CN114907884A - Multi-layer fluidized bed calcium chemical looping gasification hydrogen production device and method - Google Patents
Multi-layer fluidized bed calcium chemical looping gasification hydrogen production device and method Download PDFInfo
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- CN114907884A CN114907884A CN202210705541.9A CN202210705541A CN114907884A CN 114907884 A CN114907884 A CN 114907884A CN 202210705541 A CN202210705541 A CN 202210705541A CN 114907884 A CN114907884 A CN 114907884A
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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
- C10J3/48—Apparatus; Plants
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/14—Handling of heat and steam
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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
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- C10J3/82—Gas withdrawal means
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to a multilayer fluidized bed calcium chemical looping gasification hydrogen production device, which comprises a combustion furnace, a gasification furnace, a separator, an upper material returning device, a lower material returning device and a feeding device; the inside of the gasification furnace is divided into a gasification furnace gasification chamber and a gasification furnace cracking chamber, the bottom of the gasification furnace gasification chamber is communicated with the bottom of the combustion furnace through a lower material returning device, and the upper part of the combustion furnace is communicated with the gasification furnace cracking chamber through a separator and an upper material returning device. The hydrogen production method comprises the following steps: organic solid waste raw materials and a carbon absorbent enter a gasification chamber of a gasification furnace; carbon absorbent in-situ CO capture 2 Promoting the raw material to gasify and produce hydrogen to generate hydrogen-rich synthetic gas containing gaseous tar and semicoke, and catalytically cracking the gaseous tar in the synthetic gas into gaseous micromolecules by a carbon absorbentAnd (3) obtaining the product. The hydrogen production device and the method generate hydrogen-rich synthesis gas, semicoke and CaCO in the hydrogen production process 3 Semi-coke burning, CaCO in a burning furnace 3 Decomposition to release CO 2 Realizes the capture of CO in the hydrogen production process by one-step method 2 Simultaneously, the desulfurization and the tar removal are carried out.
Description
Technical Field
The invention relates to a hydrogen production technology which takes organic solid waste as raw material and combines a double fluidized bed reaction device with calcium chemical chain gasification, and simultaneously, the content of tar, sulfur and chlorine in product gas is greatly reduced through the design of a multilayer fluidized bed gasification furnace, and the preparation of clean hydrogen-rich gas is realized. Belongs to the technical field of organic solid waste resource utilization and hydrogen production.
Background
The organic solid wastes (agriculture and forestry organic solid wastes, livestock and poultry manure, kitchen waste, municipal sludge and the like) in China are huge in quantity and various in types. On the other hand, global hydrogen demand is rapidly increasing. Currently 92% of the global hydrogen comes from coal and natural gas and is not sustainable and environmentally friendly. The Chinese hydrogen energy alliance 'Chinese hydrogen energy and fuel cell industry white paper 2020' believes that decarburization becomes the first driving force for global hydrogen energy development, and low-carbon clean hydrogen is an important hand grip for realizing a carbon neutralization path. Low carbon and renewable energy sources have become a major trend in the development of hydrogen production technology. The organic solid waste low-carbon clean hydrogen technical route has good development prospect.
The organic solid waste calcium chemical-looping gasification hydrogen production system mainly comprises a gasification furnace and a calcining furnace, wherein the two reactors are fluidized bed reactors. Organic solid waste and steam in calcium-based CO in gasifier 2 Gasifying in the presence of absorbent, pyrolyzing and gasifying organic solid waste, and performing conversion reaction with water vapor to produce hydrogen and CO 2 The heat is absorbed by CaO, the forward progress of gasification and hydrogen production reaction is promoted (see the general reaction formula (1)), and simultaneously, the heat is provided for gasification heat absorption by CaO carbonation heat release. Produced CaCO 3 And the semicoke is sent into a calcining furnace and is regenerated into CaO (formula (2)) through air or oxygen combustion,can realize CO 2 High concentration enrichment (with oxygen) deactivated CaO is discharged. The technology integrates the gasification, hydrogen production and decarburization of organic solid wastes in one reactor, and can obtain high-concentration H 2 And realize CO 2 Removing; CaO decarbonizes and releases heat to provide heat for gasification, and CaO can inhibit tar generation.
