阅读说明：本技术 一种利用生物质材料制备烃类化合物的方法 (Method for preparing hydrocarbon compound by using biomass material ) 是由 生帆 于 2021-01-29 设计创作，主要内容包括：本发明涉及木质纤维素废弃物综合利用技术领域,尤其涉及一种利用生物质材料制备烃类化合物的方法,本发明融合化学和生物的方法利用生物质材料为原料制备生物基甲醇和生物基烃类化合物、芳烃,尤其是可以利用生物基合成气与沼气互混合成甲醇,解决了煤合成气制甲醇的氢原子比例不足的缺点,弥补了纯生物法制烃类化合物、芳烃效率低下和纯化学法过度依赖石油及分子筛催化剂等缺点,提供了一种利用生物质材料制备烃类化合物的新方法,利用可再生生物质还可以制备生物基甲醇。(The invention relates to the technical field of comprehensive utilization of lignocellulose waste, in particular to a method for preparing hydrocarbon compounds by utilizing biomass materials, which integrates chemistry and biology, utilizes the biomass materials as raw materials to prepare bio-based methanol, bio-based hydrocarbon compounds and aromatic hydrocarbon, and particularly can utilize bio-based synthesis gas and methane to be mixed into methanol, thereby overcoming the defects of insufficient hydrogen atom proportion in the preparation of the methanol by using coal synthesis gas, making up the defects of low efficiency of hydrocarbon compounds by using a pure biological method, excessive dependence on petroleum and molecular sieve catalysts by using a pure chemical method and the like, providing a novel method for preparing the hydrocarbon compounds by utilizing the biomass materials, and utilizing renewable biomass to prepare the bio-based methanol.)

1. A method for producing hydrocarbon compounds from biomass material, comprising the steps of:

A) carrying out steam explosion pretreatment on the biomass material;

B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane;

or

Carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane;

C1) decarbonizing and desulfurizing the marsh gas, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the methane, mixing the methane with methane-oxidizing bacteria, and fermenting to obtain methanol;

D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

2. The method as claimed in claim 1, wherein the concentration of carbon dioxide in the decarbonized mixture gas in the step C1) is not more than 20 wt.%.

3. The method according to claim 1, wherein in step C1), after the reaction, the method further comprises:

carrying out solid-liquid separation on the product after the reaction, and distilling the liquid after the solid-liquid separation to obtain methanol;

the distillation temperature is 72-82 ℃;

the methane-oxidizing bacteria are methylotrophus;

the fermentation temperature is 25-45 ℃, and the fermentation time is 1-10 days.

4. A method for producing hydrocarbon compounds from biomass material, comprising the steps of:

A) carrying out steam explosion pretreatment on the biomass material;

B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane;

or

Carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane;

C2) pyrolyzing and gasifying the fermentation residues to generate bio-based synthesis gas, and removing solid impurities in the biogas and the bio-based synthesis gas to obtain purified mixed gas;

decarbonizing and desulfurizing the purified gas mixture, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the purified mixed gas, mixing the purified mixed gas with methane-oxidizing bacteria, and fermenting to obtain methanol;

D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

5. The method according to claim 4, wherein in step C2), the pyrolysis gasification is carried out under an atmosphere of nitrogen;

the pyrolysis gasification comprises:

heating the fermentation residue to 700-800 ℃ at a speed of 5-50 ℃/min, and then heating to 800-1000 ℃ at a speed of 1-50 ℃/min.

6. The method according to claim 4, wherein in the step C2), the volume ratio of the biogas to the bio-based synthesis gas in the purified mixed gas is 1-10: 1-10;

the concentration of carbon dioxide in the mixed gas after decarburization is not more than 20 wt%;

after the reaction, the method further comprises the following steps:

carrying out solid-liquid separation on the product after the reaction, and distilling the liquid after the solid-liquid separation to obtain methanol;

the distillation temperature is 72-82 ℃;

the methane-oxidizing bacteria are methylotrophus;

the fermentation temperature is 25-45 ℃, and the fermentation time is 1-10 days.

7. The method as claimed in claim 1 or 2, wherein in step a), the biomass material comprises one or more of corn stover, sorghum stover and poplar;

the biomass material is dried biomass;

before the biomass material is subjected to steam explosion pretreatment, the method also comprises the following steps: mixing the biomass material with water;

the mass ratio of the water to the biomass material is 15-25: 100, respectively;

the pressure of the steam explosion is 1.0-2.0 MPa, and the time is 10-30 min.

8. The method according to claim 1 or 2, wherein in step B) the ethanol producing bacteria is saccharomyces cerevisiae; the methane producing bacteria is methane sarcina;

the enzyme for enzymolysis and fermentation comprises cellulase, pectinase, feruloyl esterase, xylanase, beta-xylosidase or laccase;

the dosage ratio of the enzyme to the pretreated biomass material is 0.1-20 FPU: 1g of a compound;

the temperature of enzymolysis fermentation is 25-52 ℃, and the time is 0.5-360 h.

9. The method according to claim 1 or 2, wherein in step D), the concentration of the methanol solution is 10 wt% to 20 wt%;

the dosage ratio of the methanol to the alkanol dehydratase is 1 g: 1-100 mg;

the temperature of enzyme catalysis is 20-40 ℃, and the time is 12-72 h.

10. The method according to claim 1 or 2, wherein in step D), the catalyst used in the reaction of the methanol under the action of the catalyst comprises ZSM-5 or SAPO-34;

the reaction temperature is 300-600 ℃, the reaction time is 12-72 hours, and the pressure is 0.1-0.4 MPa;

the water-alcohol ratio of the reaction is 0.04-0.20: 100.

Technical Field

The invention relates to the technical field of comprehensive utilization of lignocellulose waste, in particular to a method for preparing hydrocarbon compounds by using biomass materials.

