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Due to the low-carbon transformation requirement of domestic coal power units in the “carbon peak and carbon neutrality” situation, exploring a new industrialization way in solid adsorption CO2 capture technology on CCUS, and developing a new solid chemical sorbent to capture CO2 from coal-fired flue gas, are important for realizing large-scale application of such technology. Current researches on solid adsorption CO2 capture technology in China mainly focus on the theory level. This study systematically reviews and analyzes the research progress on solid sorbent materials at low, medium and high temperatures, points out the directions for further research, and identifies the research content needed for scaled application. A typical high-temperature calcium-based sorbent is used as an example to analyze the industrial applications of the entire process, including the sorbent preparation, sorbent scaling up, sorbent granulation and molding, reactor design, and CO2 capture system verification for calcium looping. This study can provide references for aspects including further key technology research and breakthroughs, the construction of a full process for solid adsorption CO2 capture with high activity and low energy requirement, and the realization of the large-scale application of solid adsorption CO2 capture technology.
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针对“双碳”形势下国内煤电机组低碳转型需求,探索CCUS技术工业化固碳新路径,开发可直接用于燃煤烟气CO2捕集的新型固体化学吸附材料,实现燃煤烟气固体吸附CO2捕集技术规模化应用具有重要意义。目前,国内固体吸附CO2捕集技术研究多以分项理论研究为主,对此,系统梳理和分析了低、中、高温固体吸附材料研究进展,指出固体吸附材料研究需拓展的方向,以及实现规模化应用需开展的研究内容。以典型高温钙基吸附剂为例,针对吸附剂放大制备、造粒成型、反应器设计及钙循环CO2捕集系统验证全过程工业化应用研究进行分析。研究内容可为下一步开展关键技术研究与突破,加快构建高活性低能耗固体吸附捕集CO2的全流程装备技术体系,实现固体吸附CO2捕集技术规模化应用提供参考。
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固体吸附CO2捕集工艺流程示意, figureFileSmall=0+Ges94K62X1ATms+9ZRhQ==, figureFileBig=bFjF6MR4QDesr+n9FI8XEQ==, tableContent=null), ArticleFig(id=1236390480431345962, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.2, caption=
Schematic diagram of CO2 adsorption process by alkali metal nitrate/nitrite doped MgO adsorbent, figureFileSmall=ihCmUEDSp7ODpMcP9NVgoA==, figureFileBig=cQhjKQOdUtVWV+RMns1fTw==, tableContent=null), ArticleFig(id=1236390480515232051, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图2, caption=
碱金属硝酸盐/亚硝酸盐掺杂MgO吸附剂对CO2的吸附过程示意, figureFileSmall=ihCmUEDSp7ODpMcP9NVgoA==, figureFileBig=cQhjKQOdUtVWV+RMns1fTw==, tableContent=null), ArticleFig(id=1236390480590729527, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.3, caption=
Sintering deactivation mechanism of CaO-based adsorbent, figureFileSmall=ukZcGlV10H2AwdlTC5IIjA==, figureFileBig=Kv07xZHUoiNQ1mBCQwUIBw==, tableContent=null), ArticleFig(id=1236390480674615614, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图3, caption=
