CN113293014A - Negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method and device - Google Patents
Negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method and device Download PDFInfo
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- 238000000197 pyrolysis Methods 0.000 claims abstract description 88
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 44
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
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- 238000000034 method Methods 0.000 claims abstract description 23
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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Abstract
The invention discloses a negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method and a device, wherein the method comprises the following steps: obtaining biochar and pyrolysis gas through biomass pyrolysis, introducing the pyrolysis gas into a chemical-looping hydrogen production system for reducing a metal oxide oxygen carrier, and simultaneously generating CO2Trapping and sequestration, the reduced oxygen carrier being regenerated by reaction with water vapour and producing hydrogen, which is used to generate electricity in a fuel cell. TheMethod and apparatus for producing no CO2And the emission of pollutants, and has the advantages of high power generation efficiency and small environmental pollution.
Description
Technical Field
The invention relates to the field of energy, in particular to a negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method and a negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation device.
Background
Hydrogen energy is a green low carbon cleaningAnd (4) energy sources. With the development of fuel cells and hydrogen energy vehicles, the development of low-carbon and high-efficiency hydrogen production technology has important significance. The development of the hydrogen energy industry has received high attention from the state. The hydrogen yield in China reaches more than 2000 kilo/a, but more than 70 percent of hydrogen is produced by coal gasification and natural gas reforming. From the sustainable development point of view, fossil energy such as coal, natural gas and the like is nonrenewable resource, and hydrogen production is accompanied by a large amount of pollutants and CO2And the emission causes serious harm to the ecological environment. With the proposal of the targets of 'carbon peak reaching' and 'carbon neutralization' in China, the development and utilization of a new energy hydrogen production technology with low carbon become more important, and the method has an important role in promoting the transformation of energy structures in China.
Chemical looping hydrogen production is a low-carbon hydrogen production technology combining a chemical looping combustion concept and hydrogen production by a steam iron method. The chemical chain process decomposes the total reaction into a plurality of sub-reactions which occur in different time and space, and realizes the conversion of materials and the in-situ separation of products by transferring substances and energy through the recycling of the metal oxide oxygen carrier in the system. Therefore, the chemical-looping hydrogen production technology has the advantages of relatively simple device, low energy consumption, less pollution emission and easy separation and purification of hydrogen products.
Biomass is a variety of organisms formed directly or indirectly through plant photosynthesis, and is an energy carrier that converts solar energy into chemical energy. Biomass itself may be considered carbon neutral, i.e. CO produced by pyrolysis or conversion of biomass2With CO absorbed from the atmosphere during its growth2In contrast, biomass is thus converted into energy, followed by capture and sequestration of waste CO2Can be considered as negative carbon emissions. Compared with fossil resources, the biomass resources have the advantages of environmental protection and low carbon emission, accord with the sustainable development concept of China, and are beneficial to long-term development of China. The biomass pyrolysis conversion technology is an important utilization form of biomass energy and can generate biochar and pyrolysis gas products simultaneously. Wherein the biochar is an environmentally friendly multifunctional material in CO2The method has the advantages of a plurality of fields of adsorption, soil treatment, sewage treatment, electrochemical energy storage and the likeGood application prospect; heavy hydrocarbons, CO, CH in pyrolysis gas products4And the reducing substances can react with the metal oxygen carrier chemically to participate in the reaction process of chemical-looping hydrogen production.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a negative-carbon-emission biomass pyrolytic carbon hydrogen-electricity poly-generation method and a negative-carbon-emission biomass pyrolytic carbon hydrogen-electricity poly-generation device, which do not generate CO2And the emission of pollutants, and has the advantages of high power generation efficiency and small environmental pollution.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
in one aspect, an embodiment of the present invention provides a negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method, including:
obtaining biochar and pyrolysis gas through biomass pyrolysis, introducing the pyrolysis gas into a chemical-looping hydrogen production system for reducing a metal oxide oxygen carrier, and simultaneously generating CO2Trapping and sequestration, the reduced oxygen carrier being regenerated by reaction with water vapour and producing hydrogen, which is used to generate electricity in a fuel cell.
Preferably, the biomass pyrolysis is carried out in a nitrogen atmosphere, and agricultural wastes are used as biomass; the agricultural waste comprises straw and rice husk.
