for vehicles and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0007] To achieve the above object, the present invention provides an alcohol-based clean fuel for vehicles, characterized in that it comprises the following components in parts by weight: 60-90 parts of methanol, 2-10 parts of ethanol, 1-5 parts of polyols, 5-15 parts of aliphatic ethers, 0.2-2 parts of catalysts, 2-6 parts of peroxides, and 1-3 parts of corrosion inhibitors;

[0008] The catalyst is a copper-nickel-zirconium complex;

[0009] The corrosion inhibitor is chitosan modified by piperazine amine methylation product.

[0010] As a further improvement, the synthesis of the catalyst comprises the following steps:

[0011] (1) The activated alumina balls were washed three times with deionized water and anhydrous ethanol, then dried in an oven at 100-130° C., and finally activated in a muffle furnace at 300-500° C. for 2-5 hours, and then naturally cooled to room temperature before being taken out;

[0012] (2) adding copper nitrate trihydrate, nickel nitrate hexahydrate and zirconium nitrate pentahydrate into deionized water and mixing them, then adding the substance obtained in step (1) into the mixed solution, impregnating for 12-24 hours at room temperature, and post-treating to obtain a catalyst.

[0013] As a further improvement, the molar addition ratio of the copper nitrate trihydrate, nickel nitrate hexahydrate and zirconium nitrate pentahydrate is 5-8:2:1.

[0014] As a further improvement, the synthesis of the corrosion inhibitor comprises the following steps:

[0015] (1) adding thionyl chloride to kojic acid, placing the mixture in a fume hood and stirring for 10-30 min at room temperature, completing the reaction, and performing post-treatment to obtain purified chlorokojic acid;

[0016] (2) adding the purified chlorokojic acid and N-methylpiperazine obtained in step (1) to an organic solvent, rapidly stirring at room temperature for 20-40 minutes, completing the reaction, and post-treating to obtain a piperazine amine methylation product;

[0017] (3) The piperazine amine methylation product obtained in step (2) and chitosan are dissolved in organic solvents to prepare a piperazine amine methylation product solution and a chitosan solution, and then the chitosan solution is slowly added dropwise to the piperazine amine methylation product solution, and pyridine is added, and the reaction is stirred for 2-5 hours. After the reaction is completed, post-treatment is performed to obtain a corrosion inhibitor.

[0018] As a further improvement, the polyol is a C3-C8 fatty alcohol.

[0019] As a further improvement, the polyol is at least one of n-butanol, n-pentanol, n-octanol, isooctyl alcohol, and 2-ethylhexanol.

[0020] In order to have a higher combustion calorific value, preferably, the polyol is 2-ethylhexanol.

[0021] As a further improvement, the aliphatic ether is a C2-C8 aliphatic ether.

[0022] As a further improvement, the aliphatic ether is at least one of dimethyl ether, methyl tert-butyl ether, ethyl propyl ether, and methyl tert-amyl ether.

[0023] In order to improve the mutual solubility and combustion characteristics, preferably, the aliphatic ether is dimethyl ether and methyl tert-butyl ether.

[0024] As a further improvement, the peroxide is at least one of hydrogen peroxide, tert-butyl hydroperoxide, and di-tert-butyl peroxide.

[0025] In order to have better stability, preferably, the peroxide is di-tert-butyl peroxide.

[0026] The present invention provides a method for preparing an alcohol-based clean fuel for vehicles, characterized in that it comprises the following steps:

[0027] Firstly, polyol, aliphatic ether, catalyst and corrosion inhibitor are mixed according to weight proportions, then methanol and ethanol are added and continue to mix, and finally peroxide is added and stirred to obtain alcohol-based clean fuel for vehicles.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The present invention provides an alcohol-based clean fuel for vehicles and a preparation method thereof, so that the prepared alcohol-based fuel has a higher octane number, indicating good anti-knock property, is not prone to knock when used in an engine, and is helpful to improve engine performance and reduce wear; has a lower sulfur content, indicating that the content of sulfur and its derivatives in the alcohol-based fuel is less, which can reduce corrosion to engine parts, and the emission of sulfur dioxide generated during combustion is low, reducing environmental pollution; has a higher density, indicating that the alcohol-based fuel contains higher energy per unit mass, can improve the combustion calorific value, is more stable during storage and transportation, and is helpful to reduce losses; has a lower copper sheet corrosion level to a certain extent, indicating that the alcohol-based fuel is less corrosive to metals during storage, transportation and use;

[0030] The alcohol-based fuel prepared by the present invention also has lower HC, CO, and NO x The emission volume shows that the alcohol-based fuel is greener and cleaner, and will not produce smog, acid rain and other hazards to the environment and human health. Among them, methanol and ethanol, as the main substances of alcohol-based fuels, can be produced from renewable resources such as wood chips, corn cobs, grains, and straw, which meets the requirements of green and clean production and promotes sustainable development. DETAILED DESCRIPTION

[0031] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0032] In the following examples, except for the catalyst and corrosion inhibitor, the other compound monomers and related reagents used can be purchased from the market, among which alumina balls were purchased from Shandong Shanruo Environmental Technology Co., Ltd., and chitosan was purchased from Huaian Runjie Industry and Trade Co., Ltd.