C+2H 2 O+CaO→CaCO 3 + 2H 2 (1)
CaCO 3 →CaO+CO 2 (2)
Although CaO can inhibit tar generation in the current calcium chemical looping gasification hydrogen production technology, the method has the following defects: firstly, the temperature of the gasification furnace is generally below 650 ℃, so that the reaction speed of calcium compounds in the catalytic cracking of tar is limited; secondly, the contact reaction time of the calcium compound and tar cannot be controlled independently and effectively. There is still much room for further reduction of tar content in the product; thirdly, if a special tar catalytic cracking reaction unit is adopted at the downstream of the gasification hydrogen production unit, the bed layer is easy to deposit carbon, and the production period is shortened; fourthly, the product gas contains H 2 And the subsequent purification system is complex, so that the hydrogen production cost is increased.
At present, no relevant patent is found to describe a reaction device capable of simultaneously carrying out hydrogen production by gasifying organic solid wastes and tar cracking and desulfurization in a reactor, and therefore the invention is provided.
Disclosure of Invention
The invention provides a device and a method for producing hydrogen by calcium chemical looping gasification of a multilayer fluidized bed in order to overcome the defects of the technical problems. By the design of the multilayer fluidized bed gasification furnace, the catalytic cracking reaction of calcium compounds on tar can be effectively promoted by prolonging the reaction time and increasing the reaction temperature, and the tar content of the hydrogen-rich synthetic gas is greatly reduced; and calcium oxide and H are oxidized in the cracking reaction chamber 2 S is subjected to a sulfuration reaction, and S element in the hydrogen-rich synthetic gas is captured, so that the aim of desulfurizing the hydrogen-rich synthetic gas is fulfilled. The S element is finally enriched in the slag of the combustion furnace in the form of calcium sulfate.
The invention relates to a multilayer fluidized bed calcium chemical looping gasification hydrogen production device, which comprises a combustion furnace, a gasification furnace, a separator, an upper material returning device, a lower material returning device and a feeding device; the method is characterized in that: the gasification furnace is internally provided with a distribution plate which divides an internal cavity of the gasification furnace into a gasification chamber of the gasification furnace positioned at the lower part and a cracking chamber of the gasification furnace positioned at the upper part, and the gasification furnace is internally provided with a vertical pipe penetrating through the distribution plate; the feeding device is used for adding organic solid waste raw materials containing carbon absorbent into the gasification chamber of the gasification furnace, the bottom of the gasification chamber of the gasification furnace is communicated with the bottom of the combustion furnace through the lower material returning device, and the upper part of the combustion furnace is communicated with the cracking chamber of the gasification furnace through the separator and the upper material returning device; the bottom and the upper end of the gasification furnace are respectively provided with a steam inlet and a synthesis gas outlet, the bottom of the combustion furnace is provided with an oxygen or air inlet, and the top of the separator is provided with a flue gas outlet.
The invention relates to a hydrogen production method of a multilayer fluidized bed calcium chemical looping gasification hydrogen production device, which comprises the following steps: mixing the organic solid waste raw material and the carbon absorbent according to a certain proportion, feeding the mixture into a gasification chamber of a gasification furnace through a feeding device, and introducing water vapor according to a certain proportion; the high-temperature circulating bed material enters a gasification chamber of a gasification furnace through a vertical pipe to provide energy for the gasification of the raw material; carbon absorbent in-situ CO capture 2 Promoting the raw materials to gasify and produce hydrogen to generate hydrogen-rich synthesis gas containing gaseous tar and semicoke; the reacted carbon absorbent and generated semicoke enter a combustion furnace along with the circulating bed material, and the semicoke is combusted, and the carbon absorbent is decomposed to release CO 2 (ii) a Circulating bed materials enter a cracking chamber of the gasification furnace from the combustion furnace to form a high-temperature material layer; the hydrogen-rich synthetic gas from the gasification chamber of the gasification furnace flows through a high-temperature material layer, the gaseous tar in the synthetic gas is catalytically cracked into gaseous micromolecule products through a carbon absorbent, and H in the synthetic gas 2 S and the carbon absorbent in the material layer are removed through a vulcanization reaction; realizes the capture of CO in the hydrogen production process by one-step method 2 Simultaneously, the desulfurization and the tar removal are carried out.
