CN117264667A

CN117264667A - Biological methanol fuel and preparation method thereof

Info

Publication number: CN117264667A
Application number: CN202311138476.7A
Authority: CN
Inventors: 姜玉辉
Original assignee: Jinjiuzhou New Energy Co ltd
Current assignee: Jinjiuzhou New Energy Co ltd
Priority date: 2023-09-05
Filing date: 2023-09-05
Publication date: 2023-12-22

Abstract

The invention belongs to the technical field of methanol fuel. The invention provides a biological methanol fuel which comprises the following raw materials in parts by mass: 85-95 parts of methanol, 3-6 parts of biomass oil, 1-3 parts of modifier, 1-2 parts of metal preservative, 1-2 parts of combustion improver and 1-2 parts of calorific value agent; the biomass oil is obtained by sequentially pyrolyzing, cooling and high-pressure hydrogenating biomass. The invention also provides a preparation method of the biological methanol fuel. The invention reasonably controls the dosage of each component, the process steps and the parameters by reasonably selecting each component, and obviously improves the performance of the biological methanol fuel. The biological methanol fuel can replace gasoline by 100%, has good storage stability, low-temperature startability and antiknock property, high combustion efficiency, low corrosiveness to an oil way system and an engine, reduced waste emission and environmental friendliness.

Description

Biological methanol fuel and preparation method thereof

Technical Field

The invention relates to the technical field of methanol fuel, in particular to a biological methanol fuel and a preparation method thereof.

Background

With the serious consumption of petroleum energy and the increasing awareness of environmental protection, the search for alternative clean energy has become a hot spot topic today. Methanol is used as fuel and has the following characteristics: the methanol has small molecular mass, simple molecular structure, methanol oxygen content up to 50%, wider ignition limit and high combustion speed, and is beneficial to reducing the emission of carbon smoke; the octane number is high, and the antiknock performance is strong; the boiling point and the solidifying point of the methanol are low, the former can enable the fuel-air mixture to be formed faster and more uniformly, the complete combustion is facilitated, and the latter can ensure that the engine works at low temperature; the gasification potential heat value of the methanol is high, and when the mixed gas is formed, the air inlet temperature can be reduced, so that the air charging coefficient is improved, the combustion performance of the engine can be improved to a certain extent, the thermal efficiency is improved, and the formation of NO and soot can be inhibited by reducing the air inlet temperature; the minimum ignition energy of methanol is lower, and the propagation speed of flame is faster during combustion. Methanol is a promising alternative energy source because of its good combustion performance.

The blending use of methanol and gasoline can reduce the emission of automobile exhaust, enhance the antiknock performance and improve the combustion performance. However, methanol gasoline has a plurality of technical problems, firstly, the polarity of methanol is strong, water is easy to be absorbed, and when the content of methanol in the methanol gasoline is high, water absorption layering is easy to occur; secondly, methanol has swelling property on the rubber part, so that the rubber part of the automobile oil supply system is swelled, softened and cracked; meanwhile, methanol has certain corrosiveness to metal, permanent damage can be caused to an engine, driving safety is affected, and the methanol gasoline has the defects of insufficient power of oleyl alcohol, large oil consumption and the like, so that the technical problems restrict the large-scale use of the methanol gasoline.

Therefore, the biological methanol fuel which can replace the gasoline by 100 percent, improve the combustion efficiency, reduce the polarity and corrosiveness and reduce the tail gas emission is researched and obtained, and has important value.

Disclosure of Invention

The invention aims to provide a biological methanol fuel and a preparation method thereof, which aims to overcome the defects in the prior art, reduce the corrosiveness of the fuel, improve the storage stability and the combustion efficiency and reduce the emission of polluted gas.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a biological methanol fuel which comprises the following raw materials in parts by mass:

85-95 parts of methanol, 3-6 parts of biomass oil, 1-3 parts of modifier, 1-2 parts of metal preservative, 1-2 parts of combustion improver and 1-2 parts of calorific value agent;

the biomass oil is obtained by sequentially pyrolyzing, cooling and high-pressure hydrogenating biomass.

Preferably, the methanol is modified by a composite molecular sieve.

Preferably, the pyrolysis temperature is 150-220 ℃, the pyrolysis time is 1-6 h, and the pyrolysis is carried out under the condition of air isolation; the high-pressure hydrogenation temperature is 300-370 ℃, and the high-pressure hydrogenation pressure is 12-18 MPa.

Preferably, the biomass comprises one or more of corn straw, soybean straw, bark and swill-cooked dirty oil.

