CN113462435A - Resource recycling catalytic utilization method for biomass gasification ash - Google Patents
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- CN113462435A CN113462435A CN202110708580.XA CN202110708580A CN113462435A CN 113462435 A CN113462435 A CN 113462435A CN 202110708580 A CN202110708580 A CN 202110708580A CN 113462435 A CN113462435 A CN 113462435A
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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
- C10J3/64—Processes with decomposition of the distillation products
- C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
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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
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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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- 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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- 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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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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
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
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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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
- C10J2300/1628—Ash post-treatment
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
A method for recycling, circulating and catalyzing and utilizing biomass gasification ash is characterized in that alkali metals and alkaline earth metals in the gasification ash are activated in a high-temperature calcination mode, then the activated alkali metals and the alkaline earth metals are used as catalysts to be mixed and gasified with biomass raw materials, the alkali metals and the alkaline earth metals in regenerated ash obtained in the process are enriched, the alkali metals and the alkaline earth metals in the regeneration are activated and catalytically utilized in a high-temperature calcination mode, and the recycling and utilization of the gasification ash are realized and high-quality gasification gas is obtained in a reciprocating mode. The invention realizes the resource utilization of the biomass gasification ash, is beneficial to the resource utilization of the gasification ash and improves the quality of the gasification gas.
Description
Technical Field
The invention belongs to the field of resource utilization of biomass gasification ash and preparation of high-quality fuel gas by catalyzing biomass gasification. The method takes biomass ash utilization as a core, and carries out cyclic (high-temperature calcination-catalysis) catalytic gasification utilization on the biomass ash so as to realize double targets of ash recycling and biomass high-efficiency gasification.
Background
The gas fuel (biomass gas) generated by biomass gasification has similar functions to the biological natural gas, can meet the requirements of domestic energy and heat supply, and realizes multi-energy complementary peak regulation. Therefore, the preparation of fuel gas by biomass gasification becomes one of the key directions for future development of biomass energy industry in China.
The main product of the biomass gasification process is gasification fuel gas, but tar and ash residues are inevitably generated as byproducts. However, this technique has the following problems:
first, the gasification efficiency and the calorific value of the gasified gas are low. Without a catalyst, higher gasification temperatures can ensure gasification efficiency, which increases energy consumption and operating costs. Therefore, the improvement of gasification efficiency and the calorific value of the gasified gas have great significance on the development and popularization of biomass gasification technology.
Secondly, the tar content in the gasified gas is high. Tar formation can reduce gasification efficiency; blocking pipelines and threatening the safe operation of equipment such as a gas turbine, an internal combustion engine and the like; the toxic substances can pose a threat to human health. Therefore, measures should be taken to reduce the amount of tar produced and to convert the biomass into clean fuel gas as much as possible.
Furthermore, there is a problem of disposal of the gasified ash. With the development of biomass gasification technology, the annual output of gasified ash gradually rises, about 50000 ten thousand tons per year. However, 70% of the ash is buried, which not only has high cost, but also occupies land resources, pollutes the environment and is not beneficial to developing circular economy. Therefore, efficient gasification of biomass is required, and problems such as disposal of ash must be considered.
In conclusion, the gasification process is optimized, clean fuel gas is efficiently prepared, tar and ash byproducts are reduced, and reasonable disposal is realized, so that the method has important significance for application and development of biomass gasification technology.
At present, the biomass catalytic gasification is widely researched and is the most effective measure for removing tar, improving the yield of gasified gas and improving the quality of the gasified gas. The commonly used catalysts are mainly nickel-based catalysts, natural ore catalysts and alkali metal catalysts. The natural ore and alkali metal catalysts have the advantages of wide sources, easiness in obtaining, relatively low cost, capability of being directly mixed with biomass raw materials to enter a gasification furnace to participate in reaction, good catalytic effect and the like, and are widely researched.
The ash is rich in alkali metals and alkaline earth metals (K, Na, Ca, Mg, etc.), especially K inorganic substances and Ca inorganic substances, which have high catalytic activity. Wherein K is the most widely used alkali metal catalyst; ca is the most main active ingredient in the commonly used natural mineral catalyst dolomite, and the dolomite calcined at high temperature has higher catalytic activity, so that the gasified ash has potential utilization value as a catalytic additive. The catalytic performance and tar removal capacity of K-class and Ca-class inorganic matters in the ash are integrated, and the gasified ash is used in the biomass gasification process, so that the potential of reducing tar content to prepare clean fuel gas and realizing full-component utilization of gasification products is realized.