The invention relates to a hydrogen production method of a multilayer fluidized bed calcium chemical looping gasification hydrogen production device, which uses calcined limestone as a carbon absorbent.
According to the hydrogen production method of the multilayer fluidized bed calcium chemical looping gasification hydrogen production device, olivine or dolomite is added into calcined limestone serving as a carbon absorbent.
The invention relates to a hydrogen production method of a multilayer fluidized bed calcium chemical looping gasification hydrogen production device, which is realized by the following steps:
a) reaction in the gasification chamber of the gasifier: the organic solid waste raw material and calcined limestone are uniformly mixed according to a certain mass ratio and enter a gasification chamber of a gasification furnace through a feeding device, and simultaneously, a cracking chamber of the gasification furnace contains CaO and CaCO 3 Feeding the ash-mixed circulating bed material into a gasification chamber of a gasification furnace through a vertical pipe so as to maintain the temperature in the gasification chamber to be not lower than 600 ℃; simultaneously, water vapor enters the gasification chamber through a water vapor inlet at the bottom of the gasification furnace; organic solid waste raw materials are pyrolyzed and gasified and are subjected to conversion reaction with water vapor to produce hydrogen, the generated CO2 is absorbed by CaO, the forward proceeding of gasification and hydrogen production reaction is promoted, and the total reaction is shown as formulas (1) and (2):
C+2H 2 O+CaO→CaCO 3 + 2H 2 (1)
CO+H 2 O+CaO→CaCO 3 +H 2 （2）
hydrogen-rich synthesis gas with main components of H2, CO2, CH4 and gaseous tar is generated by hydrogen production reaction, and a solid product semi-coke is generated; the hydrogen-rich synthetic gas enters a cracking chamber of the gasification furnace through a distribution plate; the solid product semicoke and the generated CaCO3 enter the combustion furnace through the lower return feeder along with the circulating bed material;
b) reaction in a combustion furnace: introducing air or oxygen into the combustion furnace; burning the semicoke from the gasification furnace in a combustion furnace to release heat so as to maintain the temperature in the furnace above 850 ℃; CaCO in the bed material of combustion furnaces 3 Decomposing to CaO and releasing CO 2 The total reaction is shown in formulas (3) and (4):
C+O 2 →CO 2 (3)
CaCO 3 →CaO+CO 2 (4)
flue gas generated by the combustion furnace and most of bed materials leave the combustion furnace from the upper part and enter the separator, and a part of bed materials are discharged from the bottom of the combustion furnace;
c) reaction in the cracking chamber of the gasifier: the hot fume of the combustion furnace is discharged from a fume outlet at the top end of the separator, and the high-temperature circulating bed material enters the cracking chamber of the gasification furnace from the bottom end of the separator through an upper material returning device and comes from the gas of the gasification furnaceThe 650 ℃ hydrogen-rich synthesis gas of the gasification chamber enters the cracking chamber through a distribution plate; the circulating bed material is in a bubbling fluidization state in a cracking chamber of the gasification furnace; the gaseous tar in the hydrogen-rich synthesis gas is cracked into small molecular gaseous products under the catalytic action of calcium compounds in the bed material, so that the high-temperature deep catalytic cracking of the tar is realized; h in hydrogen-rich syngas 2 S and CaO in the bed material are subjected to a vulcanization reaction to generate CaS, so that the hydrogen-rich synthesis gas is desulfurized; discharging the purified hydrogen-rich synthetic gas from the top of the cracking chamber of the gasification furnace;
the bed material in the cracking chamber of the gasification furnace enters the gasification chamber of the gasification furnace through a vertical pipe and enters the next circulation reaction process.
