CN114479951B - Biomass pyrolysis gasification method and system - Google Patents
Biomass pyrolysis gasification method and system Download PDFInfo
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- CN114479951B CN114479951B CN202011167614.0A CN202011167614A CN114479951B CN 114479951 B CN114479951 B CN 114479951B CN 202011167614 A CN202011167614 A CN 202011167614A CN 114479951 B CN114479951 B CN 114479951B
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- biomass
- gas
- pyrolysis gasification
- heat carrier
- biomass pyrolysis
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- 239000002028 Biomass Substances 0.000 title claims abstract description 179
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 97
- 238000002309 gasification Methods 0.000 title claims abstract description 85
- 239000002994 raw material Substances 0.000 claims abstract description 72
- 239000007787 solid Substances 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 119
- 239000000463 material Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
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- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
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- -1 alkali metal salt Chemical class 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 2
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- 238000003763 carbonization Methods 0.000 description 14
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Classifications
-
- 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
- C10J3/64—Processes with decomposition of the distillation products
-
- 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
-
- 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
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
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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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0909—Drying
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- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0993—Inert particles, e.g. as heat exchange medium in a fluidized or moving bed, heat carriers, sand
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- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/12—Heating the gasifier
- C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
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- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
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Abstract
The invention discloses a biomass pyrolysis gasification method and a biomass pyrolysis gasification system, wherein the method comprises the steps of firstly, carrying out rapid heating treatment on a biomass raw material to obtain a biomass raw material with carbonized surfaces; and then the obtained biomass raw material with carbonized surface is sent into a microwave pyrolyzer for gasification reaction, and synthesis gas products and solid residues are obtained after the reaction. The biomass pyrolysis gasification system comprises a preprocessor, a microwave pyrolyzer, a gas-solid separation unit and a heat carrier regenerator. According to the method, firstly, the biomass raw material is pretreated, the outer surface of the biomass raw material is rapidly carbonized to form the carbon layer, pyrolysis volatile matters released from inside to outside in the subsequent microwave pyrolysis gasification process can be subjected to pyrolysis and reforming reaction with the formed carbon layer, so that the endogenous power formed by tar is fundamentally inhibited, the biomass pyrolysis gasification efficiency is improved, the process economy is improved, and the method has good application prospects.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to a biomass microwave pyrolysis gasification method and system.
Background
The conversion of biomass into high quality gaseous fuels by means of pyrolysis is an important way to achieve efficient utilization of biomass. Compared with the conventional gasification technology, the pyrolysis is thermal conversion under the condition of oxygen insulation or oxygen isolation, so that the introduction of exogenous gas is avoided, and the biomass fuel gas with higher heat value and higher hydrogen-carbon ratio is obtained. However, in the practical application process, more tar is often generated by adopting a biomass pyrolysis method, and the tar has the characteristics of poor stability, easy coking and corrosion, so that the problems of gas path blockage and loss exist in the pyrolysis process. Aiming at the problem that tar in pyrolysis gas is difficult to clean, two removal processes, namely an inner reactor and an outer reactor, are mostly studied at present, tar removal outside the reactor is a mature method, and tar is removed on line by setting active metal catalysts with high catalytic activity, such as nickel, iron, cobalt, palladium, rhodium, lanthanum and the like, but the method has the problems of high catalyst cost and limited recycling performance, and is difficult to apply in a large scale in a short time. The method can obviously reduce the tar content in the fuel gas, but has the problems of large consumption, difficult recycling and the like, and the tar removing route in the reactor still has good development prospect due to low cost and easy maintenance from the practical application.
In order to solve the problem that tar is difficult to clean in a reactor, chinese patent 20191092072.3 discloses a method for reducing the tar content in the synthesis gas of a biomass fluidized bed gasifier, wherein fly ash loaded with calcium oxide is used as a bed material to be catalytically cracked with the tar in the gasifier, so that the tar content is effectively reduced, gasification furnace slag is reasonably utilized, and how to realize the recycling performance of the bed material is still an important technical problem for popularization of the method. Aiming at the problem of difficult recycling of catalysis in a reactor, china patent No. 201910038001.8 provides a biomass circulating fluidized bed grading pyrolysis gasification and high-temperature tar and dust removal integrated process, and medium and small particle heat carrier and pyrolysis semicoke are directly circulated back to the fluidized bed for cracking tar through gas and pyrolysis semicoke and heat carrier grading separation, and large particle heat carrier and pyrolysis semicoke are used as a high-temperature moving bed for removing residual tar, so that the use problem of the catalyst in the reactor is effectively solved. However, the regeneration of the catalyst and the gasification of the biomass are realized in the same process, which means that a great amount of combustible gas is introduced in the process of preparing fuel gas by the biomass, so that the heat value of the fuel gas is greatly influenced, and the high-quality fuel gas is not beneficial to obtaining.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a biomass pyrolysis gasification method and a biomass pyrolysis gasification system, which are characterized in that firstly, biomass raw materials are pretreated, the outer surface of the biomass raw materials is rapidly carbonized to form a carbon layer, pyrolysis volatile matters released from inside to outside in the subsequent microwave pyrolysis gasification process can be subjected to pyrolysis and reforming reaction with the formed carbon layer, the inherent power generated by tar is restrained from the root, the biomass pyrolysis gasification efficiency is improved, the economy of the process is improved, and the biomass pyrolysis gasification method has good application prospect.
