CN111378463A - Method for preparing synthesis gas by biomass pyrolysis and gasification coupling and system adopted by method - Google Patents
Method for preparing synthesis gas by biomass pyrolysis and gasification coupling and system adopted by method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
- C10B47/18—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge
- C10B47/20—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge according to the moving bed type
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
Abstract
The invention belongs to the field of biomass energy, and particularly relates to a method for preparing synthesis gas by biomass pyrolysis and gasification coupling and a system adopted by the method, which comprises the following steps: (1) feeding the biomass raw material into a microwave pyrolysis reactor for reaction to obtain a pyrolysis volatile component and a pyrolysis solid-phase material; (2) feeding the pyrolysis solid-phase material into a gasification reactor to contact with an activating agent for gasification reaction to obtain crude synthesis gas and biochar; (3) converging the pyrolysis volatile components with the raw synthesis gas, and feeding the gas into a gas reforming converter from one direction; and (3) sending the biochar into a gas reforming converter from the other direction to prepare a target product. The system adopted by the invention comprises a biomass bin (1), a microwave pyrolysis reactor (2), a gasification reactor (3), a gas reforming converter (8) and a gas-solid separator (12). The invention is beneficial to the full reaction of gas phase and solid phase, can obviously reduce the process cost of preparing the synthesis gas by biomass, and has high quality of target products.
Description
Technical Field
The invention belongs to the field of biomass energy, and particularly relates to a method for preparing synthesis gas by biomass pyrolysis and gasification coupling and an adopted system thereof.
Background
Due to the advantages of low raw material cost, wide range and the like, biomass energy is increasingly becoming an important way for replacing traditional petrochemical energy. The utilization of biomass to produce high quality fuels that can be used in transportation has been a major research goal. At present, pyrolysis oil obtained by directly pyrolyzing biomass generally has the problems of complex composition and poor property stability, and the refining and the application of the bio-oil are seriously influenced. The method for preparing the biomass synthetic oil by converting the biomass into the synthetic gas and then performing Fischer-Tropsch synthesis can overcome the bottleneck problem of the pyrolysis oil, can produce the biomass fuel with the property close to that of the conventional gasoline and diesel oil, and has a great development prospect.
The preparation of biomass synthesis gas usually adopts two technical routes of gasification and pyrolysis, wherein the gasification technology usually needs to introduce a large amount of gasification agent, combustion agent and steam, which not only causes poor quality of gasification products, but also consumes a considerable part of steam in the gasification process, resulting in complex overall process and high energy consumption. The method of biomass pyrolysis can obtain a high-quality synthesis gas product, but because pyrolysis is mostly carried out under the condition of oxygen isolation and oxygen insulation, tar is inevitably generated, and how to obtain high-quality synthesis gas and simultaneously realize the complete removal of tar is the key of opening a process route.
Aiming at the problem of poor quality of synthesis gas prepared from biomass, Chinese patent No. 201811268055.5 discloses a preparation method of biomass gasification synthesis gas, which utilizes gasification aids, namely rare earth erucic acid and potassium fluotitanate, to strengthen the cracking of biomass carbon chains and promote the generation of hydrogen, so that the quality of the biomass synthesis gas is improved. Chinese patent 201910982072.3 discloses a method for reducing tar content in biomass fluidized bed gasifier syngas, which uses fly ash loaded with calcium oxide as bed material to be transported to gasifier, so that tar can be catalytically cracked in the gasifier to effectively reduce tar content.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the method for preparing the synthesis gas by biomass pyrolysis gasification coupling, which is favorable for promoting the full reaction of gas and solid phases, is convenient for controlling the reaction process and regulating and controlling the product, can obviously reduce the process cost of preparing the synthesis gas by biomass, and has high quality of the target product.
The invention also provides a system for preparing the synthesis gas by biomass pyrolysis gasification coupling matched with the method.
