CN107601430A - Based on CaFe2O4/Ca2Fe2O5Catalytic cycle hydrogen manufacturing collaboration trapping carbon dioxide method and apparatus - Google Patents
Based on CaFe2O4/Ca2Fe2O5Catalytic cycle hydrogen manufacturing collaboration trapping carbon dioxide method and apparatus Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910004333 CaFe2O4 Inorganic materials 0.000 title claims 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011575 calcium Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000000446 fuel Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000004449 solid propellant Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims 3
- 239000012530 fluid Substances 0.000 claims 1
- 230000003134 recirculating effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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- Gas Separation By Absorption (AREA)
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Treating Waste Gases (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
本发明公开了一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法和装置，所述方法采用CaFe2O4和Ca2Fe2O5复合钙铁粉体一步反应制取高纯度氢气并捕集二氧化碳，所述反应循环进行。所述装置为叠式循环流化床或嵌套式流化床。本发明具有以下优点：本发明所述基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法通过一步反应制氢，能够同时捕集二氧化碳和高纯度的氢气；本发明所述方法采用的CaFe2O4和Ca2Fe2O5载氧体较单独使用铁基和钙基载氧体具有更好的强度，利于在流化床中使用，且反应时间较短，不易失活，制取的氢气纯度高；本发明所述的叠式循环流化床和嵌套式循环流化床装置结构简单，能够有效捕集二氧化碳和高纯度的氢气。
The invention discloses a method and device for synergistically capturing carbon dioxide by catalytic cycle hydrogen production based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 . The method uses CaFe 2 O 4 and Ca 2 Fe 2 O 5 composite calcium iron The powder is reacted in one step to produce high-purity hydrogen and capture carbon dioxide, and the reaction is carried out in a cycle. The device is stacked circulating fluidized bed or nested fluidized bed. The present invention has the following advantages: the method of the present invention based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide can simultaneously capture carbon dioxide and high-purity hydrogen through one-step hydrogen production; The CaFe 2 O 4 and Ca 2 Fe 2 O 5 oxygen carriers used in the method of the present invention have better strength than iron-based and calcium-based oxygen carriers used alone, which is beneficial to use in a fluidized bed, and the reaction time is shorter Short, not easy to deactivate, the hydrogen produced is of high purity; the stacked circulating fluidized bed and nested circulating fluidized bed devices of the present invention have a simple structure and can effectively capture carbon dioxide and high-purity hydrogen.
Description
技术领域technical field
本发明属于二氧化碳捕集技术领域，涉及一种化学链制氢技术，具体为一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法和装置。The invention belongs to the technical field of carbon dioxide capture, and relates to a chemical chain hydrogen production technology, in particular to a method and device for synergistic capture of carbon dioxide by catalytic cycle hydrogen production based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 .
背景技术Background technique
化学链制氢的基本原理是将传统的燃料与空气直接接触反应的燃烧，借助于载氧剂(Oxygen carrier)的作用分解为2个气固反应，燃料与空气无需接触，由载氧体将空气中的氧传递到燃料中。The basic principle of chemical chain hydrogen production is to decompose the traditional combustion of fuel in direct contact with air into two gas-solid reactions with the help of an oxygen carrier (Oxygen carrier). The fuel and air do not need to be in contact. Oxygen from the air is transferred to the fuel.
在以往的化学链制氢过程当中，分为气体燃料和固体燃料制氢，其中气体燃料制氢过程当中主要使用的是铁基载氧体，固体燃料制氢过程当中主要使用的是铁基或钙基载氧体。化学链燃烧与制氢技术也是洁净煤技术、固体废弃物处理等国家重大研究课题当中的关键技术。In the previous chemical chain hydrogen production process, it was divided into gas fuel and solid fuel hydrogen production. The gas fuel hydrogen production process mainly used iron-based oxygen carrier, and the solid fuel hydrogen production process mainly used iron-based or Calcium-based oxygen carrier. Chemical chain combustion and hydrogen production technology are also key technologies in major national research topics such as clean coal technology and solid waste treatment.