The first aspect of the invention provides a biomass pyrolysis gasification method, which comprises the following steps:
(1) Sending the biomass raw material into a preprocessor, and performing rapid heating treatment under the action of a heat carrier and first working gas to obtain the biomass raw material with carbonized surfaces and a gas-phase material after treatment;
(2) And (3) sending the biomass raw material with carbonized surface obtained in the step (1) into a microwave pyrolyzer, and carrying out gasification reaction under the action of a second working gas to obtain a synthesis gas product and solid residues after the reaction.
In the biomass pyrolysis gasification method of the present invention, the biomass raw material in the step (1) may be any lignocellulose-containing material derived from corn stalk, rice hull, wheat stalk, wood block, leaf, branch, etc. Preferably for densities of not more than 400kg/m 3 The biomass raw material (such as straw and the like) is subjected to shaping pretreatment, wherein the shaping pretreatment process comprises air drying, crushing and shaping treatment, and specifically comprises the steps of physically extruding the dried and crushed biomass raw material (crushed to below 2 mm) under the condition of 10-20 MPa to obtain the biomass raw material after the shaping pretreatment, wherein the maximum directional dimension of the biomass raw material after the shaping pretreatment is not more than 60mm, preferably 20-40 mm. For biomass raw materials with large density and no need of forming, such as wood blocks and the like, the biomass raw materials can be directly cut and the likeA biomass feedstock of a desired size is obtained. In general, the maximum dimension of the biomass feedstock is not more than 60mm, preferably 20 to 40mm.
In the biomass pyrolysis gasification method of the present invention, the heat carrier in the step (1) is a substance having excellent heat conduction and a certain wear resistance, and specifically may be one or more selected from natural ore, metal oxide, silicon-containing compound, molecular sieve, zeolite, preferably one or more selected from natural ore, metal oxide, silicon-containing compound and molecular sieve. Wherein the natural ore can be one or more of quartz sand, olivine, dolomite, attapulgite, palygorskite, iron ore, pyroxene, malachite, sericite, chlorite, calcite, and maishi ore, preferably one or more selected from olivine and iron ore; the metal oxide can be one or a combination of several of aluminum oxide, ferric oxide, calcium oxide, magnesium oxide, titanium oxide, nickel oxide, zirconium oxide and molybdenum oxide, and is preferably one or several of aluminum oxide, nickel oxide and zirconium oxide; the silicon-containing compound is silicon carbide and/or silicon nitride, the molecular sieve can be one or a combination of more of ZSM series molecular sieve, SAPO series molecular sieve, Y-type molecular sieve, beta molecular sieve, SSZ molecular sieve, SBA molecular sieve and MCM series molecular sieve, and is preferably one or a combination of more of ZSM series molecular sieves. Further, the heat carrier is preferably one or more selected from olivine, alumina and nickel oxide, and when the heat carrier comprises olivine, alumina and nickel oxide at the same time, the mass ratio of the olivine, the alumina and the nickel oxide is 1:0.5-5:0.05-0.5.
In the biomass pyrolysis gasification method, the granularity of the heat carrier in the step (1) is 0.1-1 mm.
In the biomass pyrolysis gasification method, the first working gas in the step (1) is one or more than two of steam, flue gas and air, and is preferably steam; the volume flow of the first working gas is 1-10 m 3 /h。
In the biomass pyrolysis gasification method according to the present invention, in a further preferred embodiment, the first working gas in the step (1) may further contain an organic carboxylic acid, where the organic carboxylic acid may be one or a combination of several of 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, picric acid, and the like, and preferably one or several of formic acid, acetic acid, and oxalic acid, and the mass ratio of the organic carboxylic acid to the first working gas is 0.01-0.1: 1.
in the biomass pyrolysis gasification method, the organic carboxylic acid in the first working gas in the step (1) can also be partially replaced by the acidic gas-phase material generated in the pretreatment process, so that the gas-phase material can be recycled, and the use of exogenous organic carboxylic acid is reduced.
