A biological methanol fuel and a preparation method thereof

Abstract

The present application belongs to the technical field of methanol fuel, and provides a kind of biological methanol fuel, including the following mass parts of raw materials: methanol 85-95 parts, biomass oil 3-6 parts, modifier 1-3 parts, metal anticorrosive 1-2 parts, combustion improver 1-2 parts, heat value agent 1-2 parts; biomass oil is obtained by pyrolysis, cooling, high-pressure hydrogenation in sequence from biomass.The present application also provides a kind of preparation method of biological methanol fuel.By reasonably selecting each component, reasonably controlling the amount of each component and process steps and parameters, the performance of biological methanol fuel is significantly improved.The biological methanol fuel of the present application can replace 100% of gasoline, has good storage stability, low-temperature startability and anti-knock property, high combustion efficiency, low corrosion to oil system and engine, reduced waste discharge, and is friendly to the environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of methanol fuel, in particular to a biological methanol fuel and a preparation method thereof. BACKGROUND

[0002] With the serious consumption of petroleum energy and the enhancement of people's environmental protection consciousness, finding alternative clean energy has become a hot topic today. Methanol as fuel has the following characteristics: the molecular weight of methanol is small, the molecular structure is simple, the oxygen content of methanol is 50%, the ignition limit is wide, the burning speed is fast, which is beneficial to reduce carbon smoke emission; the octane number is high, the anti-knock performance is strong; the boiling point and freezing point of methanol are relatively low, the former can make the fuel-air mixture form quickly and uniformly, which is beneficial to complete combustion, and the latter can ensure the engine to work at low temperature; the latent heat of methanol vaporization is high, which can reduce the intake temperature when forming the mixture, thereby improving the charging coefficient, improving the combustion performance of the engine to a certain extent, and reducing the intake temperature can also inhibit the formation of NO and carbon smoke; the minimum ignition energy of methanol is low, and the flame propagation speed during combustion is fast. Due to the good combustion performance of methanol, it is a promising alternative energy.

[0003] Using methanol and gasoline to blend can reduce the emission of automobile exhaust, at the same time, the anti-knock performance is enhanced and the combustion performance is improved. However, methanol gasoline also has many technical problems. First, methanol has strong polarity and is easy to absorb water. When the methanol content in methanol gasoline is high, water absorption and stratification are easy to occur. Second, methanol has swelling property to rubber parts, which causes swelling, softening and cracking of the rubber parts in the fuel supply system of the automobile. At the same time, methanol has certain corrosivity to metal, which can cause permanent damage to the engine, affect driving safety, and methanol gasoline also has defects such as insufficient power, high fuel consumption and the like. These technical problems restrict the large-scale use of methanol gasoline.

[0004] Therefore, it is of great value to research a biological methanol fuel which can replace 100% of gasoline, improve combustion efficiency, reduce polarity and corrosivity, and reduce exhaust emission. SUMMARY

[0005] The purpose of the present application is to provide a biological methanol fuel and a preparation method thereof to reduce the corrosivity of the fuel, improve the storage stability and combustion efficiency, and reduce the emission of pollution gas.

[0006] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical scheme:

[0007] The present application provides a biological methanol fuel, which comprises the following raw materials by mass:

[0008] Methanol 85-95 parts, biomass oil 3-6 parts, modifier 1-3 parts, metal corrosion inhibitor 1-2 parts, combustion improver 1-2 parts, heat value agent 1-2 parts;

[0009] The biomass oil is obtained by sequentially subjecting biomass to pyrolysis, cooling, and high-pressure hydrogenation.

[0010] Preferably, the methanol is methanol treated by composite molecular sieve modification.

[0011] Preferably, the pyrolysis is performed at a temperature of 150-220°C for 1-6 hours in an air-tight condition, and the high-pressure hydrogenation is performed at a temperature of 300-370°C and a pressure of 12-18 MPa.

[0012] Preferably, the biomass comprises one or more of corn stalks, soybean stalks, tree bark, and gutter oil.

[0013] Preferably, the modifier comprises one or more of isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, and maleic acid.

[0014] Preferably, the metal corrosion inhibitor comprises glycerol and / or pentaerythritol.

[0015] Preferably, the combustion improver comprises ethyl ether and / or dibutyl oxalate.

[0016] Preferably, the heat value agent comprises one or more of pentaborane, carbon dodecane, and octane.

[0017] The application also provides a preparation method of the bio-methanol fuel, which comprises mixing methanol, biomass oil, modifier, metal corrosion inhibitor, combustion improver, and heat value agent to obtain the bio-methanol fuel.