Disclosure of Invention
In order to provide a gasification ash utilization way and improve gasification efficiency, the invention provides a biomass gasification ash resource recycling catalytic utilization method, which is beneficial to resource utilization of gasification ash and improves the quality of gasification gas; alkali metals and alkaline earth metals in the gasified ash are activated by a high-temperature calcination mode and further used as catalysts to be mixed and gasified with biomass raw materials, the alkali metals and the alkaline earth metals in the regenerated ash obtained in the process are enriched, the alkali metals and the alkaline earth metals in the regeneration are activated and catalytically utilized by a high-temperature calcination mode, and the process is repeated in a circulating way, so that the resource utilization of the gasified ash is realized, and the gasified fuel gas with higher quality is obtained.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a resource recycling catalytic utilization method of biomass gasification ash comprises the following steps:
step 1, crushing and feeding biomass raw materials
The transported biomass raw materials are stored in a coarse material box, crushed by a crusher, stored in a material storage box and transported to a gasification furnace by a conveyor belt under the action of a transport motor;
step 2, separating biomass gasification ash from fuel gas
The biomass sequentially passes through four reaction stages of drying, pyrolysis, oxidation and reduction in a gasification furnace to generate gasified crude gas and gasified original ash, and the crude gas is subjected to subsequent purification, storage and other treatment; gasifying raw ash for subsequent calcination activation to be used as a catalyst;
step 3, high-temperature calcination, activation and cyclic utilization of gasified ash
Raw ash obtained by biomass gasification is sent to a high-temperature calcining device, wherein alkali metal and alkaline earth metal are activated and then are conveyed to a conveyor belt according to the proportion of the alkali metal and the alkaline earth metal to be mixed with biomass to enter a gasification furnace for catalytic gasification;
the primary circulating ash is obtained through circulation, wherein alkali metal and alkaline earth metal are further enriched, the primary circulating ash is collected in the high-temperature calcining device again, the alkali metal and alkaline earth metal are activated, and then the primary circulating ash is mixed with the biomass raw material again for catalytic gasification;
in addition, due to the enrichment of alkali metals and alkaline earth metals and the catalysis of the ash residues in the recycling process, the biomass gasification process is promoted, the tar content in the gasified fuel gas is reduced, and the heat value of the fuel gas is increased;
step 4, purifying and storing the crude fuel gas
The gasified crude gas is conveyed to a purification device, and the uncracked macromolecular tar is captured and collected. The purified gas is finally stored in a clean gas storage tank.
The invention has the following beneficial effects: the resource utilization of biomass gasification ash is realized; the alkali metal and alkaline earth metal in the ash regenerated by multiple cycles (calcination activation-catalysis) are enriched, and the catalytic action of the ash is continuously enhanced; under the catalytic action of ash, tar is catalytically cracked in the biomass gasification process, so that the tar content is reduced, the gas quality is improved, and the aim of efficiently preparing clean gas by biomass is finally fulfilled.
Drawings
FIG. 1 is a flow chart of a recycling catalytic utilization method of biomass gasification ash.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Referring to fig. 1, a resource recycling catalytic utilization method of biomass gasification ash comprises the following steps:
step 1, crushing and feeding biomass raw materials
The transported biomass raw materials are stored in a coarse material box, crushed by a crusher, stored in a material storage box and transported to a gasification furnace by a conveyor belt under the action of a transport motor;
step 2, separating biomass gasification ash from fuel gas
The biomass sequentially passes through four reaction stages of drying, pyrolysis, oxidation and reduction in a gasification furnace to generate gasified crude gas and gasified original ash, and the crude gas is subjected to subsequent purification, storage and other treatment; gasifying raw ash for subsequent calcination activation to be used as a catalyst;
step 3, high-temperature calcination, activation and cyclic utilization of gasified ash
Raw ash obtained by biomass gasification is sent to a high-temperature calcining device, wherein alkali metal and alkaline earth metal are activated and then are conveyed to a conveyor belt according to the proportion of the alkali metal and the alkaline earth metal to be mixed with biomass to enter a gasification furnace for catalytic gasification;
the primary circulating ash is obtained through circulation, wherein alkali metal and alkaline earth metal are further enriched, and the primary circulating ash is collected in the high-temperature calcining device again, activated and then mixed with the biomass raw material again for catalytic gasification;
in addition, due to the enrichment of alkali metals and alkaline earth metals and the catalysis of the ash residues in the recycling process, the biomass gasification process is promoted, the tar content in the gasified fuel gas is reduced, and the heat value of the fuel gas is increased;
step 4, purifying and storing the crude fuel gas
The gasified crude gas is conveyed to a purification device, and the uncracked macromolecular tar is captured and collected. The purified gas is finally stored in a clean gas storage tank.