Background

The low-carbon hydrocarbon compounds and the aromatic hydrocarbons are important basic raw materials of national economy, and the industrial production of the low-carbon hydrocarbon compounds and the aromatic hydrocarbons at present depends on petroleum seriously, so that the production cost of the low-carbon hydrocarbon compounds and the aromatic hydrocarbons such as ethylene, propylene and the like is also greatly influenced. However, with the increasing exhaustion of fossil energy and the emergence of a series of environmental problems caused by the use of fossil resources, many large-scale petroleum companies in the world are searching and researching new production raw materials and process technologies which can be adopted for preparing low-carbon hydrocarbon compounds such as ethylene and propylene and aromatic hydrocarbons. Lignocellulose is used as an important renewable energy source, has the characteristics of large reserves, cleanness, renewability and the like, is one of important renewable resources, has great conversion potential and is expected to get rid of the dependence on petroleum.

The preparation means of hydrocarbon compounds and aromatic hydrocarbons mainly focuses on cracking petroleum products by a chemical method to produce the hydrocarbon compounds and the aromatic hydrocarbons. Common routes include tubular furnace steam cracking to ethylene and the like. However, the means for preparing hydrocarbon compounds and aromatics by using such petroleum routes depends excessively on raw materials provided by oil refineries or gas processing plants, including refining naphtha from traditional crude oil, so that the process flow is very complicated, which is one of the reasons for high cost of hydrocarbon compounds and aromatics. At present, natural gas or coal is also used as a raw material to convert synthesis gas to prepare ethylene, and the like, so that the limitation of over depending on petroleum is broken through, but the method has the factors of low catalytic efficiency and over-high catalyst cost, and the application of the chemical method is also limited.

At present, the production of hydrocarbon compounds and aromatic hydrocarbons by a biological method has been developed. For example, Braskem in Braskem, brakem, has for the first time built a 20 ten thousand ton/year ethylene production line starting from sugar cane ethanol. However, the production of the hydrocarbon compounds and the aromatic hydrocarbons needs to require a large amount of sugarcane as raw materials, which is not universally applied in China, and in addition, the expensive ethanol catalyst is excessively relied on to prepare the hydrocarbon compounds and the aromatic hydrocarbons. Although some researchers use methane-oxidizing bacteria to prepare methanol, the biological methods have strict requirements on substrate components and excessively long reaction time, and are not effectively combined with upstream enzymolysis and fermentation processes, so that industrial production is difficult to realize.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a new method for preparing hydrocarbon compounds by using biomass materials, and bio-based methanol can be prepared by using renewable biomass.

The invention provides a method for preparing hydrocarbon compounds by using biomass materials, which comprises the following steps:

A) carrying out steam explosion pretreatment on the biomass material;

B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane;

or

Carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane;

C1) decarbonizing and desulfurizing the marsh gas, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the methane, mixing the methane with methane-oxidizing bacteria, and fermenting to obtain methanol;

D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

Preferably, in the step C1), the concentration of carbon dioxide in the mixed gas after decarburization is not more than 20 wt%.

Preferably, in step C1), after the reaction, the method further comprises:

carrying out solid-liquid separation on the product after the reaction, and distilling the liquid after the solid-liquid separation to obtain methanol;

the distillation temperature is 72-82 ℃;

the methane-oxidizing bacteria are methylotrophus;

the fermentation temperature is 25-45 ℃, and the fermentation time is 1-10 days.

The invention also provides a method for preparing hydrocarbon compounds by using the biomass material, which comprises the following steps:

A) carrying out steam explosion pretreatment on the biomass material;

B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane;

or

Carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane;

C2) pyrolyzing and gasifying the fermentation residues to generate bio-based synthesis gas, and removing solid impurities in the biogas and the bio-based synthesis gas to obtain purified mixed gas;

decarbonizing and desulfurizing the purified gas mixture, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the purified mixed gas, mixing the purified mixed gas with methane-oxidizing bacteria, and fermenting to obtain methanol;

D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

Preferably, in step C2), the pyrolysis gasification is performed under an atmosphere of nitrogen;

the pyrolysis gasification comprises:

heating the fermentation residue to 700-800 ℃ at a speed of 5-50 ℃/min, and then heating to 800-1000 ℃ at a speed of 1-50 ℃/min.

Preferably, in the step C2), the volume ratio of the biogas to the bio-based syngas in the purified mixed gas is 1-10: 1-10;

the concentration of carbon dioxide in the mixed gas after decarburization is not more than 20 wt%;

after the reaction, the method further comprises the following steps:

carrying out solid-liquid separation on the product after the reaction, and distilling the liquid after the solid-liquid separation to obtain methanol;

the distillation temperature is 72-82 ℃;

the methane-oxidizing bacteria are methylotrophus;

the fermentation temperature is 25-45 ℃, and the fermentation time is 1-10 days.

Preferably, in the step A), the biomass material comprises one or more of corn straw, sorghum straw and poplar;

the biomass material is dried biomass;

before the biomass material is subjected to steam explosion pretreatment, the method also comprises the following steps: mixing the biomass material with water;

the mass ratio of the water to the biomass material is 15-25: 100, respectively;

the pressure of the steam explosion is 1.0-2.0 MPa, and the time is 10-30 min.

Preferably, in the step B), the ethanol producing bacteria is Saccharomyces cerevisiae; the methane producing bacteria is methane sarcina;

the enzyme for enzymolysis and fermentation comprises cellulase, pectinase, feruloyl esterase, xylanase, beta-xylosidase or laccase;

the dosage ratio of the enzyme to the pretreated biomass material is 0.1-20 FPU: 1g of a compound;

the temperature of enzymolysis fermentation is 25-52 ℃, and the time is 0.5-360 h.

Preferably, in the step D), the concentration of the methanol solution is 10 wt% to 20 wt%;

the dosage ratio of the methanol to the alkanol dehydratase is 1 g: 1-100 mg;

the temperature of enzyme catalysis is 20-40 ℃, and the time is 12-72 h.