In order to solve the technical problem, the invention is realized as follows:
a method for preparing synthesis gas by biomass pyrolysis gasification coupling is implemented according to the following steps:
(1) feeding the pretreated biomass raw material into a microwave pyrolysis reactor for reaction to obtain a pyrolysis volatile component and a pyrolysis solid-phase material;
(2) feeding the pyrolysis solid-phase material obtained in the step (1) into a gasification reactor to contact with an activating agent for gasification reaction to obtain crude synthesis gas and biochar;
(3) converging the pyrolysis volatile components obtained in the step (1) and the crude synthesis gas obtained in the step (2), and feeding the mixture into a gas reforming converter from one direction; and (3) sending the biochar obtained in the step (2) into a gas reforming converter from the other direction, and preparing a target product biomass synthesis gas under the action of working gas.
As a preferable scheme, the pretreatment process in the step (1) of the invention comprises the following steps: heating the dried biomass to 120-220 ℃ under the action of high-temperature air flow, preserving heat for 1-10 minutes, cooling and crushing to be less than 5mm, and performing physical extrusion forming under the condition of 10-20 MPa to obtain a biomass raw material; the reaction temperature of the microwave pyrolysis reactor is 300-800 ℃; the reaction time is 5-30 minutes.
Further, one or a combination of more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium acetate, sodium formate or potassium formate is introduced into the gasification reaction in the step (3) of the invention.
Further, the working gas in step (3) of the present invention is one or a mixture of two or more of water vapor, carbon dioxide, carbon monoxide or oxygen; the flow of the working gas is controlled to be 0.2-2 m3/h。
Further, the activating agent in the step (2) is one or a mixture of more than two of water vapor, carbon dioxide, carbon monoxide or oxygen, and the flow rate is controlled to be 0.1-1 m3/h。
Further, potassium carbonate is introduced into the gasification reaction in the step (3) of the invention; the mass ratio of the potassium carbonate to the activating agent is 0.005-0.05: 1.
Further, introducing a preheated gas generated by the pretreatment in the step (1) into the gasification reaction in the step (2); the mass ratio of the preheating gas to the activating agent is 0.1-1: 1.
Further, the reaction temperature of the gasification reactor in the step (2) is 650-950 ℃; the reaction time is 10-40 minutes; the reaction temperature of the gas reforming converter in the step (3) is 700-900 ℃; the reaction time is 0.5-5 minutes.
The system adopted by the method for preparing the synthesis gas by biomass pyrolysis gasification coupling comprises a biomass bin, a microwave pyrolysis reactor, a gasification reactor, a gas reforming converter and a gas-solid separator;
a discharge hole of the biomass bin is communicated with a feed inlet of the microwave pyrolysis reactor; the feeding port of the gasification reactor is communicated with the pyrolysis solid-phase material outlet of the microwave pyrolysis reactor;
an activating agent inlet is fixedly arranged in the middle area of the gasification reactor; an electric grate is transversely arranged at the formed biochar discharging port at the lower part of the gasification reactor; the electric grate is provided with a molded biochar spiral discharging mechanism;
a star-shaped valve is fixedly arranged at the bottom of the gasification reactor; a powdery biochar feeding screw mechanism is fixedly arranged at the upper part of the gas reforming converter; the discharge hole of the star-shaped valve is communicated with the feed inlet of the powdery biochar feeding screw mechanism through a conveying pipeline;
a working gas inlet is fixedly arranged at the bottom of the gas reforming converter; and a gas-phase material outlet at the top of the gas reforming converter is communicated with an inlet of the gas-solid separator.
As a preferred scheme, the microwave pyrolysis reactor adopts a horizontal moving bed reactor; the gasification reactor adopts a longitudinal moving bed reactor; the gas reforming converter comprises a superior bubbling fluidized bed and a subordinate bubbling fluidized bed; the upper bubbling fluidized bed is formed by combining a cylindrical barrel and a conical barrel with a downward closing-in; the lower bubbling fluidized bed is composed of a cylindrical barrel.
Compared with the prior art, the invention has the following characteristics:
1. the invention couples the pyrolysis, gasification and reforming conversion processes of the synthesis gas prepared from biomass through three interconnected reactors, wherein the microwave pyrolysis reactor is coupled with the gasification reactor through the transportation of pyrolysis solid phase material flow, and the microwave pyrolysis reactor is coupled with the gas reforming converter through the transportation of gas phase material flow including pyrolysis volatile components. The method is not only beneficial to the control of three reaction processes, the regulation and control of products and the continuous operation of a system, but also realizes the co-production of the biomass synthesis gas and the biochar products.