In the biomass pyrolysis gasification method, the reaction temperature of the pretreatment device in the step (1) is 300-700 ℃, and the reaction time is 1-60 s, preferably 5-20 s.
In the biomass pyrolysis gasification method of the present invention, the pretreatment in the step (1) may be a moving bed reactor, preferably a downstream moving bed reactor; the upper part of the reactor is provided with a biomass feeding screw, the lower part of the reactor is provided with a heat carrier feeding screw, a first working gas inlet is arranged below the heat carrier feeding screw, the direction of the first working gas inlet is obliquely upward, and the acute angle between the direction of the first working gas inlet and the vertical direction is 30-60 degrees; the biomass raw material enters the pretreatment device from a biomass feeding screw at the upper part of the pretreatment reactor and falls down by gravity, the high-temperature heat carrier enters from a heat carrier feeding screw at the lower part of the pretreatment device and rises through the airflow carrying of the first working gas, and heat exchange is started after the biomass raw material contacts with the high-temperature heat carrier, and the first working gas is insufficient to prevent the falling of the biomass raw material due to the large weight of the biomass raw material, so that the contact time of the biomass raw material and the high-temperature heat carrier is shorter, and the surface heat exchange is mainly carried out, so that the biomass raw material with the intact surface carbonization of the outer carbonized inner layer is obtained. Typically, the surface carbonized biomass feedstock is obtained in mass percent and in gaseous phase, wherein the surface carbonized biomass feedstock comprises 65 to 85wt%.
In the biomass pyrolysis gasification method, the mass ratio of the biomass raw material to the heat carrier in the step (1) is 1:1-10.
In the biomass pyrolysis gasification method of the present invention, the second working gas in the step (2) is one or a mixture of more than two of steam, carbon dioxide, carbon monoxide and oxygen, preferably steam; the volume flow of the second working gas is controlled to be 0.2-2 m 3 /h。
In the biomass pyrolysis gasification method, an alkali metal-containing compound can be introduced in the gasification process in the step (2), wherein the alkali metal in the alkali metal-containing compound can be any one or more of sodium and potassium; the alkali metal-containing compound can be alkali metal salt and/or alkali metal alkali, and concretely the alkali metal-containing compound can be one or a combination of more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium acetate, sodium formate and potassium formate, the alkali metal-containing compound is brought into the microwave pyrolyzer through the second working gas, and the mass ratio of the alkali metal-containing compound to the second working gas is 0.005-0.1:1.
In the biomass pyrolysis gasification method, the temperature of the microwave pyrolysis reaction in the microwave pyrolyzer in the step (2) is 400-900 ℃; the reaction time is 5-30 minutes; microwave power density 0.1×10 5 ～5×10 5 W/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The pyrolysis product is a high-quality synthetic gas product and solid phase residues, wherein the solid phase residues account for 10-30wt% and the synthetic gas accounts for 70-90wt% in percentage by mass; the concentration of the high-quality synthetic gas product can reach more than 80%, the ratio of hydrogen to carbon monoxide is between 1.5 and 2.0, the carbon dioxide content is lower than 20%, the content of other impurity gases is not more than 0.5%, and the tar content in the gas is lower than 50mg/Nm 3 The synthesis gas yield of the whole process is not lower than 1.0Nm 3 /kg dry deashing biomass.
The biomass pyrolysis gasification method also comprises a step (3), wherein the content of the step (3) is as follows: and (3) carrying out gas-solid separation on the gas-phase material obtained in the step (1), enabling the solid obtained after separation and the solid residue obtained in the step (2) to enter a heat carrier regenerator, carrying out combustion regeneration under an oxygen-containing atmosphere, recycling the regenerated heat carrier to the preprocessor, and recycling high-temperature flue gas generated by combustion to the preprocessor as a first working gas. The high-temperature flue gas generated by combustion is circulated back to the preprocessor to provide heat for carbonization of the surface of biomass raw materials, so that biomass microwave pyrolysis materials with perfect external carbonization and internal integrity are obtained.
In the biomass pyrolysis gasification method, the regeneration of the heat carrier in the step (3) is performed in an oxygen-containing atmosphere, and the oxygen-containing atmosphere comprises one or a combination of more of air, oxygen and nitrogen mixed gas; preferably air, the volume flow of the oxygen-containing atmosphere is 1-10 m 3 /h; the treatment temperature of the heat carrier regenerator is 600-900 ℃; the regeneration time is 1-20 minutes.