Preferably, in the step D), the catalyst used in the reaction of the methanol under the action of the catalyst comprises ZSM-5 or SAPO-34;

the reaction temperature is 300-600 ℃, the reaction time is 12-72 hours, and the pressure is 0.1-0.4 MPa;

the water-alcohol ratio of the reaction is 0.04-0.20: 100.

the invention provides a method for preparing hydrocarbon compounds by using biomass materials, which comprises the following steps: A) carrying out steam explosion pretreatment on the biomass material; B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane; or carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane; C1) decarbonizing and desulfurizing the marsh gas, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the methane, mixing the methane with methane-oxidizing bacteria, and fermenting to obtain methanol; D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound. The method for fusing chemistry and biology of the invention utilizes biomass materials as raw materials to prepare bio-based methanol, bio-based hydrocarbon compounds and aromatic hydrocarbon, especially can utilize bio-based synthesis gas and methane to be mixed into methanol, solves the defect of insufficient hydrogen atom proportion in the preparation of methanol from coal synthesis gas, and overcomes the defects of hydrocarbon compounds prepared by a pure biological method, low aromatic hydrocarbon efficiency, excessive dependence on petroleum and molecular sieve catalysts prepared by a pure chemical method and the like. Meanwhile, the method provides a set of systematic high-value biomass conversion method, and the renewable resources are effectively utilized to produce olefin and aromatic chemicals.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention relates to a method for preparing hydrocarbon compounds by utilizing biomass materials, which comprises two methods, wherein the first method comprises the following steps:

A) carrying out steam explosion pretreatment on the biomass material;

B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane;

or

Carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane;

C1) decarbonizing and desulfurizing the marsh gas, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the methane, mixing the methane with methane-oxidizing bacteria, and fermenting to obtain methanol;

D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

In certain embodiments of the present invention, the biomass material may be a common renewable biomass feedstock, specifically, including one or more of corn stover, sorghum stover, and poplar. In certain embodiments of the invention, the biomass material is a dried biomass material.

In some embodiments of the present invention, the biomass material further comprises, prior to the steam explosion pretreatment: the biomass material is mixed with water. In certain embodiments of the present invention, the mass ratio of the water to the biomass material is 15-25: 100. in certain embodiments, the mass ratio of the water to the biomass material is 20: 100.

in some embodiments of the present invention, the pressure of the steam explosion is 1.0-2.0 MPa, and the time is 10-30 min. In certain embodiments of the invention, the steam explosion is performed in a steam explosion canister.

After the pretreatment is completed, the obtained pretreated biomass material has two treatment methods. One is that: and carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane.

In certain embodiments of the invention, the ethanol producing bacteria is saccharomyces cerevisiae.

In some embodiments of the invention, the mass ratio of the ethanol producing bacteria to the pretreated biomass material is 0.001-5: 10 to 20. In certain embodiments, the mass ratio of ethanol producing bacteria to the pretreated biomass material is 0.01: 10 or 0.001: 10.

in certain embodiments of the invention, the enzymatic fermentation employs enzymes including cellulases, pectinases, feruloyl esterases, xylanases, beta-xylosidases, or laccases. In certain embodiments of the present invention, the dosage ratio of the enzyme to the pretreated biomass material is 0.1 to 20 FPU: 1g of the total weight of the composition. In certain embodiments, the ratio of the amount of enzyme to the pretreated biomass material is 20 FPU: 1g of the total weight of the composition.

In some embodiments of the invention, the temperature of the enzymolysis fermentation is 25-52 ℃ and the time is 0.5-360 h. In certain embodiments, the temperature of the enzymatic fermentation is 30 ℃. In certain embodiments, the time for enzymatic fermentation is 96 hours, 48 hours.

In certain embodiments of the invention, the solid-liquid separation is carried out in a plate and frame filter.

In certain embodiments of the invention, the methane-producing bacteria is Methanosarcina.

In some embodiments of the invention, the mass ratio of the solid substance to the methane-producing bacteria is 50-100: 0.001 to 8. In certain embodiments, the mass ratio of the solid matter to the methane-producing bacteria is 100: 0.04, 100: 0.02, 100: 0.06 or 100: 0.008.

in some embodiments of the invention, the temperature of the anaerobic fermentation is 33-38 ℃ and the time is 24-240 hours. In certain embodiments, the temperature of the anaerobic fermentation is 35 ℃. In certain embodiments, the time for anaerobic fermentation is 240h, 180h, or 160 h.

Another method of treating pretreated biomass material is:

and carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane.

In certain embodiments of the invention, the methane-producing bacteria is Methanosarcina.

In some embodiments of the invention, the mass ratio of the methane-producing bacteria to the pretreated biomass material is 0.001-5: 10 to 20. In certain embodiments, the mass ratio of methane-producing bacteria to the pretreated biomass material is 0.01: 10 or 0.001: 10.

in some embodiments of the invention, the temperature of the enzymolysis fermentation is 25-52 ℃ and the time is 0.5-120 h. In certain embodiments, the temperature of the enzymatic fermentation is 37 ℃. In certain embodiments, the time for enzymatic fermentation is 120 hours.

After obtaining the biogas, decarbonizing and desulfurizing the biogas, and mixing the biogas with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the methane, mixing the methane with methane-oxidizing bacteria, and fermenting to obtain the methanol.

In certain embodiments of the invention, the decarbonizing comprises:

and mixing the purified mixed gas with a decarbonizing agent for decarbonization.

In certain embodiments of the invention, the decarboniser comprises lime water.

In certain embodiments of the invention, the decarbonizing is performed in a decarbonizer.

In certain embodiments of the invention, the carbon dioxide concentration in the decarbonated mixture does not exceed 20 wt.%. In certain embodiments, the carbon dioxide concentration in the decarbonated mixture is 10 wt.%, 0 wt.%, or 2 wt.%.

In certain embodiments of the invention, the desulfurizing comprises:

and mixing the decarbonized gas with a desulfurizing agent for desulfurization.

In certain embodiments of the present invention, the desulfurizing agent comprises one or more of sodium hydroxide, calcium hydroxide, and sodium carbonate.

In certain embodiments of the invention, the desulfurization is carried out in a desulfurization tower.

In certain embodiments of the present invention, the sulfur dioxide concentration of the desulfurized gaseous mixture does not exceed 20 weight percent. In certain embodiments, the concentration of sulfur dioxide in the desulfurized mixed gas is 5 wt.%, 0 wt.%, 0.5 wt.%, or 2 wt.%.

