CN106975341A - A kind of devices and methods therefor of the calcium-base absorbing agent circularly removing carbon dioxide of carrying vapour activated reactor - Google Patents
A kind of devices and methods therefor of the calcium-base absorbing agent circularly removing carbon dioxide of carrying vapour activated reactor 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 88
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 23
- 239000006096 absorbing agent Substances 0.000 title 1
- 239000002250 absorbent Substances 0.000 claims abstract description 65
- 230000002745 absorbent Effects 0.000 claims abstract description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003546 flue gas Substances 0.000 claims abstract description 55
- 239000011575 calcium Substances 0.000 claims abstract description 54
- 230000004913 activation Effects 0.000 claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 43
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 39
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 33
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 230000018044 dehydration Effects 0.000 claims abstract description 25
- 230000008929 regeneration Effects 0.000 claims abstract description 24
- 238000011069 regeneration method Methods 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000011343 solid material Substances 0.000 claims description 37
- 239000000446 fuel Substances 0.000 claims description 22
- 238000002485 combustion reaction Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002826 coolant Substances 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000498 cooling water Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000008247 solid mixture Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
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- B01D2257/504—Carbon dioxide
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
本发明公开了一种带蒸汽活化反应器的钙基吸收剂循环脱除二氧化碳的装置，包括流化床碳酸化反应器、流化床煅烧分解反应器、流化床蒸汽活化反应器、流化床失水再生反应器、第一旋风分离器、第二旋风分离器、第一返料器、第二返料器、循环物料换热器、CO2换热器、空气分离单元及各部分之间连接管道；使用蒸汽活化反应器对煅烧后失活CaO进行活性再生，通过水合‑失水反应大幅再生吸收剂孔隙结构和反应表面，可显著维持钙基吸收剂活性，抑制吸收剂活性衰退，减少失活吸收剂排放及新鲜吸收剂补充量；使用换热器充分利用高温烟气与循环物料的热量，产生高温氧气、氮气与蒸汽，提高碳捕获过程的热经济性和能量利用效率。
The invention discloses a device for removing carbon dioxide in a calcium-based absorbent cycle with a steam activation reactor, comprising a fluidized bed carbonation reactor, a fluidized bed calcination decomposition reactor, a fluidized bed steam activation reactor, a fluidized bed Bed dehydration regeneration reactor, first cyclone separator, second cyclone separator, first feeder, second feeder, circulating material heat exchanger, CO2 heat exchanger, air separation unit and various parts The pipelines are connected between them; the steam activation reactor is used to regenerate the deactivated CaO after calcination, and the pore structure and reaction surface of the absorbent can be greatly regenerated through the hydration-dehydration reaction, which can significantly maintain the activity of the calcium-based absorbent and inhibit the activity of the absorbent. Reduce the emission of deactivated absorbents and the replenishment of fresh absorbents; use heat exchangers to make full use of the heat of high-temperature flue gas and circulating materials to generate high-temperature oxygen, nitrogen and steam, and improve the thermal economy and energy utilization efficiency of the carbon capture process.
Description
技术领域technical field
本发明涉及脱除CO2的装置领域，确切地说是一种带蒸汽活化反应器的钙基吸收剂循环脱除二氧化碳的装置及其方法。The invention relates to the field of devices for removing CO2 , in particular to a device and method for removing carbon dioxide in a calcium-based absorbent cycle with a steam activation reactor.