[0033] The synthesis of the catalyst comprises the following steps:

[0034] (1) 50 g of activated alumina balls were washed three times with deionized water and anhydrous ethanol, respectively, and then dried in an oven at 110° C. for 11 h. Finally, they were activated in a muffle furnace at 500° C. for 4 h, and naturally cooled to room temperature before being taken out;

[0035] (2) 0.3 mol of copper nitrate trihydrate, 0.1 mol of nickel nitrate hexahydrate, and 0.05 mol of zirconium nitrate pentahydrate were added to 200 mL of deionized water and mixed. The substance obtained in step (1) was then added to the mixture. After being immersed at room temperature for 24 hours, the mixture was placed in an oven at 110° C. for overnight drying. The mixture was then calcined at 450° C. for 3 hours to obtain a catalyst.

[0036] The synthesis of the corrosion inhibitor includes the following steps:

[0037] (1) 150 mL of thionyl chloride was added to 71.1 g of kojic acid, and the mixture was stirred in a fume hood at room temperature for 20 min. The obtained solid was washed with petroleum ether and filtered until the filtrate was colorless. The solid was recrystallized in boiling water to obtain purified chlorokojic acid;

[0038] (2) 48.0 g of the purified chlorokojic acid obtained in step (1) and 30.0 g of N-methylpiperazine were added to 150 mL of methanol and 10 mL of formaldehyde aqueous solution, and the mixture was rapidly stirred at room temperature for 30 min. After the reaction was completed, a brown precipitate was generated. The precipitate was collected by filtration and washed with anhydrous methanol to obtain a piperazine amine methylation product;

[0039] (3) 30 g of the piperazine amine methylation product obtained in step (2) and 20 g of chitosan were dissolved in 50 mL of N,N-dimethylformamide to prepare a piperazine amine methylation product solution and a chitosan solution, and then the chitosan solution was slowly added dropwise to the piperazine amine methylation product solution, and then 10 mL of pyridine was added, and the reaction was stirred for 4 h. After the reaction was completed, 50 mL of acetone was added to terminate the reaction, and the solid precipitate was filtered to obtain a solid precipitate, and Soxhlet extraction was performed with dimethyl ketone as an extracting solution for 24 h, DMF was removed, and finally vacuum drying was performed to obtain a corrosion inhibitor.

[0040] The preparation methods of Examples 1-3 and Comparative Examples 1-2 comprise the following steps:

[0041] According to weight proportions, polyols, aliphatic ethers, catalysts and corrosion inhibitors are first mixed and stirred for 10 minutes, then methanol and ethanol are added and the mixture is continued to be mixed for 10 minutes, and finally peroxide is added and stirred and mixed for 30 minutes to obtain alcohol-based clean fuel for vehicles.

[0042] The components and contents used in Examples 1-3 and Comparative Examples 1-2 are shown in Table 1 below:

[0043] Table 1

[0044]

[0045]

[0046] The alcohol-based clean fuels for vehicles prepared in Examples 1-3 and Comparative Examples 1-2 were tested according to the inspection methods and quality indicators specified in national standards. In particular, according to GB 18352.3-2005, a Jetta FV7160CIXE vehicle was used to conduct a post-start exhaust pollutant emission test at room temperature, and the HC, CO, NO x emissions;

[0047] The test results are shown in Table 2-3, as follows:

[0048] Table 2

[0049]

[0050] Table 3

[0051]

[0052]

[0053] It can be seen from Example 2 and Comparative Examples 1-2 in Table 2 that, compared with the alcohol-based fuel prepared by using conventional catalysts such as ferrocene, or using unmodified chitosan as a buffer, the alcohol-based fuel prepared by using a copper-nickel-zirconium complex as a catalyst and using chitosan modified by a piperazine amine methylation product as a corrosion inhibitor has a higher octane number, indicating that the anti-knock property is good, and knock is not likely to occur when used in an engine, which helps to improve the performance of the engine and reduce wear; it has a lower sulfur content, indicating that the content of sulfur and its derivatives in the alcohol-based fuel is less, and the emission of sulfur dioxide generated during combustion is low, reducing environmental pollution; it has a higher density, indicating that the alcohol-based fuel contains higher energy per unit mass, can improve the combustion calorific value, is more stable during storage and transportation, and helps to reduce losses; it has a lower copper sheet corrosion level to a certain extent, indicating that the alcohol-based fuel is less corrosive to metals during storage, transportation and use.