[0018] The application has the following advantages:

[0019] The application significantly improves the performance of the bio-methanol fuel by reasonably selecting the components, controlling the amount of each component, and controlling the process steps and parameters. The bio-methanol fuel of the application can completely replace gasoline, has good storage stability, low-temperature startability, and anti-knock performance, has high combustion efficiency, has low corrosion to the oil system and engine, reduces the exhaust emission, and is environmentally friendly. DETAILED DESCRIPTION

[0020] The application provides a bio-methanol fuel, which comprises the following raw materials in parts by mass:

[0021] Methanol 85-95 parts, biomass oil 3-6 parts, modifier 1-3 parts, metal corrosion inhibitor 1-2 parts, combustion improver 1-2 parts, heat value agent 1-2 parts;

[0022] The biomass oil is obtained by pyrolysis, cooling and high-pressure hydrogenation of the biomass in sequence.

[0023] The bio-methanol fuel of the present application comprises 85-95 parts of methanol, preferably 87-92 parts, further preferably 89-91 parts, and more preferably 90 parts.

[0024] The methanol of the present application is preferably modified by composite molecular sieve.

[0025] In the present application, the modification of the composite molecular sieve extracts the polar substances, part of the harmful substances and water from the methanol, thereby greatly reducing the polarity of the methanol and the corrosion of the metal material and rubber, eliminating the oil mixing phenomenon and oil line blockage phenomenon caused by the polarity. In the process of treating the methanol by the composite molecular sieve, a small amount of formaldehyde generated by self-polymerization of the methanol is adsorbed, eliminating the formaldehyde in the tail gas and reducing the environmental pollution. The composite molecular sieve is preferably ZSM-5 / MnAPO-11 composite molecular sieve or ZSM-5 / MCM-48 composite molecular sieve.

[0026] The bio-methanol fuel of the present application comprises 3-6 parts of biomass oil, preferably 4-5.5 parts, and further preferably 4.5-5 parts.

[0027] The biomass oil of the present application is obtained by pyrolysis, cooling and high-pressure hydrogenation of the biomass in sequence. The pyrolysis temperature is preferably 150-220℃, further preferably 160-210℃, and more preferably 180-200℃. The pyrolysis time is preferably 1-6h, further preferably 2-5h, and more preferably 3-4h. The pyrolysis is preferably carried out in an air-tight condition. The high-pressure hydrogenation temperature is preferably 300-370℃, further preferably 310-360℃, and more preferably 330-350℃. The high-pressure hydrogenation pressure is preferably 12-18MPa, further preferably 13-17MPa, and more preferably 14-16MPa.

[0028] In the present application, the biomass is preferably ground to obtain biomass particles, which are then subjected to pyrolysis, cooling and high-pressure hydrogenation. The particle size of the biomass particles is preferably ≤800μm. The biomass particles are rapidly heated to the pyrolysis temperature in an air-tight condition, then rapidly cooled, and then subjected to high-pressure hydrogenation to obtain a biomass oil crude product. The biomass oil crude product is filtered to remove impurities, and then subjected to static layering to remove the water phase. The oil phase is distilled, and the organic matter with a distillation range of 100-180℃ is collected to obtain the biomass oil.

[0029] The biomass of the present application preferably comprises one or more of corn stalks, soybean stalks, tree bark and gutter oil.

[0030] The biomass raw material for preparing the biomass oil is waste biomass in the present application, which is generally treated as fuel or agricultural waste, and a large amount of resources is wasted and the environment is polluted, the present application makes full use of the waste biomass, saves energy and is beneficial to environmental protection.The biomass oil is obtained by pyrolysis and hydrogenation of biomass, and has good compatibility with oxygen-containing organic matter methanol.The active intermediates in the biomass oil can play a role with the effective components in the metal preservative and the modifier when the biomass oil is used in combination with the metal preservative and the modifier, so that the stability of the methanol fuel is improved and water absorption is prevented.

[0031] The modified methanol fuel contains 1-3 parts of the modifier, preferably 1.5-2.5 parts, and further preferably 2 parts.

[0032] The modifier preferably contains one or more of isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol and maleic acid.

[0033] The modified methanol fuel contains 1-2 parts of the metal preservative, preferably 1.2-1.8 parts, and further preferably 1.4-1.6 parts.

[0034] The metal preservative preferably contains glycerol and / or pentaerythritol.

[0035] The modified methanol fuel contains 1-2 parts of the combustion improver, preferably 1.2-1.8 parts, and further preferably 1.4-1.6 parts.