背景技术Background technique
为应对全球暖化与温室效应加剧，需对化石能源利用过程释放的大量CO2进行减排与控制，基于钙基吸收剂的化学链循环捕获CO2技术由于可与化石能源利用过程耦合而备受关注。钙基化学链技术循环捕获CO2分为碳酸化与煅烧两步骤：首先成分主要为CaO的钙基吸收剂在碳酸化反应器中与化石燃料利用过程产生的烟气中的CO2进行碳酸化反应而形成CaCO3，碳酸化反应器出口可获得低CO2浓度的烟气；随后在碳酸化反应器中形成的CaCO3进入煅烧反应器受热后分解释放出CO2，该反应器热量可由含碳燃料的纯氧燃烧或其他热源供给，反应器出口可获得高浓度的CO2，同时吸收剂煅烧分解为CaO并回送至碳酸化反应器循环利用。钙基吸收剂通过碳酸化-煅烧反应循环捕获CO2，可完成烟气中CO2的分离和富集。该技术优势如下：（1）捕获过程可与流化床技术耦合；（2）CO2捕获温度区间较高，因而可回收高品位余热并驱动蒸汽循环，降低由耦合钙循环带来的效率损失；（3）钙基吸收剂前驱体石灰石和白云石来源广泛且价格低廉；（4）捕获CO2同时可协同脱除烟气中SO2；（5）使用后的吸收剂可用于其他工业过程，比如作为水泥工业的生料。In order to cope with global warming and the intensification of the greenhouse effect, it is necessary to reduce and control the emission of a large amount of CO 2 released during the utilization of fossil energy. The technology of CO 2 capture based on calcium-based absorbents in chemical chain cycle can be coupled with the process of utilization of fossil energy. attention. Calcium-based chemical chain technology captures CO 2 in two steps: carbonation and calcination: firstly, the calcium-based absorbent mainly composed of CaO is carbonated with CO 2 in the flue gas generated by the fossil fuel utilization process in the carbonation reactor CaCO 3 is formed during the reaction, and flue gas with low CO 2 concentration can be obtained at the outlet of the carbonation reactor; then the CaCO 3 formed in the carbonation reactor enters the calcination reactor and decomposes to release CO 2 after being heated. Pure oxygen combustion of carbon fuel or other heat source supply, high concentration CO 2 can be obtained at the reactor outlet, while the absorbent is calcined and decomposed into CaO and returned to the carbonation reactor for recycling. The calcium-based absorbent captures CO 2 through the carbonation-calcination reaction cycle, which can complete the separation and enrichment of CO 2 in the flue gas. The advantages of this technology are as follows: (1) The capture process can be coupled with fluidized bed technology; (2) The CO 2 capture temperature range is relatively high, so high-grade waste heat can be recovered and the steam cycle can be driven to reduce the efficiency loss caused by the coupled calcium cycle ; (3) Limestone and dolomite, the precursors of calcium-based absorbents, are widely available and cheap; (4) Capture CO 2 and synergistically remove SO 2 from flue gas; (5) The absorbent after use can be used in other industrial processes , such as raw meal for the cement industry.
目前钙基化学链碳捕获技术主要问题在于：高温循环过程中钙基吸收剂发生不可逆的晶体结构烧结,导致吸收剂多孔结构致密化，从而阻碍CO2进入吸收剂内核参与碳酸化反应,使得吸收剂失活，即CO2捕获性能随着循环次数增加而迅速衰退。The main problem of the current calcium-based chemical chain carbon capture technology is that the calcium-based absorbent undergoes irreversible sintering of the crystal structure during the high-temperature cycle, resulting in densification of the porous structure of the absorbent, thereby preventing CO2 from entering the core of the absorbent to participate in the carbonation reaction, making the absorption Agent deactivation, that is, the CO2 capture performance decays rapidly with the increase of the cycle number.
发明内容Contents of the invention
本发明的目的在于提供一种带蒸汽活化反应器的钙基吸收剂循环脱除二氧化碳的装置及其方法。The object of the present invention is to provide a device and method for cyclically removing carbon dioxide by a calcium-based absorbent with a steam activation reactor.
上述目的通过以下方案实现：The above purpose is achieved through the following schemes:
一种带蒸汽活化反应器的钙基吸收剂循环脱除二氧化碳的装置，其特征在于：A device for cyclically removing carbon dioxide with a calcium-based absorbent with a steam activation reactor, characterized in that:
包括流化床碳酸化反应器、流化床煅烧分解反应器、流化床蒸汽活化反应器、流化床失水再生反应器、第一旋风分离器、第二旋风分离器、第一返料器、第二返料器、循环物料换热器、CO2换热器、空气分离单元及各部分之间连接管道；Including fluidized bed carbonation reactor, fluidized bed calcination decomposition reactor, fluidized bed steam activation reactor, fluidized bed dehydration regeneration reactor, first cyclone separator, second cyclone separator, first return material device, second feeder, circulating material heat exchanger, CO2 heat exchanger, air separation unit and connecting pipes between each part;
所述流化床碳酸化反应器底部设烟气入口，中下部设循环固体物料入口，上部设烟气出口；所述流化床煅烧分解反应器底部设氧气入口及排渣管，中下部分别设新鲜吸收剂、碳基燃料及循环固体物料入口，上部设烟气出口；所述流化床蒸汽活化反应器中上部设固体物料溢流口；所述流化床失水再生反应器中上部设固体物料溢流口；The bottom of the fluidized bed carbonation reactor is provided with a flue gas inlet, the middle and lower part is provided with a circulating solid material inlet, and the upper part is provided with a flue gas outlet; the bottom of the fluidized bed calcining decomposition reactor is provided with an oxygen inlet and a slagging pipe, and the middle and lower parts The inlet of fresh absorbent, carbon-based fuel and circulating solid material is set, and the upper part is equipped with a flue gas outlet; the middle and upper part of the fluidized bed steam activation reactor is provided with a solid material overflow port; the middle and upper part of the fluidized bed dehydration regeneration reactor is Set solid material overflow port;