Preferably, the pyrolysis gas is dedusted and filtered to obtain reducing gas; the biochar is used for capturing and storing CO generated by the chemical-looping hydrogen production system2。
Preferably, the chemical-looping hydrogen production system transfers substances and energy by recycling the metal oxide oxygen carrier in the system, so as to realize generation and in-situ separation of hydrogen;
the metal oxide oxygen carrier is FeOxThe metal oxide oxygen carrier firstly reacts with the reducing gas in the pyrolysis gas: CO/CnHm+FeOx→Fe+CO2+H2O; after the metal oxide oxygen carrier is reduced, introducing water vapor into the system to react: fe + H2O→FeOx+H2The metal oxide oxygen carrier is regenerated, and hydrogen is generated for power generation of the fuel cell; the value range of x is 1-1.5, the value range of n is 1-3, and the value range of m is 2-8; n and m are integers.
On the other hand, the embodiment of the invention provides a negative carbon emission biomass pyrolysis carbon hydrogen-electricity poly-generation device which comprises a biomass pyrolysis system, a chemical chain hydrogen production system, a fuel cell power generation system and CO2A capture system;
the CO is2The capture system is connected with the chemical-looping hydrogen production system and is used for capturing and storing the waste CO generated by the chemical-looping reactor2；
The CO is2The collecting system is connected with a biomass pyrolysis system, and the biochar produced by the biomass pyrolysis system is used as CO2The trapping agent of (4);
the chemical looping hydrogen production system is connected with the biomass pyrolysis system, reducing gas generated by the biomass pyrolysis system is used as fuel, and the metal oxide oxygen carrier FeO is usedxReducing the iron into Fe;
the fuel cell power generation system is connected with the chemical-looping hydrogen production system, and hydrogen generated by the chemical-looping reaction device is used as fuel to chemically react with oxygen to convert chemical energy into electric energy.
Preferably, the biomass pyrolysis system comprises a material crushing device, a drying device, a pyrolysis reaction furnace, a biochar collecting device and a pyrolysis gas dedusting and purifying device; the outlet of the material crushing device is connected with the inlet of the drying device, the outlet of the drying device is connected with the inlet of the pyrolysis reaction furnace, the first outlet of the pyrolysis reaction furnace is connected with the inlet of the biochar collecting device, and the second outlet of the pyrolysis reaction furnace is connected with the inlet of the pyrolysis gas dedusting and purifying device;
the chemical looping hydrogen production system comprises a fuel reactor, a steam reactor, a water vapor generator, a tail gas collecting device, a hydrogen purifying device and a hydrogen collecting device; the outlet of the pyrolysis gas dust removal and purification device is connected with the inlet of the fuel reactor, the first outlet of the fuel reactor is connected with the inlet of the tail gas collection device, and waterThe outlet of the steam generator is connected with the first inlet of the steam reactor, the first outlet of the steam reactor is connected with the inlet of the hydrogen purification device, and the outlet of the hydrogen purification device is connected with the inlet of the hydrogen collection device; the fuel reactor is connected with the steam reactor; the fuel cell power generation system is connected with the outlet of the hydrogen collecting device; the CO is2The trapping system is respectively connected with the outlet of the tail gas collecting device and the outlet of the biochar collecting device.
Preferably, in the fuel reactor and the steam reactor, the fuel reactor is reacted first, and FeO is generatedxReduction to Fe followed by transfer of the Fe produced to the steam reactor; in the steam reactor, Fe is converted into FeOx(ii) a Then the FeO produced is recycledxTransferring back to the fuel reactor, and continuously circulating to realize solid FeOxAnd transfer of Fe between the fuel reactor and the steam reactor.
The invention fully utilizes the carbon element in the biomass, and the biomass is pyrolyzed to generate two valuable products of biochar and pyrolysis gas. By using reducing gases (CO, C) in the pyrolysis gasnHm) As fuel, participates in the reaction process of chemical-looping hydrogen production, and waste CO generated by conversion after the reaction is finished2Capturing and sealing; the biochar can be used as CO2The adsorbent can also be applied to the fields of soil improvement, sewage treatment, energy storage and the like, and has high application value. Because the biomass is a carbon neutral resource, the carbon element in the biomass is fully utilized and the generated waste CO2After being trapped, the whole system can be regarded as negative carbon emission, and accords with the national sustainable development concept. In addition, biomass resources such as straw, rice husk and the like are utilized, the problem of environmental pollution caused by agricultural and forestry waste can be effectively relieved, and the method has a good application prospect.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a schematic diagram of the system of the present invention.
Detailed Description
As shown in fig. 1, a method for hydrogen-electricity poly-generation of biomass pyrolytic carbon with negative carbon emission of the embodiment comprises: obtaining biochar and pyrolysis gas through biomass pyrolysis, introducing the pyrolysis gas into a chemical-looping hydrogen production system for reducing a metal oxide oxygen carrier, and simultaneously generating CO2Trapping and sequestration, the reduced oxygen carrier being regenerated by reaction with water vapour and producing hydrogen, which is used to generate electricity in a fuel cell.