CaO烧结失活机理, figureFileSmall=ukZcGlV10H2AwdlTC5IIjA==, figureFileBig=Kv07xZHUoiNQ1mBCQwUIBw==, tableContent=null), ArticleFig(id=1236390480783667525, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.4, caption=
Schematic diagram of hollow spherical model and solid sphere model, figureFileSmall=k7YJ83SmOIJ+kFWP8vU8zQ==, figureFileBig=3vjcv2hB7ukkgJXG3xR6ng==, tableContent=null), ArticleFig(id=1236390480909496653, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图4, caption=
空心核壳模型与实心球模型示意, figureFileSmall=k7YJ83SmOIJ+kFWP8vU8zQ==, figureFileBig=3vjcv2hB7ukkgJXG3xR6ng==, tableContent=null), ArticleFig(id=1236390481010159956, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.5, caption=
Schematic diagram of preparation of solid adsorbent by extrusion-spheronization method, figureFileSmall=Au89Amp6rq6B4F3y/k3RsQ==, figureFileBig=49m6gc5NLGxNGjwWtlAddw==, tableContent=null), ArticleFig(id=1236390481123406168, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图5, caption=
挤出-滚圆法制备固体吸附剂示意, figureFileSmall=Au89Amp6rq6B4F3y/k3RsQ==, figureFileBig=49m6gc5NLGxNGjwWtlAddw==, tableContent=null), ArticleFig(id=1236390481232458082, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.6, caption=
Process flow diagram of the 1 MW pilot plant at Darmstadt University of Technology, figureFileSmall=rxeIuW29wvyokW/9M4IkcA==, figureFileBig=SkM1+1nD/T8lx0BtuuWTig==, tableContent=null), ArticleFig(id=1236390481312149862, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图6, caption=
达姆施塔特理工大学的1 MW试验厂工艺流程, figureFileSmall=rxeIuW29wvyokW/9M4IkcA==, figureFileBig=SkM1+1nD/T8lx0BtuuWTig==, tableContent=null), ArticleFig(id=1236390481408618859, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.7, caption=
Principle diagram of the INCAR-CSIC 1.7 MW dual fluidized bed calcium cycling demonstration device, figureFileSmall=lYUilc4HpGkWf7Z7AC6HCQ==, figureFileBig=9qo2+6awLV8mlpNaGJZcWA==, tableContent=null), ArticleFig(id=1236390481492504945, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图7, caption=
INCAR-CSIC 1.7 MW双流化床钙循环示范装置原理示意, figureFileSmall=lYUilc4HpGkWf7Z7AC6HCQ==, figureFileBig=9qo2+6awLV8mlpNaGJZcWA==, tableContent=null), ArticleFig(id=1236390481593168248, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.8, caption=
Schematic diagram of the 1.9 MW calcium cycling device at China Taiwan Industrial Technology Research Institute, figureFileSmall=dEcs91D0XKnx54q4YP1tIg==, figureFileBig=X4Fq18W3n14TJjA8/us8VA==, tableContent=null), ArticleFig(id=1236390481706414462, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图8, caption=
中国台湾工业技术研究所1.9 MW钙循环装置示意, figureFileSmall=dEcs91D0XKnx54q4YP1tIg==, figureFileBig=X4Fq18W3n14TJjA8/us8VA==, tableContent=null), ArticleFig(id=1236390481790300549, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.9, caption=