在与流化床煅烧分解反应器上部烟气出口相接的烟气管路上，设第一旋风分离器；第一旋风分离器底部与物料换热器相连；循环物料换热器出口分为两条支管，一条支管与流化床蒸汽活化反应器、流化床失水再生反应器、第一返料器依次连接，另一条支管与第一返料器直接相连；第一返料器与设于流化床碳酸化反应器中下部循环固体物料入口相连；第一旋风分离器顶部设CO2排放管路；CO2排放管路与CO2换热器相连；CO2换热器设两路冷却管道，管道内分别为来自空气分离单元的低温氧气与低温氮气；空气分离单元分别设空气入口、氮气出口与氧气出口；循环物料换热器设冷却水入口与蒸汽出口；On the flue gas pipeline connected to the upper flue gas outlet of the fluidized bed calcining decomposition reactor, a first cyclone separator is installed; the bottom of the first cyclone separator is connected to the material heat exchanger; the outlet of the circulating material heat exchanger is divided into two One branch pipe is connected to the fluidized bed steam activation reactor, the fluidized bed dehydration regeneration reactor, and the first feeder in sequence, and the other branch pipe is directly connected to the first feeder; the first feeder is connected to the device It is connected to the inlet of circulating solid material in the middle and lower part of the fluidized bed carbonation reactor; the CO 2 discharge pipeline is installed on the top of the first cyclone separator; the CO 2 discharge pipeline is connected to the CO 2 heat exchanger; the CO 2 heat exchanger is provided with two Cooling pipelines, the pipelines are respectively low-temperature oxygen and low-temperature nitrogen from the air separation unit; the air separation unit is respectively provided with an air inlet, a nitrogen outlet and an oxygen outlet; the circulating material heat exchanger is provided with a cooling water inlet and a steam outlet;
在与流化床碳酸化反应器上部烟气出口相接的烟气管路上，设第二旋风分离器；第二旋风分离器底部通过第二返料器接至流化床煅烧分解反应器循环固体物料入口；第二旋分离器顶部设烟气排放管路。On the flue gas pipeline connected to the flue gas outlet on the upper part of the fluidized bed carbonation reactor, a second cyclone separator is installed; the bottom of the second cyclone separator is connected to the fluidized bed calcining decomposition reactor for circulation through the second feeder Solid material inlet; flue gas discharge pipeline is installed on the top of the second cyclone separator.
所述装置的一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除方法，其特征在于，包括：A calcium-based absorbent carbon dioxide circulation removal method with a steam activation reactor of the device is characterized in that it includes:
（1）空气送入空气分离单元被分离为氧气与氮气，氧气经CO2换热器预热至500-900℃后送入流化床煅烧分解反应器底部作为流化介质，同时为碳基燃料燃烧提供氧化剂；氮气经CO2换热器加热后送入流化床失水再生反应器作为流化介质，同时为失水反应供热；(1) The air is sent to the air separation unit to be separated into oxygen and nitrogen. The oxygen is preheated to 500-900°C by the CO2 heat exchanger and then sent to the bottom of the fluidized bed calcination decomposition reactor as a fluidized medium, and at the same time is a carbon-based Fuel combustion provides an oxidant; nitrogen is heated by a CO2 heat exchanger and sent to a fluidized bed dehydration regeneration reactor as a fluidized medium, and at the same time provides heat for the dehydration reaction;
（2）流化床煅烧分解反应器设置温度为800-1000℃，补充的钙基吸收剂与碳基燃料送入反应器中下部物料入口，碳基燃料与步骤（1）中的预热氧气发生燃烧反应为钙基吸收剂分解供热；煅烧反应器内形成的高温CaO固体物料经第一旋风分离器分离后在循环物料换热器中冷却至400-500℃，随后CaO物料分为两部分，一部分经第一返料器输送至流化床碳酸化反应器中下部循环固体物料入口，另一部分进入流化床蒸汽活化反应器进行活化；废弃固体通过煅烧反应器底部排渣管定期排出；(2) The temperature of the fluidized bed calcination decomposition reactor is set at 800-1000°C, the supplemented calcium-based absorbent and carbon-based fuel are sent to the material inlet in the lower part of the reactor, and the carbon-based fuel and the preheated oxygen in step (1) The combustion reaction provides heat for the decomposition of the calcium-based absorbent; the high-temperature CaO solid material formed in the calcination reactor is separated by the first cyclone separator and cooled to 400-500°C in the circulating material heat exchanger, and then the CaO material is divided into two One part is transported to the middle and lower part of the fluidized bed carbonation reactor through the first return feeder to the circulating solid material inlet, and the other part enters the fluidized bed steam activation reactor for activation; waste solids are regularly discharged through the slag discharge pipe at the bottom of the calcining reactor ;