In the above process, the biomass pyrolysis is performed in a nitrogen atmosphere. Thus, gas and solid products generated by pyrolysis can be prevented from being oxidized and burned by air, and agricultural wastes are used as biomass. The agricultural waste comprises straw and rice husk. Agricultural wastes are used as biomass, so that the wastes are fully utilized, and the wastes are changed into valuables. The pyrolysis gas is dedusted and filtered to obtain CO and CnHmAnd the like. The biochar is used for capturing and storing CO generated by the chemical-looping hydrogen production system2。
In the process, the chemical-looping hydrogen production system transfers substances and energy by recycling the metal oxide oxygen carrier in the system, so that the generation and in-situ separation of hydrogen are realized. Specifically, the metal oxide oxygen carrier is FeOxThe metal oxide oxygen carrier firstly reacts with the reducing gas in the pyrolysis gas: CO/CnHm+FeOx→Fe+CO2+H2O; after the metal oxide oxygen carrier is reduced, introducing water vapor into the system to react: fe + H2O→FeOx+H2The metal oxide oxygen carrier is regenerated and hydrogen is generated for fuel cell power generation. The value range of x is 1-1.5, the value range of n is 1-3, and the value range of m is 2-8. n and m are integers. The value of x may be 1, 1.5 or 1.33.
According to the negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method, pyrolytic gas and biochar are generated by biomass pyrolysis, the pyrolytic gas is supplied to a chemical-looping hydrogen production system, high-purity hydrogen is obtained and used for power generation of a fuel cell, and meanwhile, the biochar is used for capturing waste CO in chemical-looping hydrogen production tail gas2. The invention utilizesThe biomass pyrolysis gas is used as fuel to participate in chemical looping hydrogen production, is a low-cost and low-energy-consumption hydrogen production mode, not only provides clean hydrogen energy for fuel cell power generation, but also fully utilizes carbon element in the biomass and generates waste CO2And the carbon is captured and sealed, and the whole system realizes negative carbon emission.
As shown in fig. 2, the embodiment further provides a negative carbon emission biomass pyrolysis carbon hydrogen-electricity poly-generation device, which comprises a biomass pyrolysis system, a chemical looping hydrogen production system, a fuel cell power generation system and a CO2A capture system;
the CO is2The capture system is connected with the chemical-looping hydrogen production system and is used for capturing and storing the waste CO generated by the chemical-looping reactor2(ii) a Wherein, CO2The trapping adopts an adsorption method, and the used adsorbent is biochar generated by biomass pyrolysis.
The CO is2The collecting system is connected with a biomass pyrolysis system, and the biochar produced by the biomass pyrolysis system is used as CO2The collector of (3).
The chemical looping hydrogen production system is connected with the biomass pyrolysis system, reducing gas generated by the biomass pyrolysis system is used as fuel, and the metal oxide oxygen carrier FeO is usedxReducing the reaction product into Fe.
The fuel cell power generation system is connected with the chemical-looping hydrogen production system, and hydrogen generated by the chemical-looping reaction device is used as fuel to chemically react with oxygen to convert chemical energy into electric energy.
In the above embodiment, the biomass pyrolysis system includes a material crushing device, a drying device, a pyrolysis reaction furnace, a biochar collecting device, and a pyrolysis gas dust removal and purification device; the outlet of the material crushing device is connected with the inlet of the drying device, the outlet of the drying device is connected with the inlet of the pyrolysis reaction furnace, the first outlet of the pyrolysis reaction furnace is connected with the inlet of the biochar collecting device, and the second outlet of the pyrolysis reaction furnace is connected with the inlet of the pyrolysis gas dust removal and purification device.
The chemical looping hydrogen production system comprises a fuel reactor, a steam reactor and waterThe system comprises a steam generator, a tail gas collecting device, a hydrogen purifying device and a hydrogen collecting device; the outlet of the pyrolysis gas dedusting and purifying device is connected with the inlet of the fuel reactor, the first outlet of the fuel reactor is connected with the inlet of the tail gas collecting device, the outlet of the water vapor generator is connected with the first inlet of the steam reactor, the first outlet of the steam reactor is connected with the inlet of the hydrogen purifying device, and the outlet of the hydrogen purifying device is connected with the inlet of the hydrogen collecting device; the fuel reactor is connected with the steam reactor. The fuel cell power generation system is connected with the outlet of the hydrogen collecting device. The CO is2The trapping system is respectively connected with the outlet of the tail gas collecting device and the outlet of the biochar collecting device.
