CN110982558B - A method for directly producing hydrogen and carbon monoxide from coal or biomass gasification based on chemical chain technology - Google Patents
A method for directly producing hydrogen and carbon monoxide from coal or biomass gasification based on chemical chain technology Download PDFInfo
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003245 coal Substances 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- 238000002309 gasification Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001301 oxygen Substances 0.000 claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 57
- 238000000926 separation method Methods 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 42
- 239000000446 fuel Substances 0.000 claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000571 coke Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002802 bituminous coal Substances 0.000 claims description 2
- 230000005465 channeling Effects 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000035425 carbon utilization Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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Classifications
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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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
- C10J3/56—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
-
- 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
- C10J3/723—Controlling or regulating the gasification process
-
- 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
- C10J3/725—Redox processes
-
- 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
-
- 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
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/026—Dust removal by centrifugal forces
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0028—Separation of the specific gas from gas mixtures containing a minor amount of this specific gas
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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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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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
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Abstract
本发明公开了一种基于化学链技术的煤或生物质气化直接制备氢气和一氧化碳的方法，包括：燃料反应器、氧气反应器、第一气固分离装置、第二气固分离装置、第一控制流动装置、第二控制流动装置、空气分离装置；氧化钙在燃料反应器中捕集二氧化碳，在氧气反应器中释放二氧化碳，在催化剂作用下二氧化碳和焦炭反应生成一氧化碳，氧气和二氧化碳既作为流化介质，同时也作为反应原料。本发明流程简单，操作方便，工艺原料科学易得，成本低，碳利用效率高，污染物少，环境友好。
The invention discloses a method for directly preparing hydrogen and carbon monoxide by gasification of coal or biomass based on chemical chain technology, comprising: a fuel reactor, an oxygen reactor, a first gas-solid separation device, a second gas-solid separation device, a first gas-solid separation device, A control flow device, a second control flow device, and an air separation device; calcium oxide captures carbon dioxide in the fuel reactor, releases carbon dioxide in the oxygen reactor, and reacts with coke to generate carbon monoxide under the action of a catalyst. Oxygen and carbon dioxide both act as The fluidized medium is also used as the reaction raw material. The invention has the advantages of simple process, convenient operation, scientific and easy-to-obtain process raw materials, low cost, high carbon utilization efficiency, less pollutants and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of energy and chemical industry, in particular to a method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on a chemical chain technology.
Background
The synthesis gas uses carbon monoxide and hydrogen as main components and is used as a raw material gas of chemical raw materials. The raw material range of the synthesis gas is wide, and the synthesis gas can be generated by gasifying solid fuels such as coal or coke, can be prepared from light hydrocarbons such as natural gas and naphtha, and can be produced from heavy oil by a partial oxidation method. However, in the past, the production of syngas, whether coal or natural gas as fuel, has produced large amounts of carbon dioxide, and thus, the removal of carbon dioxide or the conversion of carbon dioxide to carbon monoxide in the syngas production process is desirable to further improve system efficiency, reduce emissions, and protect the environment.
The calcium-based chemical-looping carbon capture technology is a carbon dioxide capture technology which is widely researched at present, a carbon dioxide capture device after calcium circulation combustion of a demonstration device level is available in the world, hydrogen with high purity (> 85%) can be produced and carbon dioxide can be captured in a hydrogen production process of coal gasification or methane wet reforming process and calcium circulation coupling, however, how to dispose the captured carbon dioxide becomes a new problem, pure oxygen is needed in a calcium oxide regeneration process, and the pure oxygen is only used for combusting coke to provide heat to regenerate the calcium oxide and capture the carbon dioxide, so that the system efficiency is reduced, therefore, the process is combined with a synthesis gas production process, the added value of the product produced by the whole device can be better increased, and the fuel can be efficiently utilized.
In other processes or devices for preparing hydrogen and carbon monoxide by gasifying coal or biomass based on chemical chain technology (CN103113917, CN208234855, CN101638590, CN107325846, and CN101975395), no method for in-situ conversion of carbon dioxide into carbon monoxide is mentioned or solved, and the device has a more complex structural design, which results in higher cost.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on a chemical chain technology, so that the aim of converting carbon dioxide trapped in a calcium cycle coal gasification process into carbon monoxide in situ is fulfilled, and synthesis gas (hydrogen and carbon monoxide) with adjustable proportion is directly obtained.