In certain embodiments of the present invention, CuO/ZnO/Al₂O₃Including CuO, ZnO and Al₂O₃(ii) a The CuO, ZnO and Al₂O₃The molar ratio of (A) to (B) is 1-10: 0.1-10: 1 to 10. In certain embodiments, the CuO, ZnO, and Al₂O₃In a molar ratio of 1: 1: 1. 1.5: 1: 2. 1: 2: 1. 1: 1: 2 or 1: 1.5: 2.

in certain embodiments of the invention, the temperature of the reaction is 260 ℃, 255 ℃, or 270 ℃. In certain embodiments of the present invention, after the reacting, further comprising:

and carrying out solid-liquid separation on the product after the reaction, and distilling the liquid after the solid-liquid separation to obtain the methanol.

In certain embodiments of the invention, the solid-liquid separation is carried out in a solid-liquid separator.

In certain embodiments of the invention, the temperature of the distillation is 72 to 82 ℃.

In certain embodiments of the invention, the methane-oxidizing bacteria are methylotrophus.

In certain embodiments of the invention, the OD of the methane-oxidizing bacteria₆₀₀＝0.6～1.6。

In some embodiments of the invention, the fermentation temperature is 25-45 ℃ and the fermentation time is 1-10 days. In certain embodiments, the temperature of the fermentation is 35 ℃. In certain embodiments, the fermentation time is 3 days.

In certain embodiments of the present invention, after the fermentation, further comprising:

and carrying out solid-liquid separation on the fermented substrate, and distilling the liquid after the solid-liquid separation to obtain the methanol.

In certain embodiments of the invention, the solid-liquid separation is a plate and frame filter-press separation.

In certain embodiments of the invention, the temperature of the distillation is 72 to 82 ℃.

After the methanol is obtained, mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

In certain embodiments of the invention, the methanol solution has a concentration of 10 wt% to 20 wt%. In certain embodiments of the invention, the solvent in the solution of methanol is water. The method for preparing the methanol solution is not particularly limited, and the solution can be prepared by a method well known to those skilled in the art, and specifically, the solution can be prepared by mixing methanol and water.

In certain embodiments of the invention, the methanol to alkanol dehydratase is used in a ratio of 1 g: 1-100 mg. In certain embodiments, the methanol to alkanol dehydratase is used in a ratio of 1 g: 10mg or 1 g: 12 mg.

In some embodiments of the invention, the temperature of the enzyme catalysis is 20-40 ℃ and the time is 12-72 hours. In certain embodiments, the temperature catalyzed by the enzyme is 30 ℃. In certain embodiments, the enzyme catalyzes a time of 24 hours.

In certain embodiments of the invention, the catalyst used in the reaction of methanol over the catalyst comprises ZSM-5 or SAPO-34.

In some embodiments of the invention, the reaction temperature is 300-600 ℃, the reaction time is 12-72 hours, and the pressure is 0.1-0.4 MPa. In certain embodiments, the reaction temperature is 480 ℃, 485 ℃, or 470 ℃. In certain embodiments, the reaction time is 24 hours. In certain embodiments, the reaction pressure is 0.2MPa, 0.12MPa, or 0.1 MPa.

In certain embodiments of the present invention, the water to alcohol ratio of the reaction is 0.04 to 0.20: 100. in certain embodiments, the water to alcohol ratio of the reaction is 0.1: 100.

a second method for producing hydrocarbons from biomass material comprises the steps of:

A) carrying out steam explosion pretreatment on the biomass material;

B) carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane;

or

Carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane;

C2) pyrolyzing and gasifying the fermentation residues to generate bio-based synthesis gas, and removing solid impurities in the biogas and the bio-based synthesis gas to obtain purified mixed gas;

decarbonizing and desulfurizing the purified gas mixture, and mixing with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol; or decarbonizing and desulfurizing the purified mixed gas, mixing the purified mixed gas with methane-oxidizing bacteria, and fermenting to obtain methanol;

D) mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

In certain embodiments of the present invention, the biomass material may be a common renewable biomass feedstock, specifically, including one or more of corn stover, sorghum stover, and poplar. In certain embodiments of the invention, the biomass material is a dried biomass material.

In some embodiments of the present invention, the biomass material further comprises, prior to the steam explosion pretreatment: the biomass material is mixed with water. In certain embodiments of the present invention, the mass ratio of the water to the biomass material is 15-25: 100. in certain embodiments, the mass ratio of the water to the biomass material is 20: 100.

in some embodiments of the present invention, the pressure of the steam explosion is 1.0-2.0 MPa, and the time is 10-30 min. In certain embodiments of the invention, the steam explosion is performed in a steam explosion canister.

After the pretreatment is completed, the obtained pretreated biomass material has two treatment methods. One is that: and carrying out enzymolysis fermentation on the pretreated biomass material and ethanol producing bacteria, carrying out solid-liquid separation on the obtained fermentation liquor to obtain solid matters and ethanol, and carrying out anaerobic fermentation on the solid matters and the methane producing bacteria to obtain fermentation residues and methane.

In certain embodiments of the invention, the ethanol producing bacteria is saccharomyces cerevisiae.

In some embodiments of the invention, the mass ratio of the ethanol producing bacteria to the pretreated biomass material is 0.001-5: 10 to 20. In certain embodiments, the mass ratio of ethanol producing bacteria to the pretreated biomass material is 0.01: 10 or 0.001: 10.

in certain embodiments of the invention, the enzymatic fermentation employs enzymes including cellulases, pectinases, feruloyl esterases, xylanases, beta-xylosidases, or laccases. In certain embodiments of the present invention, the dosage ratio of the enzyme to the pretreated biomass material is 0.1 to 20 FPU: 1g of the total weight of the composition.

In some embodiments of the invention, the temperature of the enzymolysis fermentation is 25-52 ℃ and the time is 0.5-360 h.

In certain embodiments of the invention, the solid-liquid separation is carried out in a plate and frame filter.

In certain embodiments of the invention, the methane-producing bacteria is Methanosarcina.