2. The method is characterized in that powdery biochar from a gasification reactor is used for reforming conversion reaction of gas, on one hand, the shape-selective effect of a biochar pore channel can be fully utilized to rapidly crack tar carried by the gas to form light oil and micromolecule gas, on the other hand, distributed active sites are utilized to promote dry/wet reforming and conversion reaction of hydrocarbon micromolecules, so that the quality of a synthetic gas product is improved, and particularly, the potassium carbonate-added working gas is preferably selected under the action of the working gas, so that the reaction activity of the biochar can be further enhanced and prolonged, and the high-quality biomass synthetic gas product is ensured to be obtained.
3. The gas reforming converter adopts the design of an upper bubbling fluidized bed and a lower bubbling fluidized bed, can realize the grading action of bed materials with different sizes and pyrolysis volatile components (including crude synthesis gas), namely the quick action of the bed materials with larger size in a dense phase region and the pyrolysis volatile components and the slow action of the bed materials with smaller size in a dilute phase region and the pyrolysis volatile components, and is favorable for promoting the full reaction of gas phase and solid phase.
4. The invention uses the generated high-temperature synthesis gas for preheating treatment of biomass to reduce microwave heating energy consumption and activate the biomass, uses the acid preheating gas generated by preheating the biomass for the activation process of the biochar to reduce consumption of an activating agent, and uses high-quality biochar for tar removal and reforming transformation of a gas product to improve the catalytic effect of the biochar and reduce the usage amount of an exogenous catalyst. Through the process innovation, the process cost for preparing the synthesis gas from the biomass can be obviously reduced, and the process economy is improved.
Drawings
FIG. 1 is a schematic diagram of a biomass pyrolysis gasification coupled syngas production system of the present invention;
in the figure: 1. a biomass silo; 2. a microwave pyrolysis reactor; 3. a gasification reactor; 4. an activator inlet; 5. a molded biochar spiral discharging mechanism; 6. an electric grate; 7. a star valve; 8. a gas reforming converter; 9. a powdery biochar feeding screw mechanism; 10. a working gas inlet; 11. a gas-phase material outlet; 12. a gas-solid separator.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples and comparative examples, all the raw materials used were commercially available unless otherwise specified.
As shown in fig. 1, the method for preparing synthesis gas by coupling pyrolysis and gasification of biomass can be implemented as follows:
(1) feeding the pretreated biomass raw material into a microwave pyrolysis reactor for reaction to obtain a pyrolysis volatile component and a pyrolysis solid-phase material;
(2) feeding the pyrolysis solid-phase material obtained in the step (1) into a gasification reactor to contact with an activating agent for gasification reaction to obtain crude synthesis gas and biochar;
(3) converging the pyrolysis volatile components obtained in the step (1) and the crude synthesis gas obtained in the step (2), and feeding the mixture into a gas reforming converter from one direction; and (3) sending the biochar obtained in the step (2) into a gas reforming converter from the other direction, and preparing a target product biomass synthesis gas under the action of working gas.
The biomass raw material in the step (1) can be derived from any substance containing lignocellulose, such as corn straws, rice hulls, wheat straws, wood blocks, leaves or branches and the like; the biomass pretreatment process comprises preheating, crushing, uniformly mixing and forming treatment; the pretreatment process in the step (1): heating the dried biomass to 120-220 ℃ under the action of high-temperature air flow, preserving heat for 1-10 minutes, cooling and crushing to be less than 5mm, and performing physical extrusion forming under the condition of 10-20 MPa to obtain a biomass raw material; the maximum direction ruler of the raw materialsThe size of the reactor is not more than 40mm, preferably 10-20 mm, the high-temperature airflow comes from a synthesis gas product in the system, the heat exchange mode is non-contact indirect heat exchange, the reaction temperature of the microwave pyrolysis reactor is 300-800 ℃, the reaction time is 5-30 minutes, and the microwave power density is 0.2 × 105～2×105W/m3(ii) a The pyrolysis product of the biomass is a pyrolysis volatile component and a pyrolysis solid-phase material, wherein the pyrolysis solid-phase material is biological semicoke, and the pyrolysis volatile component accounts for 55-75 wt% and the biological semicoke accounts for 25-45 wt% in percentage by mass; the content of non-condensable gas in the pyrolysis volatile components reaches more than 85 percent.