The biomass storage and transportation, the biomass gasification furnace, the ash recycling and calcining cycle, the gasification gas purification and storage of the system for realizing the biomass gasification ash recycling, circulating and catalyzing and utilizing method of the invention,
the process method related by the invention comprises the following steps: the transported biomass raw materials are stored in a coarse material box, crushed by a crusher, stored in a material storage box and transported to a gasification furnace by a conveyor belt under the action of a transport motor. The biomass is gasified in a gasification furnace to generate gasified crude fuel gas and gasified original ash. The crude fuel gas is subjected to subsequent purification, storage and other treatment; the gasified raw ash is activated by subsequent calcination to be used as a catalyst. The original ash passes through a high-temperature calcining device, alkali metal and alkaline earth metal in the original ash are activated, and then the activated alkali metal and alkaline earth metal are conveyed to a conveying belt according to the proportion of the activated alkali metal and the activated alkaline earth metal to be mixed with biomass to enter a gasification furnace for catalytic gasification. Thus obtaining primary circulating ash slag through circulation, and enriching alkali metal and alkaline earth metal in the recycling process. The primary circulating ash is collected in the high-temperature calcining device again, the alkali metal and the alkaline earth metal are activated, and then the activated alkali metal and the alkaline earth metal are mixed with the biomass raw material again for catalytic gasification. The secondary circulating ash is obtained in the process and is reused through the processes of high-temperature calcination, mixing with biomass raw materials and catalysis and the like. The ash and slag are recycled in such a way. Because alkali metals and alkaline earth metals are continuously enriched in ash residues in the recycling process, the catalytic action of the ash residues is continuously enhanced, the biomass gasification process is promoted, the tar content in the gasified fuel gas is reduced, and the heat value of the fuel gas is improved. The gasified crude gas is conveyed to a purification device, and the uncracked macromolecular tar is captured and collected. The purified gas is finally stored in a clean gas storage tank.
The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the examples, but rather as being defined by the claims and the equivalents thereof which can occur to those skilled in the art upon consideration of the present inventive concept.
Claims (1)
1. A resource recycling catalytic utilization method of biomass gasification ash is characterized by comprising the following steps:
step 1, crushing and feeding biomass raw materials
The transported biomass raw materials are stored in a coarse material box, crushed by a crusher, stored in a material storage box and transported to a gasification furnace by a conveyor belt under the action of a transport motor;
step 2, separating biomass gasification ash from fuel gas
The biomass sequentially passes through four reaction stages of drying, pyrolysis, oxidation and reduction in a gasification furnace to generate gasified crude gas and gasified original ash, and the crude gas is subjected to subsequent purification and storage treatment; gasifying raw ash for subsequent calcination activation to be used as a catalyst;
step 3, high-temperature calcination, activation and cyclic utilization of gasified ash
Raw ash obtained by biomass gasification is sent to a high-temperature calcining device, wherein alkali metal and alkaline earth metal are activated and then are conveyed to a conveyor belt according to the proportion of the alkali metal and the alkaline earth metal to be mixed with biomass to enter a gasification furnace for catalytic gasification;
the primary circulating ash is obtained through circulation, wherein alkali metal and alkaline earth metal are further enriched, the primary circulating ash is collected in the high-temperature calcining device again, the alkali metal and alkaline earth metal are activated, and then the primary circulating ash is mixed with the biomass raw material again for catalytic gasification;
in addition, due to the enrichment of alkali metals and alkaline earth metals and the catalysis of the ash residues in the recycling process, the biomass gasification process is promoted, the tar content in the gasified fuel gas is reduced, and the heat value of the fuel gas is increased;
step 4, purifying and storing the crude fuel gas
The gasified crude gas is conveyed to a purification device, and the uncracked macromolecular tar is captured and collected. The purified gas is finally stored in a clean gas storage tank.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN115672334A (en) * | 2022-10-27 | 2023-02-03 | 华北理工大学 | Binary metal gasification ash-based catalyst and preparation method and application thereof |
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Application publication date: 20211001 |