Schematic diagram of the 10 kW dual-fluidized bed calcium circulation device at Tsinghua University, figureFileSmall=W7Mlf743ZVcaPu/HdWDbDA==, figureFileBig=FtuZcb0LIVvCMeIWbTbeHQ==, tableContent=null), ArticleFig(id=1236390481899352460, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图9, caption=
清华大学10 kW双流化床钙循环装置示意, figureFileSmall=W7Mlf743ZVcaPu/HdWDbDA==, figureFileBig=FtuZcb0LIVvCMeIWbTbeHQ==, tableContent=null), ArticleFig(id=1236390481983238546, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.10, caption=
Schematic diagram of the 1 kg/h dual fluidized bed calcium circulation bench at Zhejiang-University, figureFileSmall=3TsuRYnebb/aFnP2nG2cmA==, figureFileBig=iiRKq+3cViqEiabgv681GQ==, tableContent=null), ArticleFig(id=1236390482117456286, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图10, caption=
浙江大学1 kg/h双流化床钙循环台架示意, figureFileSmall=3TsuRYnebb/aFnP2nG2cmA==, figureFileBig=iiRKq+3cViqEiabgv681GQ==, tableContent=null), ArticleFig(id=1236390482201342374, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Fig.11, caption=
Schematic diagram of the pilot test benches of CO2 capture developed by Huazhong University of Science and Technology, figureFileSmall=5lJjBc4uHTH1gUc2CinKiQ==, figureFileBig=1VWEkhYqxUrGf3BL+nOONg==, tableContent=null), ArticleFig(id=1236390482314588587, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=图11, caption=
华中科技大学开发的CO2捕集试验台架, figureFileSmall=5lJjBc4uHTH1gUc2CinKiQ==, figureFileBig=1VWEkhYqxUrGf3BL+nOONg==, tableContent=null), ArticleFig(id=1236390482427834802, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Tab.1, caption=
Classification and characteristics of solid adsorbent materials
, figureFileSmall=null, figureFileBig=null, tableContent=
| 类别 | 吸附温度/℃ | 吸附种类 | 典型材料 | 优点 | 缺点 | 改性方法 |
|---|
| 低温吸附材料 | <200 | 物理吸附 | 沸石、活性炭、MOF、聚合物等 | 技术成熟 | 吸附容量低,受烟气杂质影响大,需除杂、加压,能耗高 | |
| 化学吸附 | Na2CO3、K2CO3等 | 常压反应,脱附温度低 | 吸附容量低,烟气水分影响大,系统余热难利用 | 多孔载体负载 |
| 中温吸附材料 | 200~500 | 化学吸附 | MgO、水滑石等 | 常压反应,吸、脱附温度适中 | 吸附速率低 | 多孔载体负载,碱金属盐掺杂,新型合成 |
| 高温吸附材料 | >500 | 化学吸附 | CaO、Li4SiO4、钙钛矿等 | 常压反应,范围广、吸附容量大、速率快 | 易烧结,高温不利于物料输运,余热利用系统复杂 | 碱金属盐掺杂,掺杂惰性载体,新型合成 |
), ArticleFig(id=1236390482545275320, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=表1, caption=
固体吸附材料的分类及特点
, figureFileSmall=null, figureFileBig=null, tableContent=
| 类别 | 吸附温度/℃ | 吸附种类 | 典型材料 | 优点 | 缺点 | 改性方法 |
|---|
| 低温吸附材料 | <200 | 物理吸附 | 沸石、活性炭、MOF、聚合物等 | 技术成熟 | 吸附容量低,受烟气杂质影响大,需除杂、加压,能耗高 | |
| 化学吸附 | Na2CO3、K2CO3等 | 常压反应,脱附温度低 | 吸附容量低,烟气水分影响大,系统余热难利用 | 多孔载体负载 |
| 中温吸附材料 | 200~500 | 化学吸附 | MgO、水滑石等 | 常压反应,吸、脱附温度适中 | 吸附速率低 | 多孔载体负载,碱金属盐掺杂,新型合成 |
| 高温吸附材料 | >500 | 化学吸附 | CaO、Li4SiO4、钙钛矿等 | 常压反应,范围广、吸附容量大、速率快 | 易烧结,高温不利于物料输运,余热利用系统复杂 | 碱金属盐掺杂,掺杂惰性载体,新型合成 |