In a second aspect, the present invention provides a biomass pyrolysis gasification system, the system comprising:
the pretreatment device is used for receiving the biomass raw material and the first working gas, and obtaining the biomass raw material with carbonized surfaces and the gas-phase material after the reaction;
the microwave pyrolyzer is used for receiving the biomass raw material carbonized on the surface from the pre-processor and the second working gas, and obtaining a high-quality synthetic gas product and solid-phase residues through a microwave pyrolysis gasification reaction;
the gas-solid separation unit is used for receiving the gas-phase material from the preprocessor and obtaining deactivated heat carrier and gas after separation;
and the heat carrier regenerator is used for receiving the deactivated heat carrier from the gas-solid separation unit and the solid-phase residue from the microwave pyrolyzer, burning and regenerating the heat carrier in an oxygen-containing atmosphere, and obtaining the regenerated heat carrier after treatment.
In the biomass pyrolysis gasification system, the gas obtained after separation of the gas-solid separation unit is circulated back to the preprocessor through the pipeline and enters the preprocessor through the first working gas inlet.
In the biomass pyrolysis gasification system, the regenerated heat carrier obtained after the heat carrier regenerator is treated is recycled back to the pretreatment for recycling through the heat carrier feeding spiral.
In the biomass pyrolysis gasification system, the gas-solid separation unit comprises more than one stage of gas-solid separators, preferably comprises two stages of gas-solid separators, wherein the gas-solid separator I is used for receiving gas-phase materials from the preprocessor, and deactivated heat carriers and one stage of gas-phase materials are obtained after separation; the gas-solid separator II is used for receiving the first-stage gas phase material from the gas-solid separator I, and separating to obtain gas and dust. The gas-solid separator is one or more of gravity sedimentation, centrifugal separation, filter screen separation, static electricity, adsorption and the like, but is not limited to the above mode, and the gas-solid separator can be one or more of cyclone separator, cloth bag filter, electrostatic precipitator and adsorption.
In the biomass pyrolysis gasification system, the pretreatment device adopts a moving bed reactor, preferably a descending moving bed reactor, a biomass feeding screw is arranged at the upper part of the reactor, a heat carrier feeding screw is arranged at the lower part of the reactor, a first working gas inlet is arranged below the heat carrier feeding screw, the direction of the first working gas inlet is obliquely upward, and the acute angle between the direction of the first working gas inlet and the vertical direction is 30-60 percent; the biomass raw material enters the pretreatment device from a biomass feeding screw at the upper part of the pretreatment reactor and falls down by gravity, the high-temperature heat carrier enters from a heat carrier feeding screw at the lower part of the pretreatment device and rises through the airflow carrying of the first working gas, and heat exchange is started after the biomass raw material contacts with the high-temperature heat carrier, and the first working gas is insufficient to prevent the falling of the biomass raw material due to the large weight of the biomass raw material, so that the contact time of the biomass raw material and the high-temperature heat carrier is shorter, and the surface heat exchange is mainly carried out, so that the biomass raw material with the surface carbonized inside which is intact is obtained.
In the biomass pyrolysis gasification system, the microwave pyrolyzer can be any type of microwave pyrolyzer in the prior art, preferably a horizontal moving bed reactor is adopted, and further preferably a segmented non-equidistant spiral conveying knot is arranged in the reactorThe diameter of the spiral blade is 1/2-2/3 of the inner diameter of the reactor, the ratio of the screw pitch to the diameter of the spiral blade is 1:0.5-2, and the screw pitch is reduced from the feeding end to the discharging section in a segmented manner so as to ensure the stability of the material level of the bed layer; the spiral conveying structure not only plays a role in pushing and conveying, but also has a dispersing and uniformly mixing effect, prevents the phenomena of agglomeration, aggregation and blocking of materials, ensures continuous and stable movement of the materials, and the spiral type comprises spiral sheets, spiral belts, vane type and the like. The microwave pyrolyzer is provided with a certain number of microwave quartz windows on the wall, 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 and other conditions of the reactor, and generally 2-10 windows are set, so that the power density in the reactor is ensured to be 0.1 multiplied by 10 5 ～5×10 5 W/m 3 。
In the biomass pyrolysis gasification system, the heat carrier regenerator adopts the longitudinal moving bed reactor, the inside of the reactor is provided with the multistage stirring structure, the diameter of a stirring prize is 1/2-3/4 of the inner diameter of the reactor, the acute angle between the stirring prize and a horizontal plane is 5-30, the stirring level is 2-5 (the number of longitudinal layers of the stirring blades) and 180 ℃ between each stirring blade of each level, the adjacent multistage stirring blades are 90 ℃ each other, the stirring structure plays roles of loosening, dispersing and uniformly mixing, the stirring types comprise slurry type, anchor type, turbine type and the like, the longitudinal stirring moving bed prevents the heat carrier from caking, aggregation and blocking, and the continuous and stable movement of the bed layer is ensured.