其中，铁基载氧体的燃料转换效率以及二氧化碳脱除效率较低，反应时间较长，需要三步化学反应，反应装置结构相对复杂。钙基载氧体的结构强度较弱，表面易烧结，这在多次循环催化后易导致钙基催化剂失活。Among them, the fuel conversion efficiency and carbon dioxide removal efficiency of iron-based oxygen carriers are low, the reaction time is long, three-step chemical reactions are required, and the structure of the reaction device is relatively complicated. The structural strength of the calcium-based oxygen carrier is weak, and the surface is easy to sinter, which easily leads to the deactivation of the calcium-based catalyst after multiple cycles of catalysis.
发明内容Contents of the invention
解决的技术问题：为了克服现有技术的缺陷，获得一种能够通过一步反应制得高纯度氢气，并能同时捕集二氧化碳的方法，本发明提供了一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法和装置。Technical problem to be solved: In order to overcome the defects of the prior art and obtain a method that can produce high-purity hydrogen through a one-step reaction and capture carbon dioxide at the same time, the present invention provides a method based on CaFe 2 O 4 /Ca 2 Fe A method and device for synergistically capturing carbon dioxide for hydrogen production by catalytic cycle of 2 O 5 .
技术方案：一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法，所述方法采用CaFe2O4和Ca2Fe2O5复合钙铁粉体一步反应制取高纯度氢气并捕集二氧化碳，所述反应循环进行。Technical solution: a method for synergistic capture of carbon dioxide based on catalytic cycle hydrogen production based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 , the method uses CaFe 2 O 4 and Ca 2 Fe 2 O 5 composite calcium iron powder in one step The reaction produces high-purity hydrogen and captures carbon dioxide, and the reaction is cycled.
优选的，所述反应中需添加气体或固体燃料，为一氧化碳、甲烷或煤中的一种。Preferably, gas or solid fuel needs to be added in the reaction, which is one of carbon monoxide, methane or coal.
优选的，所述反应的反应式如下：Preferably, the reaction formula of the reaction is as follows:
Ca2Fe2O5+3CO→2CaO+2Fe+3CO2 (1)Ca 2 Fe 2 O 5 +3CO→2CaO+2Fe+3CO 2 (1)
CaFe2O4+3CO→CaO+2Fe+3CO2 (2)CaFe 2 O 4 +3CO→CaO+2Fe+3CO 2 (2)
2CaO+2Fe+3H2O→Ca2Fe2O5+3H2 (3)2CaO+2Fe+3H 2 O→Ca 2 Fe 2 O 5 +3H 2 (3)
CaO+2Fe+3H2O→CaFe2O4+3H2 (4)CaO+2Fe+3H 2 O→CaFe 2 O 4 +3H 2 (4)
如图1所示，一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的装置，所述装置为叠式循环流化床，包括提升管、燃料反应器和水蒸气反应器，其中提升管位于燃料反应器的上方，燃料反应器的下部和水蒸气反应器的下部通过U型返料阀B连通；水蒸气反应器的上部通过旋风分离器B、立管、U型返料阀C与提升管的下部、燃料反应器的上部连通；所述提升管的上部与旋风分离器A连通，旋风分离器A经返料管和U型返料阀A与燃料反应器连通；所述燃料反应器下方设有布风板。As shown in Figure 1, a device based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide, the device is a stacked circulating fluidized bed, including a riser, a fuel reactor And the steam reactor, wherein the riser is located above the fuel reactor, the lower part of the fuel reactor and the lower part of the steam reactor are communicated through the U-shaped return valve B; the upper part of the steam reactor is connected through the cyclone separator B, vertical pipe, U-shaped return valve C communicates with the bottom of the riser and the top of the fuel reactor; the upper part of the riser communicates with the cyclone separator A, and the cyclone A passes through the return pipe and the U-shaped return valve A and The fuel reactor is connected; the air distribution plate is arranged under the fuel reactor.