[0036] The combustion improver preferably contains diethyl ether and / or dibutyl oxalate; the combustion improver can improve the cetane number of the methanol fuel and improve the ignition performance.

[0037] The modified methanol fuel contains 1-2 parts of the heat value agent, preferably 1.2-1.8 parts, and further preferably 1.4-1.6 parts.

[0038] The heat value agent preferably contains one or more of pentaborane, carbon twelve and octane.

[0039] The modified methanol fuel of the present application greatly improves the performance of the modified methanol fuel, reduces the corrosion, improves the heat value and stability, and can be used alone or mixed with national standard gasoline at any ratio; the fuel injection system of the vehicle does not need to be cleaned, the engine of the vehicle does not need to be modified, the fuel pump, oil circuit system, nozzle oil and engine are not corroded, the swelling effect on plastic parts is equivalent to that of gasoline and diesel, and the corrosion effect on metal and rubber is equivalent to that of other fossil fuels.

[0040] The application further provides a preparation method of the biological methanol fuel.

[0041] The technical solutions provided by the application are described in detail below in combination with examples, but they should not be understood as limitations to the protection scope of the application.

[0042] Example 1

[0043] The methanol is treated in a modified tower filled with ZSM-5 / MnAPO-11 composite molecular sieve for 30 min. Corn straw is ground to obtain biomass particles with a particle size of 780 μm, and the biomass particles are pyrolyzed at 160 ℃ under air isolation for 5 h, rapidly cooled to room temperature, and then subjected to hydrogenation reaction at 310 ℃ and 13 MPa to obtain a crude biomass oil. The crude biomass oil is filtered to remove impurities, and then is subjected to static layering to remove the water phase. The oil phase is distilled, and the organic matter with a distillation range of 100-180 ℃ is collected to obtain the biomass oil.

[0044] 86 parts of the methanol treated by the composite molecular sieve, 5.5 parts of the biomass oil, 1.5 parts of n-butanol, 1.5 parts of tert-butanol, 2 parts of glycerol, 2 parts of diethyl ether and 1.5 parts of pentaborane are uniformly mixed to obtain the biological methanol fuel.

[0045] Example 2

[0046] The methanol is treated in a modified tower filled with ZSM-5 / MCM-48 composite molecular sieve for 35 min. Bark is ground to obtain biomass particles with a particle size of 750 μm, and the biomass particles are pyrolyzed at 210 ℃ under air isolation for 2 h, rapidly cooled to room temperature, and then subjected to hydrogenation reaction at 360 ℃ and 17 MPa to obtain a crude biomass oil. The crude biomass oil is filtered to remove impurities, and then is subjected to static layering to remove the water phase. The oil phase is distilled, and the organic matter with a distillation range of 100-180 ℃ is collected to obtain the biomass oil.

[0047] 93 parts of the methanol treated by the composite molecular sieve, 3 parts of the biomass oil, 1 part of isopropyl alcohol, 1 part of pentaerythritol, 1 part of dibutyl oxalate and 1 part of octane are uniformly mixed to obtain the biological methanol fuel.

[0048] Example 3

[0049] The methanol was treated by the modified tower filled with ZSM-5 / MCM-48 composite molecular sieve for 40 min. The soybean straw was ground to obtain biomass particles with a particle size of 700 μm. The biomass particles were pyrolyzed at 180 °C under air isolation for 3 h, rapidly cooled to room temperature, and then subjected to hydrogenation reaction at 340 °C and 15 MPa to obtain a crude biomass oil. The crude biomass oil was filtered to remove impurities, and then subjected to static layering to remove the water phase. The oil phase was distilled, and the organic matter with a distillation range of 100-180 °C was collected to obtain the biomass oil.

[0050] 91 parts of methanol treated by the composite molecular sieve, 5 parts of the biomass oil, 1.5 parts of maleic acid, 1 part of glycerol, 1 part of dibutyl oxalate, and 1.5 parts of carbon twelve were uniformly mixed to obtain the bio-methanol fuel.

[0051] Comparative Example 1

[0052] The step of treating methanol by the composite molecular sieve in Example 3 was omitted, and untreated methanol was directly used. Carbon twelve was omitted, and dibutyl oxalate was replaced by petroleum sulfonate. The other conditions were the same as those in Example 3.

[0053] Comparative Example 2

[0054] The pentaerythritol in Example 3 was omitted, maleic acid was replaced by octylphenyl ether, the ZSM-5 / MCM-48 composite molecular sieve was replaced by ZSM-5 single molecular sieve, and the biomass particles were pyrolyzed at 250 °C under air. The other conditions were the same as those in Example 3.