Compared with the prior art, the biomass pyrolysis gasification method and system have the following advantages:
1. in the biomass pyrolysis gasification method and system, based on the basic recognition of accelerating tar production by heat transfer and mass transfer isotropy of microwave heating behaviors, the inventor starts from changing the heating behaviors of biomass in a microwave field, obtains biomass raw materials with complete surface carbonization inside through the rapid surface contact heating of biomass raw materials with larger sizes and a heat carrier, and takes the biomass raw materials as the raw materials for the microwave pyrolysis gasification, and in the gasification process of a microwave pyrolyzer, the carbonized outer layer is preferentially heated by absorbing waves, and pyrolyzes and reforms pyrolysis volatile matters released inside, so that the internal power generated by tar is eliminated from the root, the biomass pyrolysis gasification efficiency is improved, and the tar production is reduced.
2. In the biomass pyrolysis gasification method and system, the developed downlink moving bed preprocessor-microwave pyrolysis combined process fully utilizes the biomass raw material with carbonized high temperature surface obtained in the downlink moving bed preprocessor as the biomass microwave pyrolyzer raw material, and directly carries out heating strengthening pyrolysis in a microwave field, thereby obviously reducing the energy consumption in the process of heating biomass by microwaves, improving the utilization efficiency of microwave energy and opening up a new path for combining the microwave pyrolysis technology with the conventional heating means.
3. In the biomass pyrolysis gasification method and system, the high-temperature acidic gas-phase material generated in pretreatment is used in the surface carbonization process of biomass to reduce consumption of externally-transmitted first working gas, the solid residue remained by microwave pyrolysis is used in the heat carrier regeneration process to reduce consumption of externally-transmitted energy in the regeneration process, and a small amount of cheap alkali metal compound is used in the microwave pyrolysis gasification process, so that KC (sodium carbonate) active substances can be formed with surface carbon preferentially, and further the pyrolysis efficiency of releasing pyrolysis volatile matters inside is improved. The process innovation can obviously reduce the process cost of preparing the synthetic gas from the biomass and improve the process economy.
Drawings
FIG. 1 is a schematic diagram of a biomass pyrolysis gasification process and system according to the present invention.
In the figure: 1. a biomass feed screw; 2. a preprocessor; 3. star discharger; 4. a microwave pyrolyzer; 5. a heat carrier feed screw; 6. a gas-solid separator I; 7. a gas-solid separator II; 8. a heat carrier regenerator.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention. The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. In the following examples and comparative examples, the raw materials used are all commercially available unless otherwise specified.
As shown in fig. 1, the invention provides a biomass pyrolysis gasification system, the system comprises a preprocessor 2, a microwave pyrolyzer 4, a heat carrier regenerator 8, a gas-solid separator I6 and a gas-solid separator II7, wherein pretreated biomass raw materials fall into the preprocessor 2 from a biomass feeding screw 1, the high-temperature heat carrier enters the preprocessor from a heat carrier feeding screw 5 and rises through the carrying of first working gas, the biomass raw materials and the high-temperature heat carrier are subjected to solid-solid fast contact and heat exchange to obtain surface carbonized biomass raw materials and gas phase materials with intact outer carbonized inner layers, the gas phase materials firstly enter the gas-solid separator I6 for gas-solid separation, the solid phase deactivated heat carrier obtained after separation enters the heat carrier regenerator 8, the separated first gas phase materials enter the gas-solid separator II7 for further separation, the separated gases and dust are used as first working gas, the biomass raw materials with intact surface carbonized outer carbonized enter the microwave pyrolyzer 4 through a star-shaped discharger 3, the high-quality pyrolysis products are obtained under the action of second working gas, and the high-quality pyrolysis products are obtained by the pyrolysis products, and the solid phase materials are regenerated by the heat carrier regenerator 8.
Example 1
The dried biomass is crushed to be less than 2mm, and then is subjected to physical extrusion molding under the condition of 20MPa, so as to obtain a biomass raw material, and the maximum directional size of the biomass raw material is 40mm.
Example 2
The biomass raw material of example 1 and a heat carrier 1 (the mass ratio of olivine, alumina and nickel oxide is 1:0.5:0.05) are sent into a pretreatment device according to the mass ratio of 1:5, and the water vapor flow rate of the first working gas is 5m 3 Under the action of/h, under the condition of 600 ℃ and 30 seconds of heating time, solid-solid quick contact and heat exchange are carried out to obtain biomass raw materials and gas phase materials with complete surface carbonization inside carbonization outside carbonization, and gas obtained after the gas phase materials are separated is circulated to the pre-treatmentThe processor is used. Wherein the biomass raw material with carbonized surface accounts for 65 percent; the biomass raw material carbonized on the surface is sent into a microwave pyrolyzer, and the flow of the second working gas (the mass ratio of the potassium carbonate to the water vapor is 0.05:1) is 0.5m 3 Under the action of/h, the temperature is 500 ℃; the reaction time is 30 minutes; microwave power density 1 x 10 5 W/m 3 Under the condition, a high-quality synthetic gas product is obtained, the concentration of the high-quality synthetic gas product is 81 percent, the ratio of hydrogen to carbon monoxide is 1.54, the carbon dioxide content is 18.51 percent, the content of other impurity gases is 0.49 percent, and the tar content in the gas is 48mg/Nm 3 The synthesis gas yield of the whole process was 1.08Nm 3 /kg dry deashing biomass.