（3）流化床蒸汽活化反应器设置温度为300-400℃，流化介质为蒸汽；步骤(2)产生的一部分CaO在蒸汽活化反应器中与蒸汽发生水合反应，生成的固态Ca(OH)2经固体物料溢流口送入流化床失水再生反应器内；(3) The temperature of the fluidized bed steam activation reactor is set at 300-400°C, and the fluidized medium is steam; a part of CaO produced in step (2) undergoes hydration reaction with steam in the steam activation reactor, and the generated solid Ca(OH ) 2 into the fluidized bed dehydration regeneration reactor through the solid material overflow port;
（4）流化床失水再生反应器设置温度为500-650℃，流化介质为步骤(1)产生的500-650℃的高温氮气，步骤(3)产生的固态Ca(OH)2在流化床失水再生反应器中受热失水，形成的CaO吸收剂经固体物料溢流口和第一返料器回送至流化床碳酸化反应器中下部循环固体物料入口；(4) The temperature of the fluidized bed dehydration regeneration reactor is set at 500-650°C, the fluidized medium is high-temperature nitrogen at 500-650°C generated in step (1), and the solid Ca(OH) 2 generated in step (3) is in The fluidized bed dehydration regeneration reactor is dehydrated by heating, and the formed CaO absorbent is sent back to the middle and lower part of the fluidized bed carbonation reactor through the solid material overflow port and the first feeder to the circulating solid material inlet;
（5）流化床碳酸化反应器设置温度为650-750℃，步骤(2)和步骤(4)产生的CaO与烟气中CO2发生碳酸化反应生成CaCO3，随后气固混合物进入第二旋风分离器；经第二旋风分离器分离后固体颗粒经第二返料器送至流化床煅烧反应器，开始下一循环重复使用,脱除CO2后烟气由第二分离器上部烟气管路排出；第一旋风分离器出口为碳基燃料纯氧燃烧及CaCO3分解生成的高浓度CO2，从而实现烟气中CO2的脱除与富集。(5) The temperature of the fluidized bed carbonation reactor is set at 650-750°C, the CaO produced in steps (2) and (4) reacts with the CO 2 in the flue gas to generate CaCO 3 , and then the gas-solid mixture enters the second The second cyclone separator: after being separated by the second cyclone separator, the solid particles are sent to the fluidized bed calcination reactor through the second feeder, and the next cycle starts to be reused. After removing CO2 , the flue gas is discharged from the upper part of the second separator The flue gas is discharged from the pipeline; the outlet of the first cyclone separator is the high-concentration CO 2 generated by the pure oxygen combustion of carbon-based fuel and the decomposition of CaCO 3 , so as to realize the removal and enrichment of CO 2 in the flue gas.
所述的一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除方法，其特征在于：步骤（1）所述CO2换热器设两路冷却管道，管道内分别为来自空气分离单元的氮气与氧气。The method for removing carbon dioxide by a calcium-based absorbent with a steam activation reactor is characterized in that: in the step (1), the CO2 heat exchanger is provided with two cooling pipes, and the pipes are respectively from the air separation unit of nitrogen and oxygen.
所述的一种带蒸汽活化反应器的钙基吸收剂循环脱除二氧化碳的方法，其特征在于：步骤（2）所述循环物料冷却器使用水作为冷却介质。The method for cyclically removing carbon dioxide by a calcium-based absorbent with a steam-activated reactor is characterized in that the circulating material cooler in step (2) uses water as a cooling medium.
所述的一种带蒸汽活化反应器的钙基吸收剂循环脱除二氧化碳的方法，其特征在于：步骤（2）所述第一返料器流化介质为蒸汽，蒸汽为循环物料冷却器中冷却介质水与高温物料换热后气化所形成。The method for cyclically removing carbon dioxide by a calcium-based absorbent with a steam-activated reactor is characterized in that: in step (2), the fluidized medium of the first feeder is steam, and the steam is used in the circulating material cooler. It is formed by gasification after heat exchange between cooling medium water and high-temperature materials.
所述的一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除方法，其特征在于：步骤（3）所述流化床蒸汽活化反应器的流化介质蒸汽为循环物料冷却器中冷却介质水与高温物料换热后气化所形成。The method for circulating calcium-based absorbent carbon dioxide removal with a steam activation reactor is characterized in that in step (3), the fluidized medium steam of the fluidized bed steam activation reactor is cooled in the circulating material cooler It is formed by gasification after heat exchange between medium water and high-temperature materials.
所述的一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除方法，其特征在于：步骤（4）所述第二返料器流化介质为蒸汽，蒸汽为循环物料冷却器中冷却介质水与高温物料换热后气化所形成The method for circulating carbon dioxide removal of calcium-based absorbent with a steam activation reactor is characterized in that: in step (4), the fluidized medium of the second feeder is steam, and the steam is cooled in the circulating material cooler It is formed by gasification of medium water and high-temperature material after heat exchange
所述的一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除方法，其特征在于：所述新鲜吸收剂为石灰石、白云石或其他CaO质量百分比高于20%的人工合成钙基吸收剂。The method for removing carbon dioxide circulation of a calcium-based absorbent with a steam activation reactor is characterized in that: the fresh absorbent is limestone, dolomite or other artificially synthesized calcium-based absorbents with a mass percentage of CaO higher than 20%. agent.