如图2所示，一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的装置，所述装置为嵌套式流化床，包括立管、燃料反应器、水蒸气反应器和燃料反应器引射装置，其中燃料反应器由至少一根贯穿于水蒸气反应器中的管道组成；所述燃料反应器引射装置位于燃料反应器的管道下方，燃料反应器上方顺次通过旋风分离器A、立管、U型返料阀A与水蒸气反应器的下部连通；所述水蒸气反应器下方设有水蒸气反应器室，且二者之间设有布风板；所述水蒸气反应器的上部通过旋风分离器B、返料管、U型返料阀B与燃料反应器引射装置连通。As shown in Figure 2, a device based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide, the device is a nested fluidized bed, including riser, fuel reactor , a steam reactor and a fuel reactor injection device, wherein the fuel reactor is composed of at least one pipeline running through the steam reactor; the fuel reactor injection device is located below the pipeline of the fuel reactor, and the fuel reaction The upper part of the reactor is communicated with the lower part of the steam reactor through the cyclone separator A, the standpipe, and the U-shaped return valve A in sequence; the steam reactor chamber is provided below the steam reactor, and there is a Air distribution plate; the upper part of the steam reactor communicates with the injection device of the fuel reactor through the cyclone separator B, the return pipe, and the U-shaped return valve B.
有益效果：(1)本发明所述基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法通过一步反应制氢，能够同时捕集二氧化碳和高纯度的氢气；(2)本发明所述方法采用的CaFe2O4和Ca2Fe2O5载氧体较单独使用铁基和钙基载氧体具有更好的强度，利于在流化床中使用，且反应时间较短，不易失活，制取的氢气纯度高；(3)本发明所述的叠式循环流化床和嵌套式循环流化床装置结构简单，能够有效捕集二氧化碳和高纯度的氢气。Beneficial effects: (1) The method of the present invention based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide can simultaneously capture carbon dioxide and high-purity hydrogen through one-step hydrogen production; (2) CaFe 2 O 4 and Ca 2 Fe 2 O 5 oxygen carriers used in the method of the present invention have better strength than iron-based and calcium-based oxygen carriers used alone, which is beneficial to use in a fluidized bed, and The reaction time is shorter, it is not easy to deactivate, and the purity of the produced hydrogen is high; (3) the stacked circulating fluidized bed and nested circulating fluidized bed device of the present invention are simple in structure, and can effectively capture carbon dioxide and high-purity hydrogen. of hydrogen.
附图说明Description of drawings
图1是叠式循环流化床的结构示意图；Fig. 1 is the structural representation of stacked circulating fluidized bed;
其中，1为旋风分离器A，10为立管，11为旋风分离器B，12为提升管，13为返料管，14为U型返料阀A，15为布风板，16为U型返料阀B，17为燃料反应器，18为水蒸气反应器，19为U型返料阀C；Among them, 1 is cyclone separator A, 10 is standpipe, 11 is cyclone separator B, 12 is riser, 13 is return pipe, 14 is U-shaped return valve A, 15 is air distribution plate, and 16 is U Type return valve B, 17 is a fuel reactor, 18 is a steam reactor, and 19 is a U-type return valve C;
图2是嵌套式循环流化床的结构示意图；Fig. 2 is the structural representation of nested circulating fluidized bed;
其中，2为旋风分离器A，20旋风分离器B，21为燃料反应器，22为立管，23为U型返料阀A，24为水蒸气反应器，25为布风板，26为水蒸气反应器室，27为燃料反应器引射装置，28为U型返料阀B，29为返料管；Among them, 2 is the cyclone separator A, 20 is the cyclone separator B, 21 is the fuel reactor, 22 is the riser, 23 is the U-shaped return valve A, 24 is the steam reactor, 25 is the air distribution plate, 26 is In the water vapor reactor chamber, 27 is a fuel reactor injection device, 28 is a U-shaped return valve B, and 29 is a return pipe;
图3是反应原理图；a为钙循环制氢捕集二氧化碳原理图，b为钙铁复合粉体循环制氢捕集二氧化碳原理图。Figure 3 is a schematic diagram of the reaction; a is a schematic diagram of calcium cycle hydrogen production and carbon dioxide capture, and b is a schematic diagram of calcium iron composite powder cycle hydrogen production capture carbon dioxide schematic.