Preferably, the modifier comprises one or more of isopropanol, n-butanol, tert-butanol and maleic acid.

Preferably, the metal preservative comprises glycerol and/or pentaerythritol.

Preferably, the combustion improver comprises diethyl ether and/or dibutyl oxalate.

Preferably, the heating value agent comprises one or more of pentaborane, carbazate and octane.

The invention also provides a preparation method of the biological methanol fuel, which comprises the steps of mixing methanol, biomass oil, a modifier, a metal preservative, a combustion improver and a heating value agent to obtain the biological methanol fuel.

The beneficial effects of the invention include:

the invention reasonably controls the dosage of each component, the process steps and the parameters by reasonably selecting each component, and obviously improves the performance of the biological methanol fuel. The biological methanol fuel can replace gasoline by 100%, has good storage stability, low-temperature starting performance and antiknock performance, high combustion efficiency, low corrosiveness to an oil way system and an engine, reduced exhaust emission and environmental friendliness.

Detailed Description

The bio-methanol fuel of the present invention contains 85 to 95 parts of methanol, preferably 87 to 92 parts, more preferably 89 to 91 parts, and even more preferably 90 parts.

The methanol is preferably methanol modified by a composite molecular sieve.

In the invention, the polar substances, partial harmful substances and water in the methanol are extracted by the modification treatment of the composite molecular sieve, so that the polarity of the methanol and the corrosiveness to metal materials and rubber are greatly reduced, and the oil mixing phenomenon and the oil way blocking phenomenon caused by the polarity are eliminated. In the process of treating the methanol by the composite molecular sieve, a small amount of formaldehyde polymerized by the methanol is adsorbed, so that formaldehyde in tail gas is eliminated, and environmental pollution is reduced; the composite molecular sieve is preferably ZSM-5/MnAPO-11 composite molecular sieve or ZSM-5/MCM-48 composite molecular sieve.

The bio-methanol fuel of the present invention contains 3 to 6 parts of biomass oil, preferably 4 to 5.5 parts, and more preferably 4.5 to 5 parts.

The biomass oil is obtained by sequentially pyrolyzing, cooling and high-pressure hydrogenating biomass; the pyrolysis temperature is preferably 150 to 220 ℃, more preferably 160 to 210 ℃, and even more preferably 180 to 200 ℃; the pyrolysis time is preferably 1 to 6 hours, more preferably 2 to 5 hours, and still more preferably 3 to 4 hours; pyrolysis is preferably carried out under air-insulated conditions; the temperature of the high-pressure hydrogenation is preferably 300 to 370 ℃, more preferably 310 to 360 ℃, and still more preferably 330 to 350 ℃; the pressure of the high-pressure hydrogenation is preferably 12 to 18MPa, more preferably 13 to 17MPa, and still more preferably 14 to 16MPa.

In the invention, biomass is preferably ground to obtain biomass particles, and then pyrolysis, cooling and high-pressure hydrogenation are carried out on the biomass particles, wherein the particle size of the biomass particles is preferably less than or equal to 800 mu m; under the condition of isolating air, biomass particles are rapidly heated to pyrolysis temperature, then rapidly cooled, high-pressure hydrogenation is carried out to obtain a biomass oil crude product, the biomass oil crude product is filtered to remove impurities, the biomass oil crude product is placed for layering to remove water phase, the oil phase is distilled, and organic matters with the distillation range of 100-180 ℃ are collected to obtain biomass oil.

The biomass of the invention preferably comprises one or more of corn stalks, soybean stalks, bark and swill-cooked dirty oil.

In the invention, the biomass raw materials for preparing the biomass oil are all waste biomass, and are generally treated as fuel or agricultural waste, so that a large amount of resources are wasted, and the environment is polluted. The biomass oil is obtained by biomass pyrolysis and hydrogenation, is obtained by hydrogenating an oxygen-containing organic matter, and has good compatibility with the oxygen-containing organic matter methanol. When the biomass oil is matched with the metal preservative and the modifier for use, the incompletely hydrogenated active intermediate in the biomass oil can play a role with the effective components in the metal preservative and the modifier, so that the stability of the methanol fuel is improved, and the methanol fuel is prevented from absorbing water.

The bio-methanol fuel of the present invention contains 1 to 3 parts of a modifier, preferably 1.5 to 2.5 parts, and more preferably 2 parts.

The modifier preferably comprises one or more of isopropanol, n-butanol, tert-butanol and maleic acid.

The bio-methanol fuel of the present invention contains 1 to 2 parts of a metal preservative, preferably 1.2 to 1.8 parts, and more preferably 1.4 to 1.6 parts.