所述的一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除方法，其特征在于：所述碳基燃料为煤、生物质、天然气、煤气、合成气中的一种。The method for circulating carbon dioxide removal by a calcium-based absorbent with a steam activation reactor is characterized in that: the carbon-based fuel is one of coal, biomass, natural gas, coal gas, and synthesis gas.
本发明原理如下：Principle of the present invention is as follows:
CaO在碳酸化反应器内与烟气中CO2发生碳酸化反应：CaO+CO2→CaCO3，从而烟气中CO2被脱除，形成CaCO3；脱除CO2后烟气由碳酸化反应器顶部排出；来自碳酸化反应器的CaCO3进入煅烧反应器并发生如下反应：CaCO3→CaO+CO2，该反应为吸热反应，所需热量来自煤、生物质或天然气等碳基燃料纯氧燃烧；CaCO3分解与碳基燃料纯氧燃烧产物均为CO2，故煅烧分解反应器出口为高浓度CO2,可直接用于封存或其他用途；煅烧分解反应器所形成的CaO反应活性在高温煅烧及多次循环使用后活性会出现严重衰退，即其能捕获的CO2质量下降，为维持其活性，将部分CaO送入蒸汽活化反应器，另一部分CaO直接回送至碳酸化反应器；CaO在蒸汽活化反应器中与蒸汽发生水合反应CaO+H2O→Ca(OH)2，有文献表明CaO在形成Ca(OH)2过程中颗粒体积发生膨胀，可再生烧结的CaO孔隙结构；蒸汽活化反应中形成的Ca(OH)2送入失水再生反应器，发生失水反应Ca(OH)2→CaO+H2O重新分解，形成具有发达孔隙结构的CaO吸收剂；再生CaO吸收剂回送至碳酸化反应器开始下一个循环。CaO reacts with CO 2 in the flue gas in the carbonation reactor: CaO+CO 2 →CaCO 3 , so that CO 2 in the flue gas is removed to form CaCO 3 ; after removing CO 2 , the flue gas is carbonized The top of the reactor is discharged; CaCO 3 from the carbonation reactor enters the calcination reactor and undergoes the following reaction: CaCO 3 →CaO+CO 2 , this reaction is an endothermic reaction, and the heat required comes from carbon bases such as coal, biomass or natural gas. Fuel pure oxygen combustion; CaCO 3 decomposition and carbon-based fuel pure oxygen combustion products are both CO 2 , so the outlet of the calcining decomposition reactor is high-concentration CO 2 , which can be directly used for storage or other purposes; the CaO formed by the calcining decomposition reactor The reactivity will decline severely after high-temperature calcination and repeated use, that is, the quality of CO2 it can capture will decrease. In order to maintain its activity, part of the CaO is sent to the steam activation reactor, and the other part of the CaO is directly returned to the carbonation Reactor; CaO undergoes a hydration reaction with steam in the steam activation reactor CaO+H 2 O→Ca(OH) 2 , and literature shows that CaO particles expand in the process of forming Ca(OH) 2 , which can regenerate sintered CaO Pore structure; the Ca(OH) 2 formed in the steam activation reaction is sent to the dehydration regeneration reactor, and the dehydration reaction Ca(OH) 2 →CaO+H 2 O re-decomposes to form a CaO absorbent with a well-developed pore structure; The regenerated CaO absorbent is returned to the carbonation reactor to start the next cycle.
与现有技术相比，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
（1）基于钙基吸收剂循环碳酸化-煅烧分解过程，利用CaO吸收剂碳酸化反应对烟气中CO2进行分离脱除，随后利用CaCO3煅烧分解反应完成CO2富集，所得高浓度CO2可直接封存或作他用;(1) Based on the cyclic carbonation-calcination decomposition process of calcium-based absorbent, the carbonation reaction of CaO absorbent is used to separate and remove CO 2 in the flue gas, and then the CO 2 enrichment is completed by the calcination decomposition reaction of CaCO 3 , resulting in high concentration CO 2 can be directly stored or used for other purposes;
（2）使用蒸汽活化反应器对煅烧后失活CaO进行活性再生，通过水合-失水反应大幅再生吸收剂孔隙结构和反应表面，可显著维持钙基吸收剂活性，抑制吸收剂活性衰退，减少失活吸收剂排放及新鲜吸收剂补充量；(2) Using a steam activation reactor to regenerate the deactivated CaO after calcination, the pore structure and reaction surface of the absorbent can be greatly regenerated through the hydration-dehydration reaction, which can significantly maintain the activity of the calcium-based absorbent, inhibit the activity decline of the absorbent, and reduce Discharge of deactivated absorbent and replenishment of fresh absorbent;
（3）仅对部分失活钙基吸收剂进行蒸汽活化，降低蒸汽活化反应器负荷，同时降低蒸汽使用量和能耗；(3) Steam activation is only performed on part of the deactivated calcium-based absorbent, reducing the load on the steam activation reactor, while reducing steam usage and energy consumption;
（4）使用换热器充分利用高温烟气与循环物料的热量，产生高温氧气、氮气与蒸汽，提高碳捕获过程的热经济性和能量利用效率。(4) Use a heat exchanger to make full use of the heat of high-temperature flue gas and circulating materials to generate high-temperature oxygen, nitrogen and steam, and improve the thermal economy and energy utilization efficiency of the carbon capture process.