), ArticleFig(id=1236390482654327230, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=EN, label=Tab.2, caption=
Typical calcium cycling device benches and test data at home and abroad
, figureFileSmall=null, figureFileBig=null, tableContent=
| 研究机构 | 规模 | CO2体积分数/% | 吸附材料 | 碳酸化反应器 | 煅烧反应器 | CO2捕集效率/% |
|---|
| 类型 | 直径/m | 高度/m | 温度/℃ | 类型 | 直径/m | 高度/m | 加热方式 | 温度/℃ |
|---|
| 达姆施塔特理工大学[100] | 1 MW | 10.0~12.0 | 石灰石 | CFB | 0.59 | 8.66 | 650~670 | CFB | 0.400 | 11.35 | 煤粉 | <1 000 | 90 |
| 西班牙国家研究委员会[106] | 30 kW | 3.0~25.0 | 石灰石 | CFB | 0.10 | 6.00 | 568~722 | CFB | 0.100 | 6.50 | 煤粉 | 800~900 | 70~90 |
| 西班牙国家研究委员会[102] | 1.7 MW | 12.6 | 石灰石 | CFB | 0.65 | 15.00 | 600~715 | CFB | 0.750 | 15.00 | 煤粉 | 820~950 | 40~95 |
| 中国台湾工业技术研究院[107] | 1 kW | 15.0 | 碳酸钙 | BFB | 0.10 | 2.50 | 600~700 | MB | 0.050 | 0.90 | 电加热 | 800~900 | 99 |
| 中国台湾工业技术研究院[108] | 3 kW | 15.0 | 石灰石 | BFB | 0.10 | 2.50 | 600~700 | RK | 0.270 | 5.00 | 天然气 | 500~1 000 | 99 |
| 中国台湾工业技术研究院[103] | 1.9 MW | 20.0~25.0 | 石灰石 | BFB | 3.30 | 4.20 | 650 | RK | 0.900 | 5.00 | 天然气 | 500~1 000 | 85 |
| 清华大学[104] | 10 kW | 12.5~14.5 | 白云石 | BFB | 0.15 | 1.00 | 640 | BFB | 0.117 | 1.00 | 电加热 | 850 | 95 |
| 浙江大学[105] | 1 kg/h CO2吸附 | 15.0 | 合成钙基吸附剂 | BFB | 0.12 | 3.75 | 700 | BFB | 0.120 | 3.75 | 电加热 | 900 | 90 |
| 华中科技大学 | 150 kg/h CO2吸附 | 15.0 | 合成钙基吸附剂 | CFB | — | — | 625~660 | CFB | — | — | 电加热 | 875~930 | 93~99 |
), ArticleFig(id=1236390482784350662, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236345968061370787, language=CN, label=表2, caption=
国内外典型钙循环装置台架及试验数据
, figureFileSmall=null, figureFileBig=null, tableContent=
| 研究机构 | 规模 | CO2体积分数/% | 吸附材料 | 碳酸化反应器 | 煅烧反应器 | CO2捕集效率/% |
|---|
| 类型 | 直径/m | 高度/m | 温度/℃ | 类型 | 直径/m | 高度/m | 加热方式 | 温度/℃ |
|---|
| 达姆施塔特理工大学[100] | 1 MW | 10.0~12.0 | 石灰石 | CFB | 0.59 | 8.66 | 650~670 | CFB | 0.400 | 11.35 | 煤粉 | <1 000 | 90 |
| 西班牙国家研究委员会[106] | 30 kW | 3.0~25.0 | 石灰石 | CFB | 0.10 | 6.00 | 568~722 | CFB | 0.100 | 6.50 | 煤粉 | 800~900 | 70~90 |
| 西班牙国家研究委员会[102] | 1.7 MW | 12.6 | 石灰石 | CFB | 0.65 | 15.00 | 600~715 | CFB | 0.750 | 15.00 | 煤粉 | 820~950 | 40~95 |
| 中国台湾工业技术研究院[107] | 1 kW | 15.0 | 碳酸钙 | BFB | 0.10 | 2.50 | 600~700 | MB | 0.050 | 0.90 | 电加热 | 800~900 | 99 |
| 中国台湾工业技术研究院[108] | 3 kW | 15.0 | 石灰石 | BFB | 0.10 | 2.50 | 600~700 | RK | 0.270 | 5.00 | 天然气 | 500~1 000 | 99 |
| 中国台湾工业技术研究院[103] | 1.9 MW | 20.0~25.0 | 石灰石 | BFB | 3.30 | 4.20 | 650 | RK | 0.900 | 5.00 | 天然气 | 500~1 000 | 85 |
| 清华大学[104] | 10 kW | 12.5~14.5 | 白云石 | BFB | 0.15 | 1.00 | 640 | BFB | 0.117 | 1.00 | 电加热 | 850 | 95 |
| 浙江大学[105] | 1 kg/h CO2吸附 | 15.0 | 合成钙基吸附剂 | BFB | 0.12 | 3.75 | 700 | BFB | 0.120 | 3.75 | 电加热 | 900 | 90 |
| 华中科技大学 | 150 kg/h CO2吸附 | 15.0 | 合成钙基吸附剂 | CFB | — | — | 625~660 | CFB | — | — | 电加热 | 875~930 | 93~99 |
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