In order to solve the technical problems, the invention provides a device for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on a chemical looping technology, which comprises: the system comprises a fuel reactor, an oxygen reactor, a first gas-solid separation device, a second gas-solid separation device, a first flow control device, a second flow control device and an air separation device; the calcium carbonate bed material loaded with iron or nickel enters an oxygen reactor through a first gas-solid separation device and a first control flow device to generate calcium oxide bed material loaded with iron or nickel, and the calcium oxide bed material loaded with iron or nickel enters a fuel reactor through a second gas-solid separation device and a second control flow device to generate calcium carbonate bed material loaded with iron or nickel again; the bed material is circulated between two reactors, wherein steam and coal or biomass are fed into a fuel reactor and hydrogen is produced, and oxygen is fed into an oxygen reactor and carbon monoxide is produced, wherein the oxygen is supplied from an air separation unit, which separates nitrogen from oxygen in the air to obtain pure oxygen.
Preferably, the fuel reactor and the oxygen reactor are both fluidized beds, and the flow patterns are both fast fluidized beds or pneumatic conveying beds.
Preferably, the first gas-solid separation device and the second gas-solid separation device are both one of an inertial separator and a cyclone separator, and the first gas-solid separation device and the second gas-solid separation device separate gas and solid particles generated in the reactor.
Preferably, the first control flow device and the second control flow device are each one of a V-valve, a U-valve, an L-valve, an H-valve and a J-valve, and the first control flow device and the second control flow device control bed material transfer and prevent gas channeling between reactors.
Preferably, the bed material mainly comprises calcium oxide and is loaded with iron or nickel, and the main loading method is an impregnation method.
Correspondingly, the method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on a chemical chain technology comprises the following steps:
(1) feeding coal or biomass particles with the particle size of 0.1-10mm into the bottom of a fuel reactor, lifting calcium oxide bed material particles with the particle size of 0.07-0.7mm and loaded with iron or nickel to the top of the fuel reactor, wherein in the lifting process, the iron or nickel plays a role of catalysis, the calcium oxide adsorbs carbon dioxide to generate calcium carbonate, hydrogen with the concentration of 85% is separated in a first gas-solid separation device, the temperature of the fuel reactor is controlled to be 600-800 ℃, and the inside of the reactor is in a reducing atmosphere;
(2) controlling the temperature of an oxygen reactor to be 700-950 ℃, feeding calcium carbonate bed material particles loaded with iron or nickel into the bottom of the oxygen reactor, lifting the calcium carbonate bed material particles to the top of the oxygen reactor by oxygen, heating the calcium carbonate to decompose the calcium carbonate into calcium oxide and carbon dioxide in the lifting process, reacting the carbon dioxide, coke and oxygen together to generate carbon monoxide, and separating the carbon monoxide with the concentration of 85% in a first gas-solid separation device;
(3) according to the steps (1) and (2), iron and nickel are used as catalysts for the reaction, and simultaneously, carbon deposit generated in the fuel reactor and oxygen in the oxygen reactor are subjected to partial oxidation reaction to generate carbon monoxide.
Preferably, the coal or biomass fuel particles include bituminous coal, gas coal and lignite, or are replaced by biomass particles or other carbonaceous solid waste particles.
The invention has the beneficial effects that: the invention can capture carbon dioxide while producing hydrogen by coal or biomass gasification, can directly convert the captured carbon dioxide into carbon monoxide in situ, and can produce hydrogen and carbon monoxide which are needed most in the chemical process by converting solid fuels such as coal or biomass and the like by using the double fluidized bed reactor, and can obtain synthesis gas with adjustable carbon-hydrogen ratio according to actual needs.
Drawings
FIG. 1 is a schematic structural diagram of the apparatus of the present invention.
Wherein, 1, a fuel reactor; 2. an oxygen reactor; 3. a first gas-solid separation device; 4. a second gas-solid separation device; 5. a second control flow device; 6. a first control flow device; 7. an air separation plant.