In the fuel reactor and the steam reactor, the fuel reactor firstly reacts to obtain FeOxReduction to Fe followed by transfer of the Fe produced to the steam reactor; in the steam reactor, Fe is converted into FeOx(ii) a Then the FeO produced is recycledxTransferring back to the fuel reactor, and continuously circulating to realize solid FeOxAnd transfer of Fe between the fuel reactor and the steam reactor.
When the system is used, the biomass raw materials are input into the material crushing device, the crushed biomass raw materials are crushed to the particle size of 50-200 mm, then the biomass is conveyed to the drying device for drying, the dried biomass is conveyed to the pyrolysis reaction furnace, nitrogen is used as protective gas, the pyrolysis temperature is controlled to be 600-700 ℃, and the pyrolysis time is controlled to be 0.5-2 hours. And introducing the pyrolysis gas generated in the pyrolysis reaction furnace into a pyrolysis gas dedusting and purifying device to obtain reducing gas. Specifically, the reducing gas comprises CO and CH4、CxHyAnd the like. And discharging solid biochar generated by biomass pyrolysis from the bottom of the pyrolysis reaction furnace, entering a biochar collecting device, and waiting for further use.
The reducing gas generated by the pyrolysis gas dust removal and purification device is introduced into a fuel reactor and reacts with the metal oxide oxygen carrier FeOxReaction CO/C takes placenHm+FeOx→Fe+CO2+H2O, controlling the reaction temperature to be 800-1000 ℃ until FeOxAll are reduced to Fe. Reducing gas is FeOxOxidation to CO2And H2O, flows out from the gas outlet end of the fuel reactor and enters into CO2A capture system.
The steam reactor carries the product Fe recovered by the fuel reactor, the gas inlet end is connected with a steam generator which introduces steam into the furnace, and the gas outlet end is connected with the hydrogen purification device. The steam in the steam reactor enters from the air inlet end to react with Fe to generate Fe + H2O→FeOx+H2And controlling the reaction temperature to be 800-1000 ℃, and enabling the generated hydrogen to flow out of the gas outlet end and enter a hydrogen purification device to obtain high-purity hydrogen for power generation of the fuel cell.
The fuel reactor is connected with the pyrolysis gas dust removal and purification device and carries a metal oxide oxygen carrier FeOxOutlet with said CO2Connecting a trapping system; the steam reactor carries the product Fe of the fuel reactor, the inlet of the steam reactor is connected with a steam generator which leads steam into the furnace, and the outlet of the steam reactor is connected with the hydrogen purification device.
The chemical-looping hydrogen production technology adopted by the invention produces hydrogen by the reduction and regeneration of the metal oxide oxygen carrier, and the metal oxide oxygen carrier can be recycled, thereby saving the hydrogen production cost. The chemical chain process is to decompose the reaction into multiple sub-reactions that are different in time and space, so that hydrogen and waste CO can be separated in situ2And the hydrogen purification with low energy consumption is realized. The chemical chain process is to decompose the reaction into a plurality of sub-reactions which are different in time and space, firstly, the biomass pyrolysis gas is reduced into the metal oxide oxygen carrier FeO in the fuel reactorxTo obtain Fe and CO2(ii) a Then in a steam reactor, Fe reacts with water vapor to generate hydrogen and simultaneously carry FeOxAnd (4) regenerating. Thus, hydrogen and waste CO2Produced separately in a steam reactor and a fuel reactor, which can be easily separated in situ to achieve low energy consumption hydrogen purification.
The embodiment utilizes the biomass pyrolysis coupling chemical chain technology to produce hydrogen, and has simple hydrogen production device and pure hydrogenLow chemical difficulty, avoids the consumption of fossil energy and provides clean and low-cost hydrogen for the fuel cell. Because the biomass resource has the characteristic of carbon neutrality, the carbon element in the biomass resource is converted into a biochar material or participates in the chemical chain hydrogen production process, and finally, the produced CO2Is captured and sealed, so the whole system has the characteristic of carbon negativity.
The biomass pyrolysis coupling chemical chain hydrogen production technology adopted by the embodiment of the invention does not need the participation of fossil energy in the preparation process and does not generate CO2And the discharge of pollutants, and is a clean hydrogen production mode. The prepared hydrogen is supplied to a fuel cell for power generation, the hydrogen and oxygen react to convert chemical energy into electric energy, the hydrogen-oxygen hybrid power generation system has the advantages of high power generation efficiency, small environmental pollution and the like, and the fuel cell is the most promising power generation technology at present from the viewpoint of energy conservation and environmental protection.