In order to increase the reactivity of the carbon absorbent, the carbon absorbent is activated by introducing water vapor into the combustion furnace while introducing air or oxygen into the combustion furnace.
The invention has the beneficial effects that: the invention relates to a multi-layer fluidized bed calcium chemical chain gasification hydrogen production device, which consists of a combustion furnace and a gasification furnace, wherein an inner cavity of the gasification furnace is divided into an upper cracking chamber and a lower cracking chamber and a gasification chamber by a distribution plate, the upper part of the combustion furnace is communicated with the cracking chamber through a separator and an upper return feeder, and the gasification chamber is communicated with the combustion furnace through a lower return feeder, so that the combustion furnace and the gasification furnace form a double fluidized bed reaction device, and the gasification chamber and the cracking chamber in the gasification furnace form a multi-layer fluidized bed. In the hydrogen production process, the mixture of organic solid waste raw material and carbon absorbent (CaO) generates hydrogen production reaction in a gasification chamber to generate hydrogen-rich synthesis gas and semicoke and CaCO 3 (ii) a Semi-coke burning, CaCO in a combustion furnace 3 Decomposition to release CO 2 (ii) a In the cracking chamber, tar in the hydrogen-rich synthesis gas is catalytically cracked into gaseous small molecule products, H 2 S and CaO are subjected to a vulcanization reaction to generate CaS. Realizes the capture of CO in the hydrogen production process by one-step method 2 Simultaneously, the desulfurization and the tar removal are carried out.
Therefore, the hydrogen production method of the multilayer fluidized bed calcium chemical looping gasification hydrogen production device has the following advantages:
(1) the gasification furnace is a double-layer fluidized bed consisting of a gasification chamber and a cracking chamber, and the deep catalytic cracking of tar in the hydrogen-rich synthesis gas is realized by controlling the catalytic cracking reaction temperature and time of the cracking chamber of the gasification furnace, so that the content of hydrogen-producing tar is greatly reduced;
(2) carbon deposition generated by tar cracking enters a combustion furnace along with circulating bed materials to be combusted and removed. The problem of if the low reaches set up tar schizolysis unit alone and easily deposit carbon is solved.
(3) In the cracking chamber of the gasification furnace, CaO in the bed material and H in the hydrogen-rich synthesis gas 2 S is subjected to a sulfurization reaction to trap H 2 S, sulfur is finally enriched in the slag discharged by the combustion furnace. The desulfurization in the furnace is realized.
(4) Through the three processes, the cleanliness of the prepared hydrogen can be improved, a subsequent purification system is simplified, and the investment and operation cost are reduced. And can further generate high-concentration CO through pure oxygen combustion 2 And the carbon capture is realized or the raw material of downstream production is used.
Drawings
FIG. 1 is a schematic structural diagram of a multi-layer fluidized bed calcium chemical looping gasification hydrogen production device of the invention;
FIG. 2 is a schematic diagram of the operation of the multi-layer fluidized bed calcium chemical looping gasification hydrogen production device of the invention.
In the figure: 1 combustion furnace, 2 separators, 3 upward returning charge wares, 4 gasifier cracking chambers, 5 risers, 6 distribution plates, 7 gasifier gasification chambers, 8 feeding devices, 9 downward returning charge wares, 10 auxiliary feeding devices and 11 gasifiers.
Detailed Description
The invention is further described with reference to the following figures and examples.
As shown in fig. 1 and fig. 2, a schematic structural diagram and a schematic working diagram of a multi-layer fluidized bed calcium chemical looping gasification hydrogen production device of the present invention are respectively provided, the hydrogen production device is composed of a combustion furnace 1, a gasification furnace 11, a separator 2, an upper material returning device 3, a lower material returning device 9 and a feeding device 8, a transverse distribution plate 6 is arranged in an internal cavity of the gasification furnace 11, the distribution plate 6 isolates the internal cavity of the gasification furnace 11, so that a gasification furnace cracking chamber 4 is formed at the upper part of the gasification furnace 11, and a gasification furnace gasification chamber 7 is formed at the lower part of the gasification furnace 11. The feeding device 8 is used for feeding organic solid waste raw materials containing carbon absorbent into the gasification furnace gasification chamber 7, the carbon absorbent adopts calcined limestone, and the raw materials adopt organic solid wastes, such as agriculture and forestry organic solid waste, livestock and poultry manure, kitchen waste, municipal sludge and the like.