The metal preservative according to the invention preferably comprises glycerol and/or pentaerythritol.

The biological methanol fuel of the invention contains 1 to 2 parts of combustion improver, preferably 1.2 to 1.8 parts, and more preferably 1.4 to 1.6 parts.

The combustion improver preferably comprises diethyl ether and/or dibutyl oxalate; the combustion improver can improve the cetane number of the methanol fuel and improve the ignition performance.

The biological methanol fuel of the present invention contains 1 to 2 parts of a calorific value agent, preferably 1.2 to 1.8 parts, and more preferably 1.4 to 1.6 parts.

The heating value agent of the present invention preferably comprises one or more of pentaborane, carbazate, and octane.

The modifier and the calorific value agent greatly improve the performance of the biological methanol fuel, reduce corrosiveness, improve calorific value and stability, and can be used independently or mixed with national standard gasoline in any ratio; the oil injection system of the vehicle is not required to be cleaned, the engine of the vehicle is not required to be modified, the oil pump, the oil way system, the nozzle oil and the engine are not corroded, the swelling effect on plastic parts is equivalent to that of gasoline and diesel oil, and the corrosion effect on metal and rubber is equivalent to that of other fossil fuels.

The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

The methanol is treated by a modification tower filled with ZSM-5/MnAPO-11 composite molecular sieve for 30 min. Grinding corn straw to obtain biomass particles with the particle size of 780 mu m, pyrolyzing the biomass particles at 160 ℃ under the condition of isolating air for 5 hours, rapidly cooling to room temperature, and then carrying out hydrogenation reaction at 310 ℃ and 13MPa to obtain a biomass oil crude product. Filtering the crude biomass oil to remove impurities, standing for layering to remove water phase, distilling the oil phase, and collecting organic matters with the distillation range of 100-180 ℃ to obtain biomass oil.

And uniformly mixing 86 parts by mass of methanol treated by a composite molecular sieve, 5.5 parts by mass of biomass oil, 1.5 parts by mass of n-butanol, 1.5 parts by mass of tertiary butanol, 2 parts by mass of glycerol, 2 parts by mass of diethyl ether and 1.5 parts by mass of pentaborane to obtain the biological methanol fuel.

Example 2

The methanol is processed for 35min by a modification tower filled with ZSM-5/MCM-48 composite molecular sieve. Grinding the bark to obtain biomass particles with the particle size of 750 mu m, pyrolyzing the biomass particles at 210 ℃ under the condition of isolating air for 2 hours, rapidly cooling to room temperature, and then carrying out hydrogenation reaction at 360 ℃ and 17MPa to obtain a biomass oil crude product. Filtering the crude biomass oil to remove impurities, standing for layering to remove water phase, distilling the oil phase, and collecting organic matters with the distillation range of 100-180 ℃ to obtain biomass oil.

And uniformly mixing 93 parts by mass of methanol treated by the composite molecular sieve, 3 parts by mass of biomass oil, 1 part by mass of isopropanol, 1 part by mass of pentaerythritol, 1 part by mass of dibutyl oxalate and 1 part by mass of octane to obtain the biological methanol fuel.

Example 3

Methanol is processed for 40min by a modification tower filled with ZSM-5/MCM-48 composite molecular sieve. Grinding soybean straw to obtain biomass particles with the particle size of 700 mu m, pyrolyzing the biomass particles for 3 hours at 180 ℃ under the condition of isolating air, rapidly cooling to room temperature, and then carrying out hydrogenation reaction at 340 ℃ and 15MPa to obtain a biomass oil crude product. Filtering the crude biomass oil to remove impurities, standing for layering to remove water phase, distilling the oil phase, and collecting organic matters with the distillation range of 100-180 ℃ to obtain biomass oil.

Uniformly mixing 91 parts by mass of methanol treated by a composite molecular sieve, 5 parts by mass of biomass oil, 1.5 parts by mass of maleic acid, 1 part by mass of glycerol, 1 part by mass of dibutyl oxalate and 1.5 parts by mass of carbon twelve to obtain the biological methanol fuel.

Comparative example 1

The step of treating methanol by using the composite molecular sieve of example 3 is omitted, untreated methanol is directly adopted, twelve carbon atoms are omitted, dibutyl oxalate is changed into petroleum sulfonate, and other conditions are the same as those of example 3.

Comparative example 2

Pentaerythritol in example 3 was omitted, maleic acid was changed to Xin Fenmi, ZSM-5/MCM-48 composite molecular sieve was changed to ZSM-5 single molecular sieve, biomass particles were pyrolyzed at 250℃under air conditions, and other conditions were the same as in example 3.