In some embodiments of the invention, the mass ratio of the solid substance to the methane-producing bacteria is 50-100: 0.001 to 8. In certain embodiments, the mass ratio of the solid matter to the methane-producing bacteria is 100: 0.04, 100: 0.02, 100: 0.06 or 100: 0.008.

in some embodiments of the invention, the temperature of the anaerobic fermentation is 33-38 ℃ and the time is 24-240 hours.

Another method of treating pretreated biomass material is:

and carrying out enzymolysis fermentation on the pretreated biomass material and methane producing bacteria to obtain fermentation residues and methane.

In certain embodiments of the invention, the methane-producing bacteria is Methanosarcina.

In some embodiments of the invention, the mass ratio of the methane-producing bacteria to the pretreated biomass material is 0.001-5: 10 to 20. In certain embodiments, the mass ratio of methane-producing bacteria to the pretreated biomass material is 0.01: 10.

in some embodiments of the invention, the temperature of the enzymolysis fermentation is 25-52 ℃ and the time is 0.5-120 h. In certain embodiments, the temperature of the enzymatic fermentation is 37 ℃. In certain embodiments, the time for enzymatic fermentation is 120 hours.

And after obtaining the fermentation residues, carrying out pyrolysis gasification on the fermentation residues to generate the bio-based synthesis gas.

In certain embodiments of the invention, the pyrolysis gasification is conducted under an atmosphere of nitrogen.

In certain embodiments of the invention, the pyrolysis gasification comprises:

heating the fermentation residue to 700-800 ℃ at a speed of 5-50 ℃/min, preserving the heat for 0-25 min, and heating to 800-1000 ℃ at a speed of 1-50 ℃/min.

In certain embodiments of the present invention, the ramp rate is 20 deg.C/min. In some embodiments of the invention, the temperature is 700 ℃ after the temperature is raised. In certain embodiments of the invention, the incubation time is 20 min. In certain embodiments of the invention, the re-ramping rate is 30 deg.C/min. In certain embodiments of the invention, the temperature after the second temperature increase is 1000 ℃.

The biomass is subjected to pyrolysis gasification reaction at high temperature, and macromolecules and supermolecule substances are converted into CO and CO₂、H₂C and CH₄And the like.

And after the bio-based synthesis gas is obtained, removing solid impurities in the biogas and the bio-based synthesis gas to obtain the purified mixed gas. Specifically, the biogas and the bio-based syngas may be mixed, and then the solid impurities in the mixture may be removed to obtain the purified mixture.

In certain embodiments of the invention, the removal of solid impurities is performed in a filter separator.

In some embodiments of the invention, the volume ratio of the biogas to the bio-based synthesis gas in the purified mixed gas is 1-10: 1 to 10.

After the purified mixed gas is obtained, the purified mixed gas is decarbonized and desulfurized and then mixed with CuO/ZnO/Al₂O₃Reacting at 200-300 ℃ to generate methanol. Or decarbonizing and desulfurizing the purified mixed gas, mixing the purified mixed gas with methane-oxidizing bacteria, and fermenting to obtain the methanol.

In certain embodiments of the invention, the decarbonizing comprises:

and mixing the purified mixed gas with a decarbonizing agent for decarbonization.

In certain embodiments of the invention, the decarboniser comprises lime water.

In certain embodiments of the invention, the decarbonizing is performed in a decarbonizer.

In certain embodiments of the invention, the carbon dioxide concentration in the decarbonated mixture does not exceed 20 wt.%. In certain embodiments, the carbon dioxide concentration in the decarbonated mixture is 0 wt.%.

In certain embodiments of the invention, the desulfurizing comprises:

and mixing the decarbonized gas with a desulfurizing agent for desulfurization.

In certain embodiments of the present invention, the desulfurizing agent comprises one or more of sodium hydroxide, calcium hydroxide, and sodium carbonate.

In certain embodiments of the invention, the desulfurization is carried out in a desulfurization tower.

In certain embodiments of the present invention, the sulfur dioxide concentration of the desulfurized gaseous mixture does not exceed 20 weight percent. In certain embodiments, the sulfur dioxide concentration in the desulfurized gaseous mixture does not exceed 0 weight percent.

In certain embodiments of the present invention, CuO/ZnO/Al₂O₃Including CuO, ZnO and Al₂O₃(ii) a The CuO, ZnO and Al₂O₃The molar ratio of (A) to (B) is 1-10: 0.1-10: 1 to 10. In certain embodiments, the CuO, ZnO, and Al₂O₃In a molar ratio of 1: 1: 1. 1.5: 1: 2. 1: 2: 1. 1: 1: 2 or 1: 1.5: 2.

in certain embodiments of the invention, the temperature of the reaction is 260 ℃, 255 ℃, or 270 ℃.

In certain embodiments of the present invention, after the reacting, further comprising:

and carrying out solid-liquid separation on the product after the reaction, and distilling the liquid after the solid-liquid separation to obtain the methanol.

In certain embodiments of the invention, the solid-liquid separation is carried out in a solid-liquid separator.

In certain embodiments of the invention, the temperature of the distillation is 72 to 82 ℃.

In certain embodiments of the invention, the methane-oxidizing bacteria are methylotrophus.

In certain embodiments of the invention, the OD of the methane-oxidizing bacteria₆₀₀＝0.6～1.6。

In some embodiments of the invention, the fermentation temperature is 25-45 ℃ and the fermentation time is 1-10 days.

In certain embodiments of the present invention, after the fermentation, further comprising:

and carrying out solid-liquid separation on the fermented substrate, and distilling the liquid after the solid-liquid separation to obtain the methanol.

In certain embodiments of the invention, the solid-liquid separation is a plate and frame filter-press separation.

In certain embodiments of the invention, the temperature of the distillation is 72 to 82 ℃.

After the methanol is obtained, mixing the methanol solution with alkanol dehydratase, and carrying out enzyme catalysis to obtain a hydrocarbon compound; or reacting methanol under the action of a catalyst to obtain the hydrocarbon compound.