The upper part of the combustion furnace 1 is communicated with a gasification furnace cracking chamber 4 through a separator 2 and an upper material returning device 3, so that bed materials in the combustion furnace 1 enter the gasification furnace cracking chamber 4; a vertical pipe 5 penetrating through the distribution plate 6 is provided in the gasification furnace 11 so that the bed material in the gasification furnace cracking chamber 4 flows into the gasification furnace gasification chamber 7 through the vertical pipe 5. The gasifier gasification chamber 7 is shown in communication with the combustion furnace 1 via a lower return feeder 9 so that bed material in the gasifier gasification chamber 7 enters the combustion furnace 1.
As a further improvement, the height of the upper end of the vertical pipe 5 is higher than that of the distribution plate 6 so as to maintain a material layer with a certain height on the distribution plate; the lower end of the vertical pipe 5 is inserted into a bed material layer at the bottom of the gasification chamber 7 of the gasification furnace. In order to achieve that fuel can be fed into the burner 1, the burner 1 is shown to be provided with an auxiliary feeding device 10 at the bottom, through which auxiliary feeding device 10 fuel is fed into the burner.
The invention relates to a hydrogen production method of a multilayer fluidized bed calcium chemical looping gasification hydrogen production device, which is realized by the following steps:
a) reaction in the gasification chamber of the gasifier: the organic solid waste raw material and the calcined limestone are uniformly mixed according to a certain mass ratio and enter a gasification chamber of a gasification furnace through a feeding device, and meanwhile, the pyrolysis chamber of the gasification furnace contains CaO and CaCO 3 The ash-mixed 800 ℃ circulating bed material enters the gasification chamber of the gasification furnace through a vertical pipe so as to maintain the temperature in the gasification chamber to be not lower than 600 ℃. Meanwhile, the water vapor enters the gasification chamber through a water vapor inlet at the bottom of the gasification furnace. Organic solid waste raw material is pyrolyzed and gasified and is subjected to conversion reaction with water vapor to produce hydrogen, and CO is generated 2 Is absorbed by CaO, promotes the forward progress of gasification and hydrogen production reaction, and the total reaction is shown as formulas (1) and (2):
C+2H 2 O+CaO→CaCO 3 + 2H 2 (1)
CO+H 2 O+CaO→CaCO 3 +H 2 （2）
the hydrogen production reaction produces hydrogen-rich syngas with major components of H2, CO2, CH4, and gaseous tar, as well as solid product, semicoke. The hydrogen-rich synthetic gas enters a gasification furnace through a distribution plate for crackingA chamber; semicoke as solid product and CaCO produced 3 The material enters the combustion furnace together with the circulating bed material through the lower material returning device;
b) reaction in a combustion furnace: and introducing air or oxygen into the combustion furnace. The semicoke from the gasification furnace is burnt in the combustion furnace to release heat so as to maintain the temperature in the furnace above 850 ℃. CaCO in the bed material of combustion furnaces 3 Decomposing to CaO and releasing CO 2 The total reaction is shown as formulas (3) and (4):
C+O 2 →CO 2 (3)
CaCO 3 →CaO+CO 2 (4)
flue gas generated by the combustion furnace and most of bed materials leave the combustion furnace from the upper part and enter the separator, and a part of bed materials are discharged from the bottom of the combustion furnace;
c) reaction in the cracking chamber of the gasifier: hot flue gas is discharged from a flue gas outlet at the top end of the separator, 900 ℃ circulating bed materials enter a gasification furnace cracking chamber from the bottom end of the separator through an upper material returning device, and 650 ℃ hydrogen-rich synthetic gas from the gasification furnace cracking chamber enters the cracking chamber through a distribution plate; the circulating bed material is in bubbling fluidization state in the cracking chamber of the gasification furnace, and the temperature is maintained above 800 ℃. The gaseous tar in the hydrogen-rich synthesis gas is cracked into gaseous micromolecule products under the catalytic action of calcium compounds in the bed materials, so that the high-temperature deep catalytic cracking of the tar is realized; h in hydrogen-rich syngas 2 S and CaO in the bed material are subjected to a sulfuration reaction to generate CaS, so that the hydrogen-rich synthesis gas is desulfurized. Discharging the purified hydrogen-rich synthetic gas from the top of the cracking chamber of the gasification furnace;
the top end of the vertical pipe is higher than the distribution plate to maintain the height of the material layer and control the residence time and the reaction time. The vertical pipe is inserted into the bottom of the material layer of the gasification chamber of the gasification furnace so as to control the height of the material in the vertical pipe. The bed material in the cracking chamber of the gasification furnace overflows into the vertical pipe and descends into the gasification chamber of the gasification furnace, and then enters the next circulation reaction process.