The activating agent in the step (2) is one or a mixture of more than two of water vapor, carbon dioxide, carbon monoxide and oxygen, and the flow rate is controlled to be 0.1-1 m3H, preferably steam; as a more preferable scheme, preheating gas generated by biomass pretreatment can be introduced in the gasification process, one or a combination of more of organic carboxylic acids such as formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid, succinic anhydride, glutaric acid, adipic acid, citric acid, tartaric acid, malic acid, ascorbic acid, benzoic acid, terephthalic acid, mellitic acid, salicylic acid, caffeic acid and picric acid can be introduced, the interaction of the pyrolysis solid-phase material and an activating agent is further strengthened, a biomass synthesis gas product is generated, the reaming and compatibilization effects are promoted, and the biochar is co-produced, wherein the mass ratio of the preheating gas to water vapor is preferably 0.1-1: 1.
The reaction temperature of the gasification reactor in the step (2) is 650-950 ℃, the reaction time is 10-40 minutes, and the microwave power density is 0.1 × 105～3×105W/m3. The solid-phase material is pyrolyzed to form biological coke, and gasification products of the biological coke comprise raw synthesis gas and biochar, wherein the raw synthesis gas accounts for 50-80 wt% of the gasification products, and the biochar accounts for 20-50 wt%; the content of non-condensable gases in the raw synthesis gas component reaches over 99 percent.
In the step (2), the biochar obtained from the gasification reactor is used in two parts, wherein one part is powdery and the other part is small-particle biochar used as a catalystIn the gas reforming converter, small molecular hydrocarbons in the gas are mainly reformed and converted and carried tar is removed, and the other part is directly used as a biochar product; the biochar used for the gas reforming converter accounts for 40-80% of the total amount of the biochar; the biochar has excellent surface property, wherein the specific surface area is 1000-2000 m2/g。
The working gas in the step (3) is one or a mixture of more than two of water vapor, carbon dioxide, carbon monoxide or oxygen; the flow of the working gas is controlled to be 0.2-2 m3/h。
One or a combination of more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium acetate, sodium formate or potassium formate can be introduced into the gasification reaction in the step (3). As a preferred scheme, potassium carbonate is introduced into the gasification reaction; the mass ratio of the potassium carbonate to the working gas is 0.005-0.05: 1.
The reaction temperature of the gas reforming converter in the step (3) is 700-900 ℃; the reaction time is 0.5-5 minutes; in the process of gas reforming conversion reaction, the biochar with excellent surface properties can fully utilize the shape-selective effect of a pore channel to rapidly crack with tar carried by gas to form light oil and micromolecule gas on one hand, and on the other hand, the distributed active sites are utilized to promote the dry/wet reforming and conversion reaction of hydrocarbon micromolecules, so that the quality of a synthesis gas product is improved, and particularly, the potassium carbonate-added working gas can further enhance and prolong the reaction activity of the biochar under the action of the working gas, so that a high-quality biomass synthesis gas product is obtained; the concentration of the high-quality biomass synthesis gas can reach more than 80%, the hydrogen/carbon monoxide ratio is between 1.5 and 2.2, the content of carbon dioxide is lower than 20%, the content of other impurity gases is not more than 0.5%, and the content of tar in the gas is lower than 50mg/Nm3The yield of the synthesis gas in the whole process is not lower than 1.5Nm3Per kg of dry deashed biomass.