Example 3
The biomass feedstock of example 1 was fed to a pretreatment unit at a mass ratio of 1:10 with a heat carrier 2 (olivine, alumina, nickel oxide: 1:5:0.5) at a flow rate of 10m in a first working gas (acetic acid: water vapor: 0.05:1 mass ratio) 3 Under the action of/h, under the condition of 700 ℃ and 20 seconds of heating time, carrying out solid-solid rapid contact and heat exchange to obtain the biomass raw material with perfect surface carbonization inside of external carbonization, wherein the biomass raw material with good surface carbonization accounts for 85 percent; the biomass raw material carbonized on the surface is sent into a microwave pyrolyzer, and the flow of the second working gas (the mass ratio of the potassium carbonate to the water vapor is 0.1:1) is 0.5m 3 Reacting for 8 minutes at 800 ℃ under the action of/h; microwave power density 3 x 10 5 W/m 3 Under the condition, a high-quality synthetic gas product is obtained, the concentration of the high-quality synthetic gas product is 89%, the ratio of hydrogen to carbon monoxide is 1.67, the carbon dioxide content is 10.79%, the content of other impurity gases is 0.21%, and the tar content in the gas is 25mg/Nm 3 The synthesis gas yield of the whole process was 1.75Nm 3 /kg dry deashing biomass.
Example 4
The biomass feedstock of example 1 was fed to a pretreatment unit with a mass ratio of 1:3 between the biomass feedstock and a heat carrier 3 (olivine, alumina, nickel oxide: 1:0.1), and a flow rate of a first working gas (acetic acid: water vapor: 0.1:1) was 6m 3 Under the action of/h, at 550 ℃, heatingAnd (3) under the condition of 20 seconds, carrying out solid-solid rapid contact and heat exchange to obtain biomass raw materials and gaseous materials with complete surface carbonization inside, wherein the gaseous materials are separated to obtain gaseous materials which are recycled to the preprocessor for use. Wherein the biomass raw material with carbonized surface accounts for 79 percent; the biomass raw material carbonized on the surface is sent into a microwave pyrolyzer, and the flow of the second working gas (the mass ratio of the potassium carbonate to the water vapor is 0.1:1) is 2m 3 Reacting for 8 minutes at 900 ℃ under the action of/h; microwave power density 5 x 10 5 W/m 3 Under the condition, a high-quality synthetic gas product is obtained, the concentration of the high-quality synthetic gas product is 93 percent, the ratio of hydrogen to carbon monoxide is 1.74, the carbon dioxide content is 6.81 percent, the content of other impurity gases is 0.19 percent, and the tar content in the gas is 18mg/Nm 3 The synthesis gas yield of the whole process was 1.87Nm 3 /kg dry deashing biomass.
Example 5
The biomass feedstock of example 1 was fed to a pretreatment unit with a mass ratio of 1:5 between the biomass feedstock and the heat carrier 3 (olivine, alumina, nickel oxide: 1:0.1), and a flow rate of 4m in a first working gas (acetic acid: water vapor: 0.05:1 mass ratio) was set 3 Under the action of/h, under the condition of 500 ℃ and 10 seconds of heating time, solid-solid quick contact and heat exchange are carried out, so as to obtain biomass raw materials and gaseous materials with complete surface carbonization inside the external carbonization, and the gaseous materials obtained after the separation of the gaseous materials are recycled to the preprocessor for use. Wherein the biomass raw material with carbonized surface accounts for 70 percent; the biomass raw material carbonized on the surface is sent into a microwave pyrolyzer, and the flow of the second working gas (the mass ratio of the potassium carbonate to the water vapor is 0.08:1) is 2m 3 Reacting for 10 minutes at 900 ℃ under the action of/h; microwave power density 5 x 10 5 W/m 3 Under the condition, a high-quality synthetic gas product is obtained, the concentration of the high-quality synthetic gas product is 94 percent, the ratio of hydrogen to carbon monoxide is 1.92, the carbon dioxide content is 5.85 percent, the content of other impurity gases is 0.15 percent, and the tar content in the gas is 15mg/Nm 3 The synthesis gas yield of the whole process was 1.95Nm 3 /kg dry deashing biomass.