In the reaction in the gasification chamber in the step a), substances added by the feeding device are organic solid waste raw materials, calcined limestone and olivine, and the ratio of the organic solid waste raw materials to the calcined limestone to the olivine is 10: 1: 0.2 mass ratio.
Claims (6)
1. A multi-layer fluidized bed calcium chemical looping gasification hydrogen production device comprises a combustion furnace (1), a gasification furnace (11), a separator (2), an upper material returning device (3), a lower material returning device (9) and a feeding device (8); the method is characterized in that: a distribution plate (6) is arranged in the gasification furnace, the distribution plate divides the internal cavity of the gasification furnace into a gasification chamber (7) of the gasification furnace at the lower part and a cracking chamber (4) of the gasification furnace at the upper part, and a vertical pipe (5) penetrating through the distribution plate is arranged in the gasification furnace; the feeding device (8) is used for adding organic solid waste raw materials containing carbon absorbent into the gasification furnace gasification chamber (7), the bottom of the gasification furnace gasification chamber (7) is communicated with the bottom of the combustion furnace (1) through a lower material returning device (9), and the upper part of the combustion furnace (1) is communicated with the gasification furnace cracking chamber (4) through a separator (2) and an upper material returning device (3); the bottom and the upper end of the gasification furnace (11) are respectively provided with a steam inlet and a hydrogen-rich synthetic gas outlet, the bottom of the combustion furnace (1) is provided with an oxygen or air inlet, and the top of the separator (2) is provided with a flue gas outlet.
2. A hydrogen production method based on the multilayer fluidized bed calcium chemical looping gasification hydrogen production device of claim 1 is characterized by comprising the following steps: mixing the organic solid waste raw material and the carbon absorbent according to a certain proportion, feeding the mixture into a gasification chamber (7) of a gasification furnace through a feeding device (8), and simultaneously introducing water vapor according to a certain proportion; the high-temperature circulating bed material enters a gasification chamber (7) of the gasification furnace through a vertical pipe (5) to provide energy for the gasification of the raw material; carbon absorbent in-situ CO capture 2 Promoting the raw materials to gasify and produce hydrogen to generate hydrogen-rich synthesis gas containing gaseous tar and semicoke; CO capture 2 The generated carbocoal and the carbon absorbent enter a combustion furnace (1) along with the circulating bed material, the carbocoal is combusted, and the carbon absorbent is decomposed to release CO 2 (ii) a Circulating bed materials enter a gasification furnace cracking chamber (4) from a combustion furnace to form a high-temperature material layer; the hydrogen-rich synthetic gas from the gasification furnace gasification chamber (7) flows through a high-temperature material layer, the gaseous tar in the synthetic gas is catalytically cracked into gaseous micromolecule products through a carbon absorbent, and H in the synthetic gas 2 S and the carbon absorbent in the material layer are removed through a vulcanization reaction; realizes the capture of CO in the hydrogen production process by one-step method 2 Simultaneously, the desulfurization and the tar removal are carried out.