附图说明Description of drawings
图1是本发明所述一种带蒸汽活化反应器的钙基吸收剂二氧化碳循环脱除装置及方法示意图。Fig. 1 is a schematic diagram of a calcium-based absorbent carbon dioxide circulation removal device and method with a steam activation reactor according to the present invention.
图中：1. 新鲜吸收剂入口；2.碳基燃料入口；3.氧气入口；4.排渣管；5.流化床煅烧分解反应器；6.第一旋风分离器；7.循环物料换热器；8.流化床蒸汽活化反应器；9.流化床失水再生反应器；10.第一返料器；11.烟气入口；12.流化床碳酸化反应器；13.第二旋风分离器；14.脱除CO2后烟气排放管路；15.第二返料器；16.空气分离单元；17.CO2换热器；18.CO2富集烟气；19.空气；20.氮气；21.高温氮气；22.氧气；23.高温氧气；24.冷却水；25.蒸汽；26.蒸汽；27.氮气；28.蒸汽；29.蒸汽；30.固体物料溢流口；31.固体物料溢流口；32.循环固体物料入口；33.循环固体物料入口；34.烟气出口；35.烟气出口。In the figure: 1. fresh absorbent inlet; 2. carbon-based fuel inlet; 3. oxygen inlet; 4. slag discharge pipe; 5. fluidized bed calcination decomposition reactor; 6. first cyclone separator; 7. circulating material Heat exchanger; 8. Fluidized bed steam activation reactor; 9. Fluidized bed dehydration regeneration reactor; 10. First feeder; 11. Flue gas inlet; 12. Fluidized bed carbonation reactor; 13 .The second cyclone separator; 14. The flue gas discharge pipeline after removing CO 2 ; 15. The second feeder; 16. Air separation unit; 17. CO 2 heat exchanger; 18. CO 2 enriched flue gas ;19. Air; 20. Nitrogen; 21. High temperature nitrogen; 22. Oxygen; 23. High temperature oxygen; 24. Cooling water; 25. Steam; 26. Steam; 27. Nitrogen; 28. Steam; 29. Steam; 30. Solid material overflow port; 31. Solid material overflow port; 32. Circulating solid material inlet; 33. Circulating solid material inlet; 34. Flue gas outlet; 35. Flue gas outlet.
具体实施方式detailed description
下面结合附图，对本发明的实现方式进行说明。The implementation of the present invention will be described below with reference to the accompanying drawings.
本发明所述钙基吸收剂CO2循环脱除装置包括流化床碳酸化反应器12、流化床煅烧分解反应器5、流化床蒸汽活化反应器8、流化床失水再生反应器9、第一旋风分离器6、第二旋风分离器13、第一返料器10、第二返料器15、循环物料换热器7、CO2换热器17、空气分离单元16及各部分之间连接管道；The calcium-based absorbent CO2 circulation removal device of the present invention comprises a fluidized bed carbonation reactor 12, a fluidized bed calcining decomposition reactor 5, a fluidized bed steam activation reactor 8, and a fluidized bed dehydration regeneration reactor 9. The first cyclone separator 6, the second cyclone separator 13, the first feeder 10, the second feeder 15, the circulating material heat exchanger 7, the CO2 heat exchanger 17, the air separation unit 16 and each connecting pipes between parts;
所述流化床碳酸化反应器12底部设烟气入口11，中下部设循环固体物料入口33，上部设烟气出口34；所述流化床煅烧分解反应器5底部设氧气入口3及排渣管4，中下部分别设新鲜吸收剂入口1、碳基燃料入口2及循环固体物料入口32，上部设烟气出口35；所述流化床蒸汽活化反应器8中上部设固体物料溢流口30；所述流化床失水再生反应器9中上部设固体物料溢流口31；The bottom of the fluidized bed carbonation reactor 12 is provided with a flue gas inlet 11, the middle and lower part is provided with a circulating solid material inlet 33, and the upper part is provided with a flue gas outlet 34; the bottom of the fluidized bed calcining decomposition reactor 5 is provided with an oxygen inlet 3 and exhaust The slag pipe 4 has a fresh absorbent inlet 1, a carbon-based fuel inlet 2, and a circulating solid material inlet 32 in the middle and lower parts, and a flue gas outlet 35 in the upper part; a solid material overflow is set in the upper part of the fluidized bed steam activation reactor 8. Port 30; the upper part of the fluidized bed dehydration regeneration reactor 9 is provided with a solid material overflow port 31;