The system adopted by the method for preparing the synthesis gas by biomass pyrolysis gasification coupling comprises a biomass bin 1, a microwave pyrolysis reactor 2, a gasification reactor 3, a gas reforming converter 8 and a gas-solid separator 12;
a discharge hole of the biomass bin 1 is communicated with a feed hole of the microwave pyrolysis reactor 2; a feeding port of the gasification reactor 3 is communicated with a pyrolysis solid-phase material outlet of the microwave pyrolysis reactor 2;
an activating agent inlet 4 is fixedly arranged in the middle area of the gasification reactor 3; an electric grate 6 is transversely arranged at the discharge port of the formed biochar at the lower part of the gasification reactor 3; the electric grate 6 is provided with a molded biochar spiral discharging mechanism 5;
a star-shaped valve 7 is fixedly arranged at the bottom of the gasification reactor 3; a powdery biochar feeding screw mechanism 9 is fixedly arranged at the upper part of the gas reforming converter 8; the discharge hole of the star-shaped valve 7 is communicated with the feed inlet of the powdery biochar feed screw mechanism 9 through a conveying pipeline;
a working gas inlet 10 is fixedly arranged at the bottom of the gas reforming converter 8; the gas phase material outlet 11 at the top of the gas reforming converter 8 is communicated with the inlet of a gas-solid separator 12.
The microwave pyrolysis reactor 2 adopts a horizontal moving bed reactor; the gasification reactor adopts a longitudinal moving bed reactor; the gas reforming converter 8 comprises an upper bubbling fluidized bed and a lower bubbling fluidized bed; the upper bubbling fluidized bed is formed by combining a cylindrical barrel and a conical barrel with a downward closing-in; the lower bubbling fluidized bed is composed of a cylindrical barrel.
The biomass raw material after preheating treatment enters a microwave pyrolysis reactor 2 from a biomass bin 1, the pyrolysis solid phase material obtained after reaction directly enters a gasification reactor 3, an activating agent enters from an activating agent inlet 4 of the gasification reactor 3 and is subjected to gasification reaction with the pyrolysis solid phase material to generate crude synthesis gas and biochar, wherein under the action of an electric grate 6, one part of formed biochar is discharged through a formed biochar spiral discharging mechanism 5 and is used as a biochar product, the other part of powdered biochar is discharged through a star-shaped valve 7 and enters from a powdered biochar feeding spiral mechanism 9 at the upper part of a gas reforming converter 8, the generated crude synthesis gas and pyrolysis volatile components are converged and then enter from the lower part of the gas reforming converter 8, and working gas enters from a working gas inlet 10 at the bottom of the gas reforming converter 8 under the action of the working gas, the biochar and pyrolysis volatiles generate tar cracking, gas reforming and water-vapor transformation reaction, the generated gas-phase material rich in the synthesis gas enters a gas-solid separator 12 through a gas-phase material outlet 11 at the top of the gas reforming converter 8, and a high-quality biomass synthesis gas product is obtained after gas-solid separation.
The microwave pyrolysis reactor adopts a horizontal moving bed reactor, a segmented non-equidistant spiral conveying structure is arranged in the horizontal moving bed reactor, the diameter of a spiral blade is 1/2-2/3 of the inner diameter of the reactor, the ratio of the pitch to the diameter of the spiral blade is 1: 0.5-2, and the pitch is reduced in a segmented manner from a feeding end to a discharging section so as to ensure the stability of the material level of a bed layer; the spiral conveying structure not only plays a role in pushing and conveying, but also has a dispersing and uniformly mixing role, prevents the phenomena of material agglomeration, aggregation and material blockage, and ensures continuous and stable movement of materials, and the spiral type comprises a spiral piece type, a spiral belt type, a vane type and the like.
The gasification reactor adopts a longitudinal moving bed reactor, a multistage stirring structure is arranged in the reactor, the diameter of a stirring rewarding piece is 1/2-3/4 of the inner diameter of the reactor, the acute angle formed by the stirring rewarding piece and the horizontal plane is 5-30 ℃, the stirring stage number is 2-5 (the number of longitudinal layers of stirring blades), 180 degrees are formed between every two stirring blades of each stage, the distance between every two adjacent stirring blades is 90 degrees, the stirring structure plays roles in loosening, dispersing and uniformly mixing, the stirring type comprises a paddle type, an anchor type, a turbine type and the like, the longitudinal stirring moving bed prevents the phenomena of material caking, aggregation and material blocking, and the continuous and stable movement of the material is ensured.