Comparative example 1
The biomass feedstock of example 1 was fed into a microwave pyrolyzer at a flow rate of 4m in a second working gas (mass ratio of potassium carbonate to water vapor of 0.08:1) 3 Reacting for 10 minutes at 900 ℃ under the action of/h; microwave power density 5 x 10 5 W/m 3 Under the condition, a synthesis gas product is obtained, the concentration of the synthesis gas product is 77.45 percent, the ratio of hydrogen to carbon monoxide is 0.88, the carbon dioxide content is 11.9 percent, the content of other impurity gases is 10.65 percent, and the tar content in the gas is 15mg/Nm 3 The synthesis gas yield of the whole process was 1.95Nm 3 /kg dry deashing biomass.
Claims (27)
1. A method of biomass pyrolysis gasification, the method comprising:
(1) Sending the biomass raw material into a preprocessor, and performing rapid heating treatment under the action of a heat carrier and first working gas to obtain the biomass raw material with an intact surface carbonized outer layer and an intact inner layer and a gaseous material;
(2) Sending the biomass raw material with carbonized surfaces obtained in the step (1) into a microwave pyrolyzer, and carrying out gasification reaction under the action of second working gas to obtain a synthesis gas product and solid residues after the reaction;
the maximum directional dimension of the biomass raw material in the step (1) is 20-60 mm;
the reaction temperature of the preprocessor in the step (1) is 300-700 ℃ and the reaction time is 1-60 s;
the preprocessor in the step (1) adopts a downlink moving bed reactor; the upper part of the reactor is provided with a biomass feeding screw, and the lower part of the reactor is provided with a heat carrier feeding screw.
2. The biomass pyrolysis gasification process according to claim 1, wherein the maximum directional dimension of the biomass feedstock in the step (1) is 20 to 40mm.
3. The biomass pyrolysis gasification process according to claim 1, wherein the biomass feedstock density is no greater than 400kg/m 3 When in shaping pretreatment, shapingThe pretreated biomass raw material is sent into a pretreatment device, the shaping pretreatment process comprises air drying, crushing and shaping treatment, and specifically comprises the steps of physically extruding the biomass raw material which is dried and crushed to be less than 2mm under the condition of 10-20 MPa to obtain the shaped pretreated biomass raw material, wherein the maximum directional size of the shaped pretreated biomass raw material is 20-40 mm.
4. The biomass pyrolysis gasification method according to claim 1, wherein the heat carrier in the step (1) is one or more selected from olivine, alumina and nickel oxide, and when the olivine, alumina and nickel oxide are included at the same time, the mass ratio of olivine, alumina and nickel oxide is 1:0.5-5:0.05-0.5.
5. The biomass pyrolysis gasification process according to claim 1, wherein the particle size of the heat carrier in step (1) is 0.1 to 1mm.
6. The biomass pyrolysis gasification process according to claim 1, wherein the first working gas in step (1) is one or a combination of two or more of steam, flue gas, and air; the volume flow of the first working gas is 1-10 m 3 /h。
7. The biomass pyrolysis gasification process according to claim 1, wherein the first working gas in step (1) is steam.
8. The biomass pyrolysis gasification process according to claim 1, wherein the first working gas in step (1) contains an organic carboxylic acid, which is one or a combination of several of 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, picric acid, and the mass ratio of the organic carboxylic acid to the first working gas is 0.01 to 0.1:1.
9. the biomass pyrolysis gasification method according to claim 8, wherein the organic carboxylic acid is one or more of formic acid, acetic acid and oxalic acid.
10. The biomass pyrolysis gasification process according to claim 1, wherein the reaction time of the pre-processor in step (1) is 5 to 20 seconds.
11. The biomass pyrolysis gasification method according to claim 1, wherein a first working gas inlet is arranged below the heat carrier feeding screw in the step (1), the direction of the first working gas inlet is obliquely upward, and the acute angle between the direction of the first working gas inlet and the vertical direction is 30-60 degrees.
12. The biomass pyrolysis gasification process according to claim 1, wherein the mass ratio of the biomass raw material to the heat carrier in the step (1) is 1:1 to 10.
13. The biomass pyrolysis gasification process according to claim 1, wherein the second working gas in step (2) is one or a mixture of two or more of steam, carbon dioxide, carbon monoxide, and oxygen; the volume flow of the second working gas is controlled to be 0.2-2 m 3 /h。
14. The biomass pyrolysis gasification process according to claim 1, wherein an alkali metal-containing compound is introduced into the gasification process in the step (2), and the alkali metal in the alkali metal-containing compound is any one or more of sodium and potassium; the alkali metal-containing compound is an alkali metal salt and/or an alkali metal base.