In certain embodiments of the invention, the methanol solution has a concentration of 10 wt% to 20 wt%. In certain embodiments of the invention, the solvent in the solution of methanol is water. The method for preparing the methanol solution is not particularly limited, and the solution can be prepared by a method well known to those skilled in the art, and specifically, the solution can be prepared by mixing methanol and water.

In certain embodiments of the invention, the methanol to alkanol dehydratase is used in a ratio of 1 g: 1-100 mg.

In some embodiments of the invention, the temperature of the enzyme catalysis is 20-40 ℃ and the time is 12-72 hours.

In certain embodiments of the invention, the catalyst used in the reaction of methanol over the catalyst comprises ZSM-5 or SAPO-34.

In some embodiments of the invention, the reaction temperature is 300-600 ℃, the reaction time is 12-72 hours, and the pressure is 0.1-0.4 MPa. In certain embodiments, the temperature of the reaction is 480 ℃ or 510 ℃. In certain embodiments, the reaction time is 24 hours. In certain embodiments, the pressure of the reaction is 0.2MPa or 0.1 MPa.

In certain embodiments of the present invention, the water to alcohol ratio of the reaction is 0.04 to 0.20: 100. in certain embodiments, the water to alcohol ratio of the reaction is 0.20: 100.

in certain embodiments of the present invention, the starting material for the reaction of methanol over the catalyst also includes toluene for the synthesis of para-dihydroxytoluene.

The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.

In order to further illustrate the present invention, a method for preparing hydrocarbon compounds by using biomass materials according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.

The starting materials used in the following examples are all generally commercially available.

Example 1

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 20min under the steam pressure of 1.5MPa to carry out steam explosion pretreatment; collecting the corn straws subjected to steam explosion pretreatment, conveying the corn straws into a fermentation tank, adding cellulase according to the proportion of 20FPU/g of the straws subjected to steam explosion, adding saccharomyces cerevisiae powder (the mass ratio of the saccharomyces cerevisiae powder to the straws subjected to steam explosion is 0.01: 10), and performing enzymolysis and fermentation for 96 hours at 30 ℃ to produce a large amount of ethanol. And (3) performing solid-liquid separation on the fermentation liquor by using a plate-and-frame filter, inoculating the solid matter into Methanosarcina pusilla (the mass ratio of the solid matter to the Methanosarcina pusilla is 50: 0.02), and performing anaerobic fermentation at 35 ℃ for 240 hours to produce biogas.

And introducing the biogas into a decarbonizing tower filled with lime water to maintain the carbon dioxide concentration in the decarbonized gas at 10 wt%, and introducing the biogas into a desulfurizing tower filled with sodium carbonate particles to perform desulfurization, wherein the sulfur dioxide concentration in the desulfurized mixed gas is 5 wt%. And then introducing the gas into a fermentation culture medium of methylotrophic bacteria for fermentation for 3d at 35 ℃ for producing methanol, performing plate-and-frame filter pressing separation on a substrate, setting the kettle temperature in a distillation tower at 72 ℃ for distillation, and collecting distillate as refined methanol.

The produced methanol and water are prepared into a 10 wt% methanol solution, alkanol dehydratase (the dosage ratio of the methanol to the alkanol dehydratase is 1 g: 10mg) is added into a reactor, the reaction is catalyzed for 24 hours at 30 ℃, and the produced gas is collected to be ethylene.

Example 2

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 25min under the steam pressure of 1.0MPa to carry out steam explosion pretreatment; conveying the corn straws subjected to steam explosion pretreatment to a fermentation tank, adding methane sarcina (the mass ratio of the methane sarcina to the corn straws subjected to steam explosion pretreatment is 0.001: 10), and performing enzymolysis fermentation for 120 hours at 37 ℃ in a high-solid anaerobic reactor to produce biogas.

And (3) introducing the methane into a decarbonizing tower filled with lime water, completely removing carbon dioxide, and introducing into a desulfurizing tower filled with sodium carbonate for complete desulfurization. Then introducing the gas filled with CuO/ZnO/Al₂O₃(including CuO, ZnO and Al)₂O₃(ii) a The CuO, ZnO and Al₂O₃In a molar ratio of 1: 1: 1) the reaction kettle is catalyzed at 260 ℃, the product after the reaction is subjected to solid-liquid separation in a solid-liquid separator, and the liquid after the solid-liquid separation is distilled at 72 ℃ to obtain the methanol.

Introducing the generated methanol into a reaction kettle filled with a molecular sieve of ZSM-5, and setting the reaction temperature to be 480 ℃, the reaction pressure to be 0.2MPa and the water-alcohol ratio to be 0.1: 100. the fixed carbon value of the spent catalyst is 6.1 percent, the operation is continued for 24 hours, the product is collected to be the prepared olefin, and the final yield of the olefin is 7.5 percent.

Example 3

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 10min under the steam pressure of 1.5MPa to carry out steam explosion pretreatment; collecting the corn straws subjected to steam explosion pretreatment, conveying the corn straws into a fermentation tank, adding cellulase according to the proportion of 20FPU/g of the straws subjected to steam explosion, adding saccharomyces cerevisiae powder (the mass ratio of the saccharomyces cerevisiae powder to the straws subjected to steam explosion is 0.01: 10), and performing enzymolysis fermentation for 48 hours at 30 ℃ to produce a large amount of ethanol. And (3) performing solid-liquid separation on the fermentation liquor by using a plate-and-frame filter, inoculating the solid matter into Methanosarcina pusilla (the mass ratio of the solid matter to the Methanosarcina pusilla is 50: 0.01), and performing anaerobic fermentation at 35 ℃ for 180 hours to produce biogas.

And (3) introducing the methane into a decarbonizing tower filled with lime water, completely removing carbon dioxide, and introducing into a desulfurizing tower filled with sodium carbonate for complete desulfurization. Then introducing the gas filled with CuO/ZnO/Al₂O₃(including CuO, ZnO and Al)₂O₃(ii) a The CuO, ZnO and Al₂O₃In a molar ratio of1.5: 1: 2) the reaction kettle of (1) is catalyzed at 255 ℃, the product after the reaction is subjected to solid-liquid separation in a solid-liquid separator, and the liquid after the solid-liquid separation is distilled at 78 ℃ to generate the methanol.