Detailed Description
As shown in fig. 1, an apparatus for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology comprises: the system comprises a fuel reactor, an oxygen reactor, a first gas-solid separation device, a second gas-solid separation device, a first flow control device, a second flow control device and an air separation device; the calcium carbonate bed material loaded with iron or nickel enters an oxygen reactor through a first gas-solid separation device and a first control flow device to generate calcium oxide bed material loaded with iron or nickel, and the calcium oxide bed material loaded with iron or nickel enters a fuel reactor through a second gas-solid separation device and a second control flow device to generate calcium carbonate bed material loaded with iron or nickel again; the bed material is circulated between two reactors, wherein steam and coal or biomass are fed into a fuel reactor and hydrogen is produced, and oxygen is fed into an oxygen reactor and carbon monoxide is produced, wherein the oxygen is supplied from an air separation unit, which separates nitrogen from oxygen in the air to obtain pure oxygen.
A method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on a chemical chain technology comprises the following steps:
(1) feeding coal or biomass particles with the particle size of 0.1-10mm into the bottom of a fuel reactor, lifting calcium oxide bed material particles with the particle size of 0.07-0.7mm and loaded with iron or nickel to the top of the fuel reactor, wherein in the lifting process, the iron or nickel plays a role of catalysis, the calcium oxide adsorbs carbon dioxide to generate calcium carbonate, hydrogen with the concentration of 85% is separated in a first gas-solid separation device, the temperature of the fuel reactor is controlled to be 600-800 ℃, and the inside of the reactor is in a reducing atmosphere;
(2) controlling the temperature of the oxygen reactor to 700-950 ℃, feeding the calcium carbonate bed material particles loaded with iron or nickel into the bottom of the oxygen reactor, lifting the calcium carbonate bed material particles to the top of the oxygen reactor by oxygen, and heating and decomposing the calcium carbonate into calcium oxide and carbon dioxide in the lifting process. The carbon dioxide, coke and oxygen react together to generate carbon monoxide, and the carbon monoxide with the concentration of 85% is separated in a first gas-solid separation device;
(3) according to the steps (1) and (2), iron and nickel are used as catalysts for the reaction, and meanwhile, carbon deposit generated in the fuel reactor can also be partially oxidized with oxygen in the oxygen reactor to generate carbon monoxide.
Example 1:
the process method comprises a fuel reactor, an oxygen reactor, a first gas-solid separation device, a second gas-solid separation device, a first flow control device, a second flow control device and an air separation device; the calcium carbonate bed material loaded with iron or nickel enters an oxygen reactor through a first gas-solid separation device and a first control flow device to generate calcium oxide bed material loaded with iron or nickel, and the calcium oxide bed material loaded with iron or nickel enters a fuel reactor through a second gas-solid separation device and a second control flow device to generate calcium carbonate bed material loaded with iron or nickel again; the bed material circulates between two reactors, in which steam and coal or biomass are fed into a fuel reactor and hydrogen is produced, and oxygen is fed into an oxygen reactor and carbon monoxide is produced.
The fuel reactor and the oxygen reactor described in this example are both fluidized beds, and the flow patterns are both fast bed flow patterns or pneumatic transport bed flow patterns.
In this embodiment, the gas-solid separation device is one of an inertial separator and a cyclone separator, and the gas-solid separation device separates gas and solid particles generated in the reactor.
In the embodiment, the first flow control device and the second flow control device are all one of a V valve, a U valve, an L valve, an H valve and a J valve, and the flow control devices control bed material transmission and prevent gas back-flowing between reactors.
The bed material used in this example was mainly composed of calcium oxide and loaded with iron or nickel, and the main loading method was impregnation.
The process method for directly preparing hydrogen and carbon monoxide by using the device is characterized by comprising the following specific process steps:
(1) feeding coal or biomass particles with the particle size of 0.1-10mm into the bottom of a fuel reactor, lifting calcium oxide bed material particles with the particle size of 0.07-0.7mm and loaded with iron or nickel to the top of the fuel reactor, wherein in the lifting process, the iron or nickel plays a role of catalysis, the calcium oxide adsorbs carbon dioxide to generate calcium carbonate, hydrogen with the concentration of 85% is separated in a first gas-solid separation device, the temperature of the fuel reactor is controlled to be 600-800 ℃, and the inside of the reactor is in a reducing atmosphere;
(2) controlling the temperature of the oxygen reactor to 700-950 ℃, feeding the calcium carbonate bed material particles loaded with iron or nickel into the bottom of the oxygen reactor, lifting the calcium carbonate bed material particles to the top of the oxygen reactor by oxygen, and heating and decomposing the calcium carbonate into calcium oxide and carbon dioxide in the lifting process. The carbon dioxide, coke and oxygen react together to generate carbon monoxide, and the carbon monoxide with the concentration of 85% is separated in a first gas-solid separation device;
(3) according to the steps (1) and (2), iron and nickel are used as catalysts for the reaction, and meanwhile, carbon deposit generated in the fuel reactor can also be partially oxidized with oxygen in the oxygen reactor to generate carbon monoxide.