The gas reforming converter is an upper bubbling fluidized bed reactor and a lower bubbling fluidized bed reactor, wherein the upper bubbling fluidized bed is formed by combining a cylindrical barrel and a conical barrel with a downward closing-in, and an obtuse angle a between a vertical surface of a cylindrical porous sleeve and an inclined surface of the conical nonporous sleeve is 120-160 ℃; the lower bubbling fluidized bed is composed of a cylindrical barrel; the outer diameter of the cylinder of the lower bubbling fluidized bed accounts for 1/4-1/2 of the inner diameter of the cylinder of the upper bubbling fluidized bed; the upper bubbling fluidized bed and the lower bubbling bed are connected through a conical cylinder; the two-stage bubbling fluidized bed reactor can realize the grading action of bed materials with different sizes and pyrolysis volatile components (including crude synthesis gas), namely the quick action of the bed materials with larger size in a dense phase region and the pyrolysis volatile components and the slow action of the bed materials with smaller size in a dilute phase region and the pyrolysis volatile components, and is favorable for promoting the full reaction of gas phase and solid phase.
The microwave pyrolysis reactor and the gasification reactor are respectively provided with a certain number of microwave quartz windows on the wall of the reactor, each window corresponds to one microwave generator, the power of a single microwave generator is 500-2000W, the specific number of the windows is set according to the volume of the reactor and other conditions, the number of the windows is generally 2-10, and the power density in the reactor is ensured to be 0.1 × 105～3×105W/m3。
The gas-solid separator is based on one or more of gravity settling, centrifugal separation, filter screen separation, static electricity, adsorption and the like, but is not limited to the above means, and can be specifically one or more of a cyclone separator, a cloth bag filter, an electrostatic dust collector and an adsorption separator.
Examples
Heating the dried biomass to 180 ℃ under the action of high-temperature airflow, preserving heat for 10 minutes, cooling and crushing the biomass to be less than 5mm, and carrying out physical extrusion forming under the condition of 15MPa to obtain a biomass raw material with the maximum dimension of 10mm, wherein the gas generated in the preheating process is preheating gas I.
Feeding the biomass raw material into a microwave pyrolysis reactor, and pyrolyzing at 700 deg.C for 20 min and with microwave power density of 0.5 × 105W/m3Under the condition, obtaining gaseous pyrolysis volatile components and pyrolysis solid-phase materials, wherein the pyrolysis volatile components account for 60%, and the biological semicoke accounts for 40%; directly feeding the pyrolysis solid-phase material into a gasification reactor, and reacting at 850 deg.C for 20 min with activator flow of 0.5m3The mass ratio of the preheated gas I to the water vapor is 1:1, and the microwave power density is 2 × 105W/m3Under the condition, obtaining crude synthesis gas and biochar, wherein the crude synthesis gas and the biochar are crude65wt% of synthetic gas component, 35wt% of biochar and 1200m of biochar specific surface area2Per g, 60 percent of the biochar is sent into a gas reforming reactor, and is combined with raw synthesis gas and pyrolysis volatile matters which enter the gas reforming reactor, and the flow rate of working gas is 1m3Reaction is carried out under the action of/h (the mass ratio of potassium carbonate to water vapor is 0.02: 1) to generate a gas phase product rich in synthesis gas, the gas phase product is subjected to gas-solid separation to obtain a high-quality biomass synthesis gas product, the concentration of the biomass synthesis gas is 83.7 percent, the hydrogen/carbon monoxide ratio is 2.05, the carbon dioxide content is 16 percent, other impurity gases are 0.3 percent, and the tar content in the gas is 30mg/Nm3The synthesis gas yield is 1.8Nm3Per kg of dry deashed biomass.