具体实施方式detailed description
以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。The following examples further illustrate the content of the present invention, but should not be construed as limiting the present invention. Without departing from the spirit and essence of the present invention, the modifications and substitutions made to the methods, steps or conditions of the present invention all belong to the scope of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.
实施例1Example 1
一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法，所述方法采用CaFe2O4和Ca2Fe2O5复合钙铁粉体一步反应制取高纯度氢气并捕集二氧化碳，所述反应循环进行。A method based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide, the method is prepared by one-step reaction of CaFe 2 O 4 and Ca 2 Fe 2 O 5 composite calcium iron powder High-purity hydrogen and capture of carbon dioxide, the reaction is cycled.
所述反应中需添加气体或固体燃料，本实施例选用一氧化碳。Gas or solid fuel needs to be added in the reaction, and carbon monoxide is selected in this embodiment.
所述反应的反应式如下：The reaction formula of described reaction is as follows:
Ca2Fe2O5+3CO→2CaO+2Fe+3CO2 (1)Ca 2 Fe 2 O 5 +3CO→2CaO+2Fe+3CO 2 (1)
CaFe2O4+3CO→CaO+2Fe+3CO2 (2)CaFe 2 O 4 +3CO→CaO+2Fe+3CO 2 (2)
2CaO+2Fe+3H2O→Ca2Fe2O5+3H2 (3)2CaO+2Fe+3H 2 O→Ca 2 Fe 2 O 5 +3H 2 (3)
CaO+2Fe+3H2O→CaFe2O4+3H2 (4)CaO+2Fe+3H 2 O→CaFe 2 O 4 +3H 2 (4)
采用如图1所示的叠式循环流化床进行上述反应，所述装置为：Adopt stacked circulating fluidized bed as shown in Figure 1 to carry out above-mentioned reaction, described device is:
一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的装置，所述装置为叠式循环流化床，包括提升管12、燃料反应器17和水蒸气反应器18，其中提升管12位于燃料反应器17的上方，燃料反应器17的下部和水蒸气反应器18的下部通过U型返料阀B 16连通；水蒸气反应器18的上部通过旋风分离器B 11、立管10、U型返料阀C 19与提升管12的下部、燃料反应器17的上部连通；所述提升管12的上部与旋风分离器A 1连通，旋风分离器A1经返料管13和U型返料阀A 14与燃料反应器17连通；所述燃料反应器17下方设有布风板15。A device based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide, the device is a stacked circulating fluidized bed, including a riser 12, a fuel reactor 17 and a steam reaction 18, wherein the riser 12 is located above the fuel reactor 17, the lower part of the fuel reactor 17 and the lower part of the steam reactor 18 communicate through a U-shaped return valve B 16; the upper part of the steam reactor 18 passes through a cyclone separator B 11, standpipe 10, U-shaped material return valve C 19 communicate with the bottom of riser 12 and the top of fuel reactor 17; the top of said riser 12 communicates with cyclone separator A1, and cyclone separator A1 is returned The material pipe 13 and the U-shaped return valve A 14 communicate with the fuel reactor 17; the air distribution plate 15 is arranged under the fuel reactor 17.