[0055] The stability, corrosion, and tail gas content of the methanol fuels in Examples 1-3 and Comparative Examples 1-2 were tested.

[0056] The bio-methanol fuels in Examples 1-3 were stored at 25 °C for 24 months without layering. The methanol fuel in Comparative Example 1 was stored at 25 °C for 12 months, and obvious layering phenomenon occurred. The methanol fuel in Comparative Example 2 was stored at 25 °C for 14 months, and obvious layering phenomenon occurred. With the extension of time, the layering phenomenon in Comparative Examples 1 and 2 became more obvious.

[0057] The methanol fuels in Examples 1-3 and Comparative Examples 1-2 were used in cars of the same type. The methanol fuel in each example or comparative example was used in 5 cars, each car was run for 50,000 kilometers under the same conditions, and the corrosion of the oil system and engine and the tail gas content were detected to obtain the average values of the effects of the methanol fuels in Examples 1-3 and Comparative Examples 1-2.

[0058] The car of the examples 1-3 does not need to clean the oil injection system of the car during running, the engine does not need to be modified, and there is no corrosion phenomenon of the oil pump, oil way system, oil injection nozzle and engine of the car after running 50000km; the car of the comparative example 1 has obvious corrosion phenomenon of the oil pump, oil way system, oil injection nozzle and engine after running 25000km, the car of the comparative example 2 has obvious corrosion phenomenon of the oil pump, oil way system, oil injection nozzle and engine after running 20000km, and the corrosion phenomenon of the cars of the comparative examples 1 and 2 is more serious with the increase of running kilometers.

[0059] The formaldehyde content of the exhaust gas of the car of the example 1 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%; the formaldehyde content of the exhaust gas of the car of the example 2 is 0.28mg / L, the formic acid content is 0.33mg / L, the CO content is 0.16%, the benzene content is 0.52%, and the sulfur content is 0.014%; the formaldehyde content of the exhaust gas of the car of the example 3 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%; the formaldehyde content of the exhaust gas of the car of the comparative example 1 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%; the formaldehyde content of the exhaust gas of the car of the comparative example 2 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%.

[0060] The present application obtains 100% replacement of gasoline by reasonably selecting the components, controlling the amount of each component and the specific process step parameters, has low corrosion to the oil way system, has good storage stability, low temperature startability and anti-knock property, has high combustion efficiency and is environment-friendly. As can be seen from the examples and comparative examples, changing the components or specific step parameters of the present application will result in the performance of the bio-methanol fuel being reduced.

[0061] The above only describes the preferred embodiments of the present application, and it should be noted that the ordinary skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A bio-methanol fuel, characterized by, consists of the following raw materials in parts by mass: Methanol 85~95 parts, biomass oil 3~6 parts, modifier 1~3 parts, metal corrosion inhibitor 1~2 parts, combustion improver 1~2 parts, heat value agent 1~2 parts; The methanol is methanol modified by composite molecular sieve; the composite molecular sieve is ZSM-5 / MnAPO-11 composite molecular sieve or ZSM-5 / MCM-48 composite molecular sieve; The biomass oil is prepared as follows: biomass is sequentially subjected to pyrolysis, cooling, high-pressure hydrogenation to obtain biomass oil crude product, the biomass oil crude product is subjected to impurity removal by filtration, water phase removal by standing and layering, and oil phase distillation, and the organic matter with a distillation range of 100~180℃ is collected to obtain biomass oil; the pyrolysis temperature is 150~220℃, and the pyrolysis time is 1~6h; the pyrolysis is carried out in an air-isolated condition; the high-pressure hydrogenation temperature is 300~370℃, and the high-pressure hydrogenation pressure is 12~18MPa; The modifier is selected from one or more of isopropyl alcohol, n-butyl alcohol, t-butyl alcohol and maleic acid; The metal corrosion inhibitor is glycerol and / or pentaerythritol; The combustion improver is diethyl ether and / or dibutyl oxalate; The heat value agent is selected from one or more of pentaborane, carbon twelve and octane.

2. The bio-methanol fuel of claim 1, wherein, The biomass is selected from one or more of corn stalks, soybean stalks and tree bark.

3. The method of producing a bio-methanol fuel according to claim 1 or 2, characterized by, Methanol, biomass oil, modifier, metal corrosion inhibitor, combustion improver and heat value agent are mixed to obtain bio-methanol fuel.