It should be understood that the detailed description of the present invention is only for illustrating the present invention and is not limited by the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention can be modified or substituted equally to achieve the same technical effects; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A method for preparing synthesis gas by biomass pyrolysis gasification coupling is characterized by comprising the following steps:
(1) feeding the pretreated biomass raw material into a microwave pyrolysis reactor for reaction to obtain a pyrolysis volatile component and a pyrolysis solid-phase material;
(2) feeding the pyrolysis solid-phase material obtained in the step (1) into a gasification reactor to contact with an activating agent for gasification reaction to obtain crude synthesis gas and biochar;
(3) converging the pyrolysis volatile components obtained in the step (1) and the crude synthesis gas obtained in the step (2), and feeding the mixture into a gas reforming converter from one direction; and (3) sending the biochar obtained in the step (2) into a gas reforming converter from the other direction, and preparing a target product biomass synthesis gas under the action of working gas.
2. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 1, wherein: the pretreatment process in the step (1): heating the dried biomass to 120-220 ℃ under the action of high-temperature air flow, preserving heat for 1-10 minutes, cooling and crushing to be less than 5mm, and performing physical extrusion forming under the condition of 10-20 MPa to obtain a biomass raw material; the reaction temperature of the microwave pyrolysis reactor is 300-800 ℃; the reaction time is 5-30 minutes.
3. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 2, wherein: and (3) introducing one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium acetate, sodium formate or potassium formate into the gasification reaction.
4. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 3, wherein: the working gas in the step (3) is one or a mixture of more than two of water vapor, carbon dioxide, carbon monoxide or oxygen; the flow of the working gas is controlled to be 0.2-2 m3/h。
5. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 4, wherein: the activating agent in the step (2) is one or a mixture of more than two of water vapor, carbon dioxide, carbon monoxide or oxygen, and the flow rate is controlled to be 0.1-1 m3/h。
6. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 5, wherein: introducing potassium carbonate into the gasification reaction in the step (3); the mass ratio of the potassium carbonate to the working gas is 0.005-0.05: 1.
7. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 6, wherein: introducing the preheated gas generated by the pretreatment in the step (1) into the gasification reaction in the step (2); the mass ratio of the preheating gas to the activating agent is 0.1-1: 1.
8. The method for preparing the synthesis gas by coupling the pyrolysis and gasification of the biomass according to claim 7, wherein: the reaction temperature of the gasification reactor in the step (2) is 650-950 ℃; the reaction time is 10-40 minutes; the reaction temperature of the gas reforming converter in the step (3) is 700-900 ℃; the reaction time is 0.5-5 minutes.
9. The system adopted by the biomass pyrolysis gasification coupling synthesis gas preparation method according to any one of claims 1 to 8, is characterized in that: comprises a biomass bin (1), a microwave pyrolysis reactor (2), a gasification reactor (3), a gas reforming converter (8) and a gas-solid separator (12);
a discharge hole of the biomass bin (1) is communicated with a feed hole of the microwave pyrolysis reactor (2); a feeding port of the gasification reactor (3) is communicated with a pyrolysis solid-phase material outlet of the microwave pyrolysis reactor (2);
an activating agent inlet (4) is fixedly arranged in the middle area of the gasification reactor (3); an electric grate (6) is transversely arranged at the discharge port of the formed biochar at the lower part of the gasification reactor (3); the electric grate (6) is provided with a spiral discharging mechanism (5) for molded biochar;
a star-shaped valve (7) is fixedly arranged at the bottom of the gasification reactor (3); a powdery biochar feeding screw mechanism (9) is fixedly arranged at the upper part of the gas reforming converter (8); the discharge hole of the star-shaped valve (7) is communicated with the feed inlet of the powdery biochar feed screw mechanism (9) through a conveying pipeline;
a working gas inlet (10) is fixedly arranged at the bottom of the gas reforming converter (8); and a gas-phase material outlet (11) at the top of the gas reforming converter (8) is communicated with an inlet of a gas-solid separator (12).
10. The system adopted by the biomass pyrolysis and gasification coupled synthesis gas production method according to claim 9, is characterized in that: the microwave pyrolysis reactor (2) adopts a horizontal moving bed reactor; the gasification reactor adopts a longitudinal moving bed reactor; the gas reforming converter (8) comprises an upper bubbling fluidized bed and a lower bubbling fluidized bed; the upper bubbling fluidized bed is formed by combining a cylindrical barrel and a conical barrel with a downward closing-in; the lower bubbling fluidized bed is composed of a cylindrical barrel.
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