The methanol fuels of examples 1 to 3 and comparative examples 1 to 2 were tested for stability, corrosiveness and tail gas content.

The bio-methanol fuels of examples 1 to 3 were not layered when stored at 25 ℃ for 24 months, the methanol fuel of comparative example 1 was significantly layered when stored at 25 ℃ for 12 months, the methanol fuel of comparative example 2 was significantly layered when stored at 25 ℃ for 14 months, and the layering of comparative examples 1 and 2 was more significantly improved as time was prolonged.

The methanol fuels of examples 1-3 and comparative examples 1-2 are used for cars with identical models, each methanol fuel of examples or comparative examples is used for 5 cars, each car runs for 50000 km under the same condition, and the corrosion condition and the tail gas content of an oil circuit system and an engine are detected to obtain the average value of the corresponding effects of the methanol fuels of examples 1-3 and comparative examples 1-2.

In the running process of the sedan in the embodiments 1-3, the oil injection system of the sedan is not required to be cleaned, the engine is not required to be refitted, and the oil pump, the oil circuit system, the oil injection nozzle and the engine of the sedan after 50000 km running have no corrosion phenomenon; the oil pump, the oil circuit system, the oil nozzle and the engine of the car of the comparative example 1 are obviously corroded after the car runs for 25000 km, the oil pump, the oil circuit system, the oil nozzle and the engine of the car of the comparative example 2 are obviously corroded after the car runs for 20000 km, and the corrosion of the cars of the comparative examples 1 and 2 is more serious along with the increase of the running mileage.

In the tail gas discharged from the car in the example 1, the formaldehyde content is 0.3mg/L, the formic acid content is 0.35mg/L, the CO content is 0.15%, the benzene content is 0.5% and the sulfur content is 0.012%; in the tail gas discharged from the car in example 2, the formaldehyde content was 0.28mg/L, the formic acid content was 0.33mg/L, the CO content was 0.16%, the benzene content was 0.52% and the sulfur content was 0.014%; in the tail gas discharged from the car in the example 3, the formaldehyde content is 0.26mg/L, the formic acid content is 0.30mg/L, the CO content is 0.16%, the benzene content is 0.46%, and the sulfur content is 0.011%; in the tail gas discharged by the car in comparative example 1, the formaldehyde content is 2.5mg/L, the formic acid content is 4.6mg/L, the CO content is 2.2%, the benzene content is 1.8% and the sulfur content is 0.8%; in the tail gas discharged from the car in comparative example 2, the formaldehyde content is 2.1mg/L, the formic acid content is 4.8mg/L, the CO content is 2.5%, the benzene content is 1.9% and the sulfur content is 1.2%.

According to the invention, through reasonably selecting each component and controlling the dosage of each component and specific process step parameters, 100% of the bio-methanol fuel which is used for replacing gasoline, has low corrosiveness to an oil circuit system, good storage stability, low-temperature starting property and antiknock property, high combustion efficiency and environment friendliness is obtained. From the examples and comparative examples, it is understood that changing the components or specific step parameters of the present invention results in reduced performance of the bio-methanol fuel.

The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims

1. The biological methanol fuel is characterized by comprising the following raw materials in parts by mass:

2. The bio-methanol fuel of claim 1 wherein the methanol is a composite molecular sieve modified methanol.

3. The bio-methanol fuel according to claim 1, wherein the pyrolysis is performed under air-insulated conditions at a temperature of 150-220 ℃ for a period of 1-6 hours; the high-pressure hydrogenation temperature is 300-370 ℃, and the high-pressure hydrogenation pressure is 12-18 MPa.

4. A bio-methanol fuel according to claim 2 or 3, wherein the biomass comprises one or more of corn stover, soybean stover, bark and swill-cooked dirty oil.

5. The bio-methanol fuel as in claim 4, wherein the modifier comprises one or more of isopropanol, n-butanol, t-butanol, and maleic acid.

6. The bio-methanol fuel of claim 4 wherein the metal preservative comprises glycerol and/or pentaerythritol.

7. The bio-methanol fuel according to claim 5 or 6, wherein the combustion improver comprises diethyl ether and/or dibutyl oxalate.

8. The bio-methanol fuel of claim 7 wherein the heating value agent comprises one or more of pentaborane, carba-dodecane, and octane.

9. The method for preparing the biological methanol fuel according to any one of claims 1 to 8, wherein methanol, biomass oil, modifier, metal preservative, combustion improver and heating value agent are mixed to obtain the biological methanol fuel.