The generated methanol and water are prepared into 12 wt% methanol solution, alkanol dehydratase (the dosage ratio of the methanol to the alkanol dehydratase is 1 g: 10mg) is added into a reactor, the reaction is catalyzed for 24 hours at 30 ℃, and the generated gas is collected to be ethylene.

Example 4

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 30min under the steam pressure of 1.0MPa to carry out steam explosion pretreatment; collecting the corn straws subjected to steam explosion pretreatment, conveying the corn straws into a fermentation tank, adding cellulase according to the proportion of 20FPU/g of the straws subjected to steam explosion, adding saccharomyces cerevisiae powder (the mass ratio of the saccharomyces cerevisiae powder to the straws subjected to steam explosion is 0.01: 10), and performing enzymolysis fermentation for 72 hours at 32 ℃ to produce a large amount of ethanol. And (3) performing solid-liquid separation on the fermentation liquor by using a plate-and-frame filter, inoculating the solid matter into methane sarcina (the mass ratio of the solid matter to the methane sarcina is 50: 0.03), and performing anaerobic fermentation at 35 ℃ for 180 hours to produce biogas.

And (3) introducing the methane into a decarbonizing tower filled with lime water, completely removing carbon dioxide, and introducing into a desulfurizing tower filled with sodium carbonate for complete desulfurization. Then introducing the gas filled with CuO/ZnO/Al₂O₃(including CuO, ZnO and Al)₂O₃(ii) a The CuO, ZnO and Al₂O₃In a molar ratio of 1: 2: 1) the reaction kettle of (1) is catalyzed and reacted at 270 ℃, the product after the reaction is subjected to solid-liquid separation in a solid-liquid separator, and the liquid after the solid-liquid separation is distilled at 80 ℃ to generate the methanol.

Introducing the generated methanol into a reaction kettle filled with a molecular sieve of ZSM-5, setting the reaction temperature to be 485 ℃, the reaction pressure to be 0.12MPa and the water-alcohol ratio to be 0.08: 100. the fixed carbon value of the spent catalyst is 6.1 percent, the operation is continued for 24 hours, and the product is collected to be the prepared hydrocarbon compound.

Example 5

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 20min under the steam pressure of 1.5MPa to carry out steam explosion pretreatment; collecting the corn straws subjected to steam explosion pretreatment, conveying the corn straws into a fermentation tank, adding cellulase according to the proportion of 10FPU/g of the straws subjected to steam explosion, adding saccharomyces cerevisiae powder (the mass ratio of the saccharomyces cerevisiae powder to the straws subjected to steam explosion is 0.01: 10), and performing enzymolysis and fermentation for 96 hours at 30 ℃ to produce a large amount of ethanol. And (3) performing solid-liquid separation on the fermentation liquor by using a plate-and-frame filter, inoculating the solid matter into Methanosarcina pusilla (the mass ratio of the solid matter to the Methanosarcina pusilla is 50: 0.004), and performing anaerobic fermentation at the temperature of 35 ℃ for 160h to produce biogas.

And introducing the biogas into a decarbonizing tower filled with lime water to maintain the carbon dioxide concentration in the decarbonized gas at 10 wt%, and introducing the biogas into a desulfurizing tower filled with sodium carbonate particles to perform desulfurization, wherein the sulfur dioxide concentration in the desulfurized mixed gas is 2 wt%. And then introducing the gas into a fermentation culture medium of methylotrophic bacteria for fermentation for 3d at 35 ℃ for producing methanol, performing plate-and-frame filter pressing separation on a substrate, setting the kettle temperature in a distillation tower at 72 ℃ for distillation, and collecting distillate as refined methanol.

Introducing the generated methanol into a reaction kettle filled with a molecular sieve of ZSM-5, setting the reaction temperature to be 470 ℃, the reaction pressure to be 0.12MPa and the water-alcohol ratio to be 0.1: 100. the fixed carbon value of the spent catalyst is 6.1 percent, the operation is continued for 24 hours, and the product is collected to be the prepared hydrocarbon compound.

Example 6

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 20min under the steam pressure of 1.5MPa to carry out steam explosion pretreatment; conveying the corn straws subjected to steam explosion pretreatment to a fermentation tank, adding methane sarcina (the mass ratio of the methane sarcina to the corn straws subjected to steam explosion pretreatment is 0.01: 10), and performing enzymolysis fermentation for 96 hours at 37 ℃ in a high-solid anaerobic reactor to produce biogas.

And introducing the biogas into a decarbonizing tower filled with lime water to maintain the carbon dioxide concentration in the decarbonized gas at 10 wt%, and introducing the biogas into a desulfurizing tower filled with sodium carbonate particles to perform desulfurization, wherein the sulfur dioxide concentration in the desulfurized mixed gas is 0.5 wt%. And then introducing the gas into a fermentation culture medium of methylotrophic bacteria for fermentation for 3d at 35 ℃ for producing methanol, performing plate-and-frame filter pressing separation on a substrate, setting the kettle temperature in a distillation tower at 72 ℃ for distillation, and collecting distillate as refined methanol.

The produced methanol and water are prepared into a 10 wt% methanol solution, alkanol dehydratase (the dosage ratio of the methanol to the alkanol dehydratase is 1 g: 10mg) is added into a reactor, the reaction is catalyzed for 24 hours at 30 ℃, and the produced gas is collected to be ethylene.

Example 7

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 20min under the steam pressure of 1.5MPa to carry out steam explosion pretreatment; conveying the corn straws subjected to steam explosion pretreatment to a fermentation tank, adding methane sarcina (the mass ratio of the methane sarcina to the corn straws subjected to steam explosion pretreatment is 0.01: 10), and performing enzymolysis fermentation for 96 hours at 37 ℃ in a high-solid anaerobic reactor to produce biogas.