在与流化床煅烧分解反应器5上部烟气出口相接的烟气管路上，设第一旋风分离器6；第一旋风分离器6底部与循环物料换热器7相连；循环物料换热器7出口分为两条支管，一条支管与流化床蒸汽活化反应器8、流化床失水再生反应器9、第一返料器10依次连接，另一条支管与第一返料器10直接相连；第一返料器10与设于流化床碳酸化反应器12中下部的循环固体物料入口33相连；第一旋风分离器6顶部设CO2排放管路；CO2排放管路与CO2换热器17相连；空气分离单元16分别设空气19入口、氮气20出口与氧气22出口；CO2换热器17设两路冷却管道，管道内分别为来自空气分离单元16的氮气20与氧气22；循环物料换热器7设冷却水入口24与蒸汽出口25；On the flue gas pipeline connected to the flue gas outlet on the upper part of the fluidized bed calcining decomposition reactor 5, a first cyclone separator 6 is provided; the bottom of the first cyclone separator 6 is connected to the circulating material heat exchanger 7; the circulating material heat exchange The outlet of the device 7 is divided into two branch pipes, one branch pipe is connected with the fluidized bed steam activation reactor 8, the fluidized bed dehydration regeneration reactor 9, and the first feeder 10 in sequence, and the other branch pipe is connected with the first feeder 10 Directly connected; the first return feeder 10 is connected to the circulating solid material inlet 33 located at the middle and lower part of the fluidized bed carbonation reactor 12; the top of the first cyclone separator 6 is provided with a CO discharge pipeline; the CO discharge pipeline is connected to the The CO2 heat exchanger 17 is connected; the air separation unit 16 is respectively provided with an air 19 inlet, a nitrogen 20 outlet and an oxygen 22 outlet ; and oxygen 22; the circulating material heat exchanger 7 is provided with a cooling water inlet 24 and a steam outlet 25;
在与流化床碳酸化反应器12上部烟气出口相接的烟气管路上，设第二旋风分离器13；第二旋风分离器13底部通过连接第二返料器15接至流化床煅烧分解反应器5循环固体物料入口32；第二旋分离器13顶部设烟气排放管路14，出口为脱除CO2后烟气。On the flue gas pipeline connected to the flue gas outlet on the upper part of the fluidized bed carbonation reactor 12, a second cyclone separator 13 is set; the bottom of the second cyclone separator 13 is connected to the fluidized bed by connecting the second feeder 15 The calcining and decomposition reactor 5 circulates the solid material inlet 32; the second cyclone separator 13 is provided with a flue gas discharge pipeline 14 at the top, and the outlet is the flue gas after removing CO 2 .
实施例1Example 1
空气19送入空气分离单元16被分离为氮气20与氧气22；氮气20经CO2换热器加热为高温氮气21送入流化床失水再生反应器9作为流化介质，同时为失水反应Ca(OH)2→CaO+H2O供热；氧气22经CO2换热器预热为高温氧气23送入流化床煅烧分解反应器5底部氧气入口3作为流化介质，同时为碳基燃料纯氧燃烧提供氧化剂；The air 19 is sent to the air separation unit 16 to be separated into nitrogen 20 and oxygen 22; the nitrogen 20 is heated by a CO 2 heat exchanger to become high-temperature nitrogen 21 and sent to the fluidized bed dehydration regeneration reactor 9 as a fluidized medium, and at the same time is dehydration The reaction Ca(OH) 2 →CaO+H 2 O provides heat; the oxygen 22 is preheated by the CO 2 heat exchanger to become high-temperature oxygen 23 and sent to the fluidized bed calcining decomposition reactor 5. Pure oxygen combustion of carbon-based fuels provides oxidants;
流化床煅烧分解反应器5温度为800-1000℃，新鲜钙基吸收剂与碳基燃料分别送入反应器中下部新鲜吸收剂入口1和碳基燃料入口2，碳基燃料与高温氧气23发生燃烧反应为钙基吸收剂分解反应CaCO3→CaO+CO2供热；煅烧反应器内形成的高温CaO固体物料经第一旋风分离器6分离后在循环物料换热器7中冷却至400-500℃，随后CaO物料分为两部分，一部分经第一返料器10输送至流化床碳酸化反应器12中下部循环固体物料入口33，另一部分进入流化床蒸汽活化反应器8进行活化；废弃固体通过流化床煅烧分解反应器5底部排渣管4定期排出；The temperature of the fluidized bed calcination decomposition reactor 5 is 800-1000°C, fresh calcium-based absorbent and carbon-based fuel are respectively fed into the fresh absorbent inlet 1 and carbon-based fuel inlet 2 in the middle and lower part of the reactor, and the carbon-based fuel and high-temperature oxygen 23 The combustion reaction provides heat for the calcium-based absorbent decomposition reaction CaCO 3 →CaO+CO 2 ; the high-temperature CaO solid material formed