The chemical reaction performed in step (1) described in this example includes:
CaO+CO2→CaCO3
coal/biomass+heat→gases+tar+char
C+H2O→CO+H2
C+2H2O→CO2+2H2
CO+H2O→CO2+H2
Tars+H2O→gases+hydrocarbons
hydrocarbons+H2O→H2+CO2+CO。
the chemical reaction performed in step (2) described in this example includes:
CaCO3→CaO+CO2
2C+O2→2CO
C+CO2→2CO。
the chemical reaction performed in step (3) described in this example includes:
2C+O2→2CO。
Claims (6)
1. a method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on a chemical chain technology is characterized by comprising the following steps:
(1) feeding coal or biomass particles with the particle size of 0.1-10mm into the bottom of a fuel reactor, lifting calcium oxide bed material particles with the particle size of 0.07-0.7mm and loaded with iron or nickel to the top of the fuel reactor, wherein in the lifting process, the iron or nickel plays a role of catalysis, the calcium oxide adsorbs carbon dioxide to generate calcium carbonate, hydrogen with the concentration of 85% is separated in a first gas-solid separation device, the temperature of the fuel reactor is controlled to be 600-800 ℃, and the inside of the reactor is in a reducing atmosphere;
(2) controlling the temperature of an oxygen reactor to be 700-950 ℃, feeding calcium carbonate bed material particles loaded with iron or nickel into the bottom of the oxygen reactor, lifting the calcium carbonate bed material particles to the top of the oxygen reactor by oxygen, heating the calcium carbonate to decompose the calcium carbonate into calcium oxide and carbon dioxide in the lifting process, reacting the carbon dioxide, coke and oxygen together to generate carbon monoxide, and separating the carbon monoxide with the concentration of 85% in a first gas-solid separation device;
(3) according to the steps (1) and (2), iron and nickel are used as catalysts for the reaction, and simultaneously, carbon deposit generated in the fuel reactor and oxygen in the oxygen reactor are subjected to partial oxidation reaction to generate carbon monoxide.
2. The method for direct production of hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology as claimed in claim 1, wherein the coal comprises bituminous coal, gas coal and lignite.
3. The method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology according to claim 1, wherein the device for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology is utilized, and the device comprises: the system comprises a fuel reactor, an oxygen reactor, a first gas-solid separation device, a second gas-solid separation device, a first flow control device, a second flow control device and an air separation device; the calcium carbonate bed material loaded with iron or nickel enters an oxygen reactor through a first gas-solid separation device and a first control flow device to generate calcium oxide bed material loaded with iron or nickel, and the calcium oxide bed material loaded with iron or nickel enters a fuel reactor through a second gas-solid separation device and a second control flow device to generate calcium carbonate bed material loaded with iron or nickel again; the bed material is circulated between two reactors, wherein steam and coal or biomass are fed into a fuel reactor and hydrogen is produced, and oxygen is fed into an oxygen reactor and carbon monoxide is produced, wherein the oxygen is supplied from an air separation unit, which separates nitrogen from oxygen in the air to obtain pure oxygen.
4. The method for direct production of hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology as claimed in claim 3, wherein the fuel reactor and the oxygen reactor are both fluidized beds, and the flow pattern is either fast fluidized bed or pneumatic transport bed.
5. The method for directly preparing hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology as claimed in claim 3, wherein the first gas-solid separation device and the second gas-solid separation device are both one of inertial separator and cyclone separator, and the first gas-solid separation device and the second gas-solid separation device separate gas and solid particles generated in the reactor.
6. The method for direct production of hydrogen and carbon monoxide by coal or biomass gasification based on chemical looping technology as claimed in claim 3, wherein the first control flow device and the second control flow device are each one of V valve, U valve, L valve, H valve and J valve, and the first control flow device and the second control flow device control bed material transfer and prevent gas channeling between reactors.
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