Claims (7)
1. A negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method is characterized by comprising the following steps:
obtaining biochar and pyrolysis gas through biomass pyrolysis, introducing the pyrolysis gas into a chemical-looping hydrogen production system for reducing a metal oxide oxygen carrier, and simultaneously generating CO2Trapping and sequestration, the reduced oxygen carrier being regenerated by reaction with water vapour and producing hydrogen, which is used to generate electricity in a fuel cell.
2. The negative carbon biomass pyrolytic carbon hydrogen-electricity poly-generation method according to claim 1, wherein the biomass pyrolysis is performed in nitrogen atmosphere, using agricultural waste as biomass; the agricultural waste comprises straw and rice husk.
3. The negative carbon emission biomass pyrolytic carbon hydrogen-electricity poly-generation method according to claim 1, wherein the pyrolysis gas is dedusted and filtered to obtain reducing gas; the biochar is used for capturing and storing CO generated by the chemical-looping hydrogen production system2。
4. The method for the poly-generation of hydrogen and electricity from biomass pyrolytic carbon with negative carbon emission according to claim 1, wherein the chemical looping hydrogen production system transfers substances and energy by recycling metal oxide oxygen carriers in the system to realize the generation and in-situ separation of hydrogen;
the metal oxide oxygen carrier is FeOxThe metal oxide oxygen carrier firstly reacts with the reducing gas in the pyrolysis gas: CO/CnHm+FeOx→Fe+CO2+H2O; after the metal oxide oxygen carrier is reduced, introducing water vapor into the system to react: fe + H2O→FeOx+H2The metal oxide oxygen carrier is regenerated, and hydrogen is generated for power generation of the fuel cell; the value range of x is 1-1.5, the value range of n is 1-3, and the value range of m is 2-8; n and m are integers.
5. The device for negative carbon emission biomass pyrolysis carbon hydrogen-electricity poly-generation is characterized by comprising a biomass pyrolysis system, a chemical chain hydrogen production system, a fuel cell power generation system and CO2A capture system;
the CO is2The capture system is connected with the chemical-looping hydrogen production system and is used for capturing and storing the waste CO generated by the chemical-looping reactor2；
The CO is2The collecting system is connected with a biomass pyrolysis system, and the biochar produced by the biomass pyrolysis system is used as CO2The trapping agent of (4);
the chemical looping hydrogen production system is connected with the biomass pyrolysis system, reducing gas generated by the biomass pyrolysis system is used as fuel, and the metal oxide oxygen carrier FeO is usedxReducing the iron into Fe;
the fuel cell power generation system is connected with the chemical-looping hydrogen production system, and hydrogen generated by the chemical-looping reaction device is used as fuel to chemically react with oxygen to convert chemical energy into electric energy.
6. The negative carbon emission biomass pyrolysis carbon hydrogen and electricity poly-generation device according to claim 5, wherein the biomass pyrolysis system comprises a material crushing device, a drying device, a pyrolysis reaction furnace, a biochar collecting device and a pyrolysis gas dedusting and purifying device; the outlet of the material crushing device is connected with the inlet of the drying device, the outlet of the drying device is connected with the inlet of the pyrolysis reaction furnace, the first outlet of the pyrolysis reaction furnace is connected with the inlet of the biochar collecting device, and the second outlet of the pyrolysis reaction furnace is connected with the inlet of the pyrolysis gas dedusting and purifying device;
the chemical looping hydrogen production system comprises a fuel reactor, a steam reactor, a water vapor generator, a tail gas collecting device, a hydrogen purifying device and a hydrogen collecting device; the outlet of the pyrolysis gas dedusting and purifying device is connected with the inlet of the fuel reactor, the first outlet of the fuel reactor is connected with the inlet of the tail gas collecting device, the outlet of the water vapor generator is connected with the first inlet of the steam reactor, the first outlet of the steam reactor is connected with the inlet of the hydrogen purifying device, and the outlet of the hydrogen purifying device is connected with the inlet of the hydrogen collecting device; the fuel reactor is connected with the steam reactor; the fuel cell power generation system is connected with the outlet of the hydrogen collecting device; the CO is2The trapping system is respectively connected with the outlet of the tail gas collecting device and the outlet of the biochar collecting device.
7. The negative carbon biomass pyrolysis carbon hydrogen and electricity poly-generation device according to claim 6, wherein in the fuel reactor and the steam reactor, the fuel reactor is firstly reacted, FeOxReduction to Fe followed by transfer of the Fe produced to the steam reactor; in the steam reactor, Fe is converted into FeOx(ii) a Then the FeO produced is recycledxTransferring back to the fuel reactor, and continuously circulating to realize solid FeOxAnd transfer of Fe between the fuel reactor and the steam reactor.
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