反应过程如下：CaFe2O4和Ca2Fe2O5在燃料反应器17中和一氧化碳发生反应，反应式如式(1)和(2)所示，生成氧化钙、铁单质和二氧化碳，其中氧化钙和铁单质通过U型返料阀B16进入水蒸气反应器18，与水蒸气反应生成Ca2Fe2O5、CaFe2O4和氢气，反应式如式(3)和(4)所示。生成的Ca2Fe2O5、CaFe2O4和氢气通过旋风分离器B 11分离，Ca2Fe2O5、CaFe2O4进入立管10并通过U型返料阀C 19进入提升管12，氢气和水蒸气则进入冷凝器，以获得高纯度氢气。二氧化碳进入提升管12挟带U型返料阀C 19排出的Ca2Fe2O5和CaFe2O4一起进入旋风分离器A1进行气固分离，其中Ca2Fe2O5和CaFe2O4通过返料管13和U型返料阀A14再次进入燃料反应器17，二氧化碳则在旋风分离器A1中被分离并通过冷凝器后捕集。The reaction process is as follows: CaFe 2 O 4 and Ca 2 Fe 2 O 5 react with carbon monoxide in the fuel reactor 17, and the reaction formula is shown in formulas (1) and (2), generating calcium oxide, iron element and carbon dioxide, wherein Calcium oxide and iron enter the steam reactor 18 through the U-shaped return valve B16, and react with water vapor to generate Ca 2 Fe 2 O 5 , CaFe 2 O 4 and hydrogen. The reaction formula is as shown in formulas (3) and (4). Show. The generated Ca 2 Fe 2 O 5 , CaFe 2 O 4 and hydrogen are separated by the cyclone separator B 11, Ca 2 Fe 2 O 5 and CaFe 2 O 4 enter the riser 10 and enter the riser through the U-shaped return valve C 19 12. Hydrogen and water vapor enter the condenser to obtain high-purity hydrogen. Carbon dioxide enters the riser 12 and the Ca 2 Fe 2 O 5 and CaFe 2 O 4 discharged from the U-shaped return valve C 19 enter the cyclone separator A1 together for gas-solid separation, wherein Ca 2 Fe 2 O 5 and CaFe 2 O 4 Through the return pipe 13 and the U-shaped return valve A14, it enters the fuel reactor 17 again, and the carbon dioxide is separated in the cyclone separator A1 and captured after passing through the condenser.
实施例2Example 2
一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的方法，所述方法采用CaFe2O4和Ca2Fe2O5复合钙铁粉体一步反应制取高纯度氢气并捕集二氧化碳，所述反应循环进行。A method based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide, the method is prepared by one-step reaction of CaFe 2 O 4 and Ca 2 Fe 2 O 5 composite calcium iron powder High-purity hydrogen and capture of carbon dioxide, the reaction is cycled.
所述反应中需添加气体或固体燃料，本实施例选用一氧化碳。Gas or solid fuel needs to be added in the reaction, and carbon monoxide is selected in this embodiment.