And introducing the biogas into a decarbonizing tower filled with lime water to maintain the carbon dioxide concentration in the decarbonized gas at 10 wt%, and introducing the biogas into a desulfurizing tower filled with sodium carbonate particles to perform desulfurization, wherein the sulfur dioxide concentration in the desulfurized mixed gas is 2 wt%. And then introducing the gas into a fermentation culture medium of methylotrophic bacteria for fermentation for 3d at 35 ℃ for producing methanol, performing plate-and-frame filter pressing separation on a substrate, setting the kettle temperature in a distillation tower at 72 ℃ for distillation, and collecting distillate as refined methanol.

Introducing the generated methanol into a reaction kettle filled with a molecular sieve of ZSM-5, and setting the reaction temperature to be 480 ℃, the reaction pressure to be 0.1MPa and the water-alcohol ratio to be 0.1: 100. the fixed carbon value of the spent catalyst is 6.1 percent, the spent catalyst is continuously operated for 24 hours, and products are collected to be the prepared hydrocarbon compounds such as ethylene, propylene and the like.

Example 8

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 22min under the steam pressure of 1.5MPa to carry out steam explosion pretreatment; conveying the corn straws subjected to steam explosion pretreatment to a fermentation tank, adding methane sarcina (the mass ratio of the methane sarcina to the corn straws subjected to steam explosion pretreatment is 0.01: 10), and performing enzymolysis fermentation for 96 hours at 37 ℃ in a high-solid anaerobic reactor to produce biogas.

And (3) introducing the methane into a decarbonizing tower filled with lime water, completely removing carbon dioxide, and introducing into a desulfurizing tower filled with sodium carbonate for complete desulfurization. Then introducing the gas filled with CuO/ZnO/Al₂O₃(CuO, ZnO and Al)₂O₃(ii) a The CuO, ZnO and Al₂O₃In a molar ratio of 1: 1: 2) the reaction kettle of (1) is catalyzed and reacted at 260 ℃, the product after the reaction is subjected to solid-liquid separation in a solid-liquid separator, and the liquid after the solid-liquid separation is distilled at 80 ℃ to generate the methanol.

The generated methanol and water are prepared into 17 wt% methanol solution, alkanol dehydratase (the dosage ratio of the methanol to the alkanol dehydratase is 1 g: 12mg) is added into a reactor, the reaction is catalyzed for 24 hours at 30 ℃, and the generated gas is collected to be ethylene.

Example 9

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 25min under the steam pressure of 1.0MPa to carry out steam explosion pretreatment; conveying the corn straws subjected to steam explosion pretreatment to a fermentation tank, adding methane sarcina (the mass ratio of the methane sarcina to the corn straws subjected to steam explosion pretreatment is 0.01: 10), and performing enzymolysis fermentation for 120 hours at 37 ℃ in a high-solid anaerobic reactor to produce biogas.

Under the atmosphere of nitrogen, the fermentation residue after anaerobic fermentation is heated to 700 ℃ at a speed of 20 ℃/min and stays for 20min, and then is heated to 1000 ℃ at a speed of 30 ℃/min to generate the bio-based synthesis gas.

And mixing the biogas and the bio-based synthesis gas, and removing solid impurities through a filter separator to obtain purified mixed gas.

And introducing the purified mixed gas into a decarbonizing tower filled with lime water, completely removing carbon dioxide, and introducing into a desulfurizing tower filled with sodium carbonate for complete desulfurization.Then introducing the gas filled with CuO/ZnO/Al₂O₃(including CuO, ZnO and Al)₂O₃(ii) a The CuO, ZnO and Al₂O₃In a molar ratio of 1: 1: 2) the reaction kettle of (1) is catalyzed at 255 ℃, the product after the reaction is subjected to solid-liquid separation in a solid-liquid separator, and the liquid after the solid-liquid separation is distilled at 82 ℃ to generate methanol.

Introducing the generated methanol into a reaction kettle filled with a molecular sieve of ZSM-5, and setting the reaction temperature to be 480 ℃, the reaction pressure to be 0.2MPa and the water-alcohol ratio to be 0.2: 100. the fixed carbon value of the spent catalyst is 6.1 percent, the spent catalyst is continuously operated for 24 hours, and products are collected to be the prepared hydrocarbon compounds such as ethylene, propylene and the like.

Example 10

Adding water (the mass ratio of water to the dry corn straws is 20: 100) into 500kg of dry corn straws, then sending the mixture into a steam explosion tank, and reacting for 25min under the steam pressure of 1.0MPa to carry out steam explosion pretreatment; conveying the corn straws subjected to steam explosion pretreatment to a fermentation tank, adding methane sarcina (the mass ratio of the methane sarcina to the corn straws subjected to steam explosion pretreatment is 0.01: 10), and performing enzymolysis fermentation for 360 hours at 37 ℃ in a high-solid anaerobic reactor to produce biogas.

Under the atmosphere of nitrogen, the fermentation residue after anaerobic fermentation is heated to 700 ℃ at a speed of 20 ℃/min and stays for 20min, and then is heated to 1000 ℃ at a speed of 30 ℃/min to generate the bio-based synthesis gas.

And mixing the biogas and the bio-based synthesis gas, and removing solid impurities through a filter separator to obtain purified mixed gas.

And introducing the purified mixed gas into a decarbonizing tower filled with lime water, completely removing carbon dioxide, and introducing into a desulfurizing tower filled with sodium carbonate for complete desulfurization. Then introducing the gas filled with CuO/ZnO/Al₂O₃(including CuO, ZnO and Al)₂O₃(ii) a The CuO, ZnO and Al₂O₃In a molar ratio of 1: 1.5: 2) the reaction kettle of (1) is catalyzed and reacted at 270 ℃, the product after the reaction is subjected to solid-liquid separation in a solid-liquid separator, and the liquid after the solid-liquid separation is distilled at 79 ℃ to generate methanol.

Introducing the generated methanol into a reaction kettle filled with a molecular sieve of ZSM-5, and setting the reaction temperature to be 510 ℃, the reaction pressure to be 0.1MPa and the water-alcohol ratio to be 0.2: 100. the carbon value of the spent catalyst is 8.1 percent, the operation is continued for 24 hours, and the product is collected to be the prepared p-dihydroxytoluene.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.