[0054] From the comparison between Example 2 and Comparative Examples 1-2 in Table 3 and the 92# gasoline sold on the market, it can be seen that the alcohol-based fuel prepared by the present invention has lower HC, CO, NO and other emissions after combustion. x The emission volume shows that the alcohol-based fuel is greener and cleaner, and will not produce smog, acid rain and other hazards to the environment and human health. Among them, methanol and ethanol, as the main substances of alcohol-based fuels, can be produced from renewable resources such as sawdust, corn cobs, grains, straw, etc., meeting the requirements of green and clean production and promoting sustainable development.

[0055] It can be seen from the test results of Examples 1-3 that the alcohol-based clean fuel for vehicles prepared by the preparation method provided by the present invention has a higher octane number, indicating that the anti-knock property is good and knock is not likely to occur when used in the engine; it has a lower sulfur content, indicating that the emission of sulfur dioxide generated when the alcohol-based fuel is burned is low and environmental pollution is reduced; it has a higher density, indicating that the alcohol-based fuel can increase the combustion calorific value and is more stable during storage and transportation; it has a lower copper sheet corrosion level to a certain extent, indicating that the alcohol-based fuel is less corrosive to metals during storage, transportation and use; it has lower HC, CO, NO x The emissions show that the alcohol-based fuel is greener and cleaner, and raw materials such as methanol and ethanol can be produced from renewable resources such as wood chips, corn cobs, grains, and straw, promoting sustainable development.

[0056] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. An alcohol-based clean fuel for vehicles, characterized in that: The invention comprises the following components in parts by weight: 60-90 parts of methanol, 2-10 parts of ethanol, 1-5 parts of polyols, 5-15 parts of aliphatic ethers, 0.2-2 parts of catalysts, 2-6 parts of peroxides, and 1-3 parts of corrosion inhibitors; The catalyst is a copper-nickel-zirconium complex; The corrosion inhibitor is chitosan modified by piperazine amine methylation product.

2. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The synthesis of the catalyst comprises the following steps: (1) The activated alumina balls were washed three times with deionized water and anhydrous ethanol, then dried in an oven at 100-130° C., and finally activated in a muffle furnace at 300-500° C. for 2-5 hours, and then naturally cooled to room temperature before being taken out; (2) adding copper nitrate trihydrate, nickel nitrate hexahydrate and zirconium nitrate pentahydrate into deionized water and mixing them, then adding the substance obtained in step (1) into the mixed solution, impregnating for 12-24 hours at room temperature, and post-treating to obtain a catalyst.

3. The alcohol-based clean fuel for vehicles according to claim 2, characterized in that: The molar addition ratio of the copper nitrate trihydrate, nickel nitrate hexahydrate and zirconium nitrate pentahydrate is 5-8:2:

1.

4. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The synthesis of the corrosion inhibitor comprises the following steps: (1) adding thionyl chloride to kojic acid, placing the mixture in a fume hood and stirring for 10-30 min at room temperature, completing the reaction, and performing post-treatment to obtain purified chlorokojic acid; (2) adding the purified chlorokojic acid and N-methylpiperazine obtained in step (1) to an organic solvent, rapidly stirring at room temperature for 20-40 minutes, completing the reaction, and post-treating to obtain a piperazine amine methylation product; (3) The piperazine amine methylation product obtained in step (2) and chitosan are dissolved in organic solvents to prepare a piperazine amine methylation product solution and a chitosan solution, and then the chitosan solution is slowly added dropwise to the piperazine amine methylation product solution, and pyridine is added, and the reaction is stirred for 2-5 hours. After the reaction is completed, post-treatment is performed to obtain a corrosion inhibitor.

5. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The polyol is a C3-C8 fatty alcohol.

6. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The polyol is at least one of n-butanol, n-pentanol, n-octanol, isooctyl alcohol and 2-ethylhexanol.

7. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The aliphatic ether is a C2-C8 aliphatic ether.

8. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The aliphatic ether is at least one of dimethyl ether, methyl tert-butyl ether, ethyl propyl ether and methyl tert-amyl ether.

9. The alcohol-based clean fuel for vehicles according to claim 1, characterized in that: The peroxide is at least one of hydrogen peroxide, tert-butyl hydroperoxide and di-tert-butyl peroxide.

10. The method for preparing an alcohol-based clean fuel for vehicles according to any one of claims 1 to 9, characterized in that: The following steps are involved: Firstly, polyol, aliphatic ether, catalyst and corrosion inhibitor are mixed according to weight proportions, then methanol and ethanol are added and continue to mix, and finally peroxide is added and stirred to obtain alcohol-based clean fuel for vehicles.

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