所述反应的反应式如下：The reaction formula of described reaction is as follows:
Ca2Fe2O5+3CO→2CaO+2Fe+3CO2 (1)Ca 2 Fe 2 O 5 +3CO→2CaO+2Fe+3CO 2 (1)
CaFe2O4+3CO→CaO+2Fe+3CO2 (2)CaFe 2 O 4 +3CO→CaO+2Fe+3CO 2 (2)
2CaO+2Fe+3H2O→Ca2Fe2O5+3H2 (3)2CaO+2Fe+3H 2 O→Ca 2 Fe 2 O 5 +3H 2 (3)
CaO+2Fe+3H2O→CaFe2O4+3H2 (4)CaO+2Fe+3H 2 O→CaFe 2 O 4 +3H 2 (4)
采用如图2所示的嵌套式循环流化床进行上述反应，所述装置为：Adopt nested circulating fluidized bed as shown in Figure 2 to carry out above-mentioned reaction, described device is:
一种基于CaFe2O4/Ca2Fe2O5的催化循环制氢协同捕集二氧化碳的装置，所述装置为嵌套式流化床，包括立管22、燃料反应器21、水蒸气反应器24和燃料反应器引射装置27，其中燃料反应器21由至少一根贯穿于水蒸气反应器24中的管道组成；所述燃料反应器引射装置27位于燃料反应器21的管道下方，燃料反应器21上方顺次通过旋风分离器A2、立管22、U型返料阀A23与水蒸气反应器24的下部连通；所述水蒸气反应器24下方设有水蒸气反应器室26，且二者之间设有布风板25；所述水蒸气反应器24的上部通过旋风分离器B 20、返料管29、U型返料阀B 28与燃料反应器引射装置27连通。A device based on CaFe 2 O 4 /Ca 2 Fe 2 O 5 catalytic cycle hydrogen production and co-capture of carbon dioxide, the device is a nested fluidized bed, including a standpipe 22, a fuel reactor 21, a steam reaction Device 24 and fuel reactor injection device 27, wherein fuel reactor 21 is made up of at least one pipeline that runs through the steam reactor 24; Said fuel reactor injection device 27 is positioned at the pipeline below of fuel reactor 21, The top of the fuel reactor 21 communicates with the lower part of the steam reactor 24 through the cyclone separator A2, the standpipe 22, and the U-shaped return valve A23 in sequence; the steam reactor chamber 26 is provided below the steam reactor 24, And there is an air distribution plate 25 between the two; the upper part of the steam reactor 24 communicates with the fuel reactor injection device 27 through the cyclone separator B 20 , the return pipe 29 , and the U-shaped return valve B 28 .
反应过程如下：Ca2Fe2O5和CaFe2O4在燃料反应器引射装置27和燃料反应器21中与碳氢燃料发生反应，反应式如式(1)和(2)所示，生成氧化钙、铁单质和二氧化碳，其中氧化钙和铁单质通过旋风分离器A 2、立管22和U型返料阀A 23进入水蒸气反应器24，二氧化碳则被旋风分离器A 2分离并通过冷凝器后捕集。在水蒸气反应器24中，水蒸气先进入水蒸气反应器气室26，并通过布风板5均匀的进入水蒸气反应器24，与水蒸气反应生成Ca2Fe2O5、CaFe2O4和氢气，反应式如式(3)和(4)所示。生成的Ca2Fe2O5、CaFe2O4、和氢气以及过量的水蒸气通过旋风分离器B 20气固分离，分离的氢气和水蒸气进入冷凝器，以获得高纯度氢气，Ca2Fe2O5和CaFe2O4则通过返料管29和U型返料阀B 28返回燃料反应器引射装置27中。The reaction process is as follows: Ca 2 Fe 2 O 5 and CaFe 2 O 4 react with hydrocarbon fuel in the fuel reactor injection device 27 and the fuel reactor 21, and the reaction formula is shown in formulas (1) and (2), Generate calcium oxide, iron element and carbon dioxide, wherein calcium oxide and iron element enter steam reactor 24 by cyclone separator A 2, standpipe 22 and U-type return valve A 23, and carbon dioxide is then separated by cyclone separator A 2 and Collected after passing through the condenser. In the steam reactor 24, water vapor first enters the air chamber 26 of the steam reactor, and then enters the steam reactor 24 evenly through the air distribution plate 5, and reacts with the water vapor to form Ca 2 Fe 2 O 5 , CaFe 2 O 4 and hydrogen, the reaction formula is shown in formulas (3) and (4). The generated Ca 2 Fe 2 O 5 , CaFe 2 O 4 , hydrogen and excess water vapor are separated from gas to solid by cyclone separator B 20, and the separated hydrogen and water vapor enter the condenser to obtain high-purity hydrogen, Ca 2 Fe 2 O 5 and CaFe 2 O 4 are then returned to the injection device 27 of the fuel reactor through the return pipe 29 and the U-shaped return valve B 28 .
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