3. A hydrogen production method based on the multilayer fluidized bed calcium chemical looping gasification hydrogen production device of claim 2, characterized in that calcined limestone is used as a carbon absorbent.
4. A carbon absorbent according to claim 3, characterized in that olivine or dolomite is added to the calcined limestone as the carbon absorbent.
5. A hydrogen production method based on the multilayer fluidized bed calcium chemical looping gasification hydrogen production device of claim 2 is characterized by specifically comprising the following steps of:
a) reaction in gasifier gasification chamber: the organic solid waste raw material and calcined limestone are uniformly mixed according to a certain mass ratio and enter a gasification furnace gasification chamber (7) through a feeding device (8), and a gasification furnace cracking chamber (4) contains CaO and CaCO 3 The ash-mixed circulating bed material enters a gasification chamber (7) of the gasification furnace through a vertical pipe (5) so as to maintain the temperature in the gasification chamber to be not lower than 600 ℃; simultaneously, water vapor enters the gasification chamber through a water vapor inlet at the bottom of the gasification furnace; organic solid waste raw material is pyrolyzed and gasified and is subjected to conversion reaction with water vapor to produce hydrogen, and CO is generated 2 Is absorbed by CaO, promotes the forward progress of gasification and hydrogen production reaction, and the total reaction is shown as formulas (1) and (2):
C+2H 2 O+CaO→CaCO 3 + 2H 2 (1)
CO+H 2 O+CaO→CaCO 3 +H 2 （2）
the hydrogen production reaction generates H as the main component 2 、CO、CO 2 、CH 4 And a hydrogen-rich syngas of gaseous tar, and a solid product, char; the hydrogen-rich synthesis gas enters a gasification furnace cracking chamber (4) through a distribution plate (6); semi-coke of solid product and generated CaCO 3 Enters the combustion furnace (1) together with the circulating bed material through the lower material returning device (9);
b) reaction in a combustion furnace: to the combustion furnace(1) Introducing air or oxygen; burning the semicoke from the gasification furnace (11) in a combustion furnace to release heat so as to maintain the temperature in the furnace above 850 ℃; CaCO in the bed material of combustion furnaces 3 Decomposing to CaO and releasing CO 2 The total reaction is shown as formulas (3) and (4):
C+O 2 →CO 2 (3)
CaCO 3 →CaO+CO 2 (4)
flue gas generated by the combustion furnace and most of bed materials leave the combustion furnace (1) from the top end and enter a separator (2), and a part of bed materials are discharged from the bottom of the combustion furnace;
c) reaction in the gasifier cracking chamber: hot flue gas of a combustion furnace is discharged from a flue gas outlet at the top end of the separator (2), high-temperature circulating bed materials enter a gasification furnace cracking chamber (4) from the bottom end of the separator (2) through an upper material return device (3), and meanwhile hydrogen-rich synthetic gas from a gasification furnace gasification chamber (7) enters the cracking chamber (4) through a distribution plate (6); the circulating bed material is in a bubbling fluidization state in the cracking chamber (4) of the gasification furnace; the gaseous tar in the hydrogen-rich synthesis gas is cracked into gaseous micromolecule products under the catalytic action of calcium compounds in the material layer, so that the high-temperature deep catalytic cracking of the tar is realized; h in hydrogen-rich syngas 2 S and CaO in the material layer are subjected to a vulcanization reaction to generate CaS, so that the hydrogen-rich synthesis gas is desulfurized; the purified hydrogen-rich synthetic gas is discharged from the top of the gasification furnace cracking chamber (4);
bed materials in the cracking chamber (4) of the gasification furnace enter the gasification chamber (7) of the gasification furnace through a vertical pipe (5) and enter the next circulation reaction process.
6. A hydrogen production method based on the multilayer fluidized bed calcium chemical looping gasification hydrogen production device as claimed in claim 5, characterized in that in order to increase the reactivity of the carbon absorbent, air or oxygen is introduced into the combustion furnace (1) and water vapor is introduced at the same time to activate the carbon absorbent.
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