in the calcination reactor is separated by the first cyclone separator 6 and then cooled to 400 °C in the circulating material heat exchanger 7 -500°C, then the CaO material is divided into two parts, one part is transported to the lower circulating solid material inlet 33 of the fluidized bed carbonation reactor 12 through the first feeder 10, and the other part enters the fluidized bed steam activation reactor 8 for Activation; waste solids are regularly discharged through the slag discharge pipe 4 at the bottom of the fluidized bed calcination decomposition reactor 5;
循环物料换热器7换热管道进口为液态冷却水24，经换热后形成过热蒸汽25，蒸汽25分为蒸汽26、蒸汽28和蒸汽29，分别送往作为流化床蒸汽活化反应器8、第一返料器10、第二返料器15作为流化介质；The inlet of the heat exchange pipe of the circulating material heat exchanger 7 is liquid cooling water 24, which forms superheated steam 25 after heat exchange, and the steam 25 is divided into steam 26, steam 28 and steam 29, which are respectively sent to the fluidized bed steam activation reactor 8 , the first return device 10, the second return device 15 as fluidized medium;
流化床蒸汽活化反应器温度为300-400℃，流化介质为蒸汽26；来自循环物料换热器7的一部分CaO在蒸汽活化反应器中与蒸汽发生水合反应，生成的固态Ca(OH)2经固体物料溢流口30送入流化床失水再生反应器9内；The temperature of the fluidized bed steam activation reactor is 300-400°C, and the fluidized medium is steam 26; a part of CaO from the circulating material heat exchanger 7 undergoes hydration reaction with steam in the steam activation reactor, and the solid Ca(OH) produced 2. Send the solid material into the fluidized bed dehydration regeneration reactor 9 through the overflow port 30;
流化床失水再生反应器9温度为500-650℃，流化介质为高温氮气21，来自溢流口30的固态Ca(OH)2在流化床失水再生反应器9中受热失水Ca(OH)2→CaO+H2O，形成的CaO吸收剂经固体物料溢流口31和第一返料器10回送至流化床碳酸化反应器中下部循环固体物料入口33；The temperature of the fluidized bed dehydration regeneration reactor 9 is 500-650°C, the fluidized medium is high temperature nitrogen 21, and the solid Ca(OH) 2 from the overflow port 30 is heated and dehydrated in the fluidized bed dehydration regeneration reactor 9 Ca(OH) 2 →CaO+H 2 O, the formed CaO absorbent is returned to the middle and lower circulating solid material inlet 33 of the fluidized bed carbonation reactor through the solid material overflow port 31 and the first feeder 10;
流化床碳酸化反应器12温度为650-750℃，来自第一返料器10的 CaO与烟气入口11进入的烟气中的CO2发生碳酸化反应生成CaCO3，随后气固混合物进入第二旋风分离器13；经第二旋风分离器13分离后固体颗粒经第二返料器15送至流化床煅烧分解反应器5，开始下一循环重复使用,脱除CO2后烟气由第二分离器上部烟气管路14排出；第一旋风分离器6出口为碳基燃料纯氧燃烧及CaCO3分解生成的高浓度CO2富集烟气，经CO2换热器17冷却降温后得到CO2富集烟气18并排出，从而实现烟气中CO2的脱除与富集。The temperature of the fluidized bed carbonation reactor 12 is 650-750°C, the CaO from the first feeder 10 reacts with the CO 2 in the flue gas entering the flue gas inlet 11 to generate CaCO 3 , and then the gas-solid mixture enters The second cyclone separator 13; the solid particles separated by the second cyclone separator 13 are sent to the fluidized bed calcining decomposition reactor 5 through the second feeder 15, and the next cycle is started to be reused, and the flue gas is removed after CO2 Discharged from the flue gas pipeline 14 at the upper part of the second separator; the outlet of the first cyclone separator 6 is the high-concentration CO2 -enriched flue gas generated by the pure oxygen combustion of carbon - based fuel and the decomposition of CaCO3, which is cooled by the CO2 heat exchanger 17 After cooling down, the CO 2 enriched flue gas 18 is obtained and discharged, thereby realizing the removal and enrichment of CO 2 in the flue gas.
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