15. The biomass pyrolysis gasification process according to claim 14, wherein the alkali metal-containing compound is one or a combination of several of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium acetate, sodium formate, and potassium formate, the alkali metal-containing compound is brought into the microwave pyrolyzer through the second working gas, and the mass ratio of the alkali metal-containing compound to the second working gas is 0.005 to 0.1:1.
16. The biomass pyrolysis gasification method according to claim 1, wherein the microwave pyrolysis reaction temperature in the microwave pyrolyzer in the step (2) is 400 to 900 ℃; the reaction time is 5-30 minutes; microwave power density 0.1×10 5 ～5×10 5 W/m 3 。
17. The biomass pyrolysis gasification process according to claim 1, wherein the biomass pyrolysis gasification process comprises a step (3), and the content of the step (3) is: and (3) carrying out gas-solid separation on the gas-phase material obtained in the step (1), enabling the solid obtained after separation and the solid residue obtained in the step (2) to enter a heat carrier regenerator, carrying out combustion regeneration under an oxygen-containing atmosphere, recycling the regenerated heat carrier to the preprocessor, and recycling high-temperature flue gas generated by combustion as a first working gas to the preprocessor.
18. The biomass pyrolysis gasification process according to claim 17, wherein the heat carrier regeneration in step (3) is performed under an oxygen-containing atmosphere comprising one or a combination of several of air, oxygen and nitrogen mixtures; the volume flow of the oxygen-containing atmosphere is 1-10 m 3 /h; the treatment temperature of the heat carrier regenerator is 600-900 ℃; the regeneration time is 1-20 minutes.
19. The biomass pyrolysis gasification method according to any one of claims 1 to 18, wherein a biomass pyrolysis gasification system adopted in the method comprises:
the pretreatment device is used for receiving the biomass raw material and the first working gas, and obtaining the biomass raw material with carbonized surfaces and the gas-phase material after the reaction;
the microwave pyrolyzer is used for receiving the biomass raw material carbonized on the surface from the pre-processor and the second working gas, and obtaining a high-quality synthetic gas product and solid-phase residues through a microwave pyrolysis gasification reaction;
the gas-solid separation unit is used for receiving the gas-phase material from the preprocessor and obtaining deactivated heat carrier and gas after separation;
and the heat carrier regenerator is used for receiving the deactivated heat carrier from the gas-solid separation unit and the solid-phase residue from the microwave pyrolyzer, burning and regenerating the heat carrier in an oxygen-containing atmosphere, and obtaining the regenerated heat carrier after treatment.
20. The biomass pyrolysis gasification process according to claim 19, wherein the gas separated by the gas-solid separation unit is recycled back to the pre-processor through the pipeline and enters the pre-processor through the first working gas inlet.
21. The biomass pyrolysis gasification process according to claim 19, wherein the regenerated heat carrier obtained after the heat carrier regenerator treatment is recycled back to the pretreatment cycle for use through a heat carrier feed screw.
22. The biomass pyrolysis gasification process according to claim 19, wherein the gas-solid separation unit comprises more than one stage of gas-solid separators.
23. The biomass pyrolysis gasification process according to claim 22, wherein the gas-solid separation unit comprises a two-stage gas-solid separator, wherein the gas-solid separator I is configured to receive the gas phase material from the pre-processor, and to obtain the deactivated heat carrier and the first-stage gas phase material after separation; the gas-solid separator II is used for receiving the first-stage gas phase material from the gas-solid separator I, and separating to obtain gas and dust.
24. The biomass pyrolysis gasification method according to claim 19, wherein a first working gas inlet is arranged below the heat carrier feeding screw, the direction of the first working gas inlet is obliquely upward, and the acute angle between the direction of the first working gas inlet and the vertical direction is 30-60 degrees.
25. The biomass pyrolysis gasification process according to claim 19, wherein the microwave pyrolyzer employs a horizontal moving bed reactor.
26. The biomass pyrolysis gasification process according to claim 25, wherein a segmented non-equidistant spiral conveying structure is arranged in the reactor, the diameter of the spiral blades is 1/2-2/3 of the inner diameter of the reactor, the ratio of the screw pitch to the diameter of the spiral blades is 1:0.5-2, and the screw pitch is gradually reduced from the feeding end to the discharging section.
27. The biomass pyrolysis gasification process according to claim 19, wherein the heat carrier regenerator adopts a longitudinal moving bed reactor, a multistage stirring structure is arranged in the reactor, the diameter of stirring prize plates is 1/2-3/4 of the inner diameter of the reactor, the acute angle between the stirring prize plates and the horizontal plane is 5-30 degrees, the stirring stage number is 2-5 stages, 180 degrees are formed between each stirring blade of each stage, and 90 degrees are formed between every two adjacent multistage stirring blades.
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