林海周,吴大卫,范永春,罗必雄,裴爱国,方梦祥
LIN Haizhou,WU Dawei,FAN Yongchun,LUO Bixiong,PEI Aiguo,FANG Mengxiang

• 1:中国能源建设集团广东省电力设计研究院有限公司
• 2:中国电力工程顾问集团有限公司
• 3:中国能源建设股份有限公司
• 4:浙江大学能源清洁利用国家重点实验室

摘要(Abstract)：

燃烧后化学吸收技术是现阶段最成熟的燃煤电厂烟气CO_2捕集技术之一。由于传统的胺基吸收剂再生能耗较高，不利于化学吸收碳捕集技术的推广应用。液-液两相吸收剂能大幅降低再生能耗，具备替代传统吸收剂的前景。综述了两相吸收剂的技术特点和研发进展，根据吸收剂组成将两相吸收剂分成混合胺型两相吸收剂(活性胺+三级胺分相剂+水)、有机溶剂型两相吸收剂(活性胺+有机溶剂分相剂+水)和无水型两相吸收剂(活性胺+三级胺/有机溶剂分相剂)3种类型，重点对这3种类型两相吸收剂的分相行为、能耗、黏度、吸收负荷等特性进行分析。其中有机溶剂型两相吸收剂在能耗(1.5～3.2 GJ/t)、黏度(可控制在20 mPa·s以下)和成本(有机溶剂分相剂+水更具成本潜力)等方面优势相对更明显。两相吸收剂作为新型吸收剂，相比传统胺吸收剂在工业应用方面仍存在富相黏度较高、吸收剂成本较高、分相稳定控制难等较多挑战。为加快两相吸收剂的工程应用，未来需要在低能耗配方体系优化、降低富相黏度和吸收剂损耗、提升分相控制能力以及开展长周期运行测试，提升工艺稳定和可靠性等方面开展更深入研究。
Post-combustion chemical absorption is one of the most mature technologies for CO_2 capture from coal-fired power plants. However, the high energy consumption for regeneration of traditional amine-based solvents is not conducive to the commercial application of chemical absorption technology. Liquid-liquid biphasic solvents, which can greatly reduce the regeneration energy consumption, have the prospect of replacing traditional solvents. The technical characteristics and solvents development of liquid-liquid biphasic solvents were reviewed in this paper. The liquid-liquid biphasic solvents can be divided into three types according to the composition, namely blending amine type(active amine + tertiary amine phase separation agent + water), organic solvent type(active amine + organic solvent phase separation agent + water) and water-free type(active amine + tertiary amine/organic solvent phase separation agent). The analysis focused on the phase separation behavior, energy consumption, viscosity and CO_2 absorption load of three different type biphasic solvents. Among them, organic solvent type biphasic solvents have more advantages in regeneration energy consumption(1.5-3.2 GJ/t), viscosity(can be controlled below 20 mPa·s), and cost(organic solvent phase separation agent + water shows better potential in cost). As a new type of solvent, liquid-liquid biphasic solvents still face many challenges in industrial application compared to traditional solvents, such as high viscosity of rich phase, high cost of solvents and difficult in phase separation control, etc. In order to accelerate the industrial application of biphasic solvents, it is necessary to carry out more in-depth research on optimizing the formula system with low energy consumption, reducing the rich phase viscosity and the loss of solvents, improving the phase separation control ability and carry out long cycle operation tests to improve process stability and reliability.

关键词(KeyWords)： 二氧化碳捕集;化学吸收法;液-液两相吸收剂;工业应用;再生能耗;黏度
CO_2 capture;chemical absorption;liquid-liquid biphasic solvents;industrial application;regeneration energy consumption;viscosity

Abstract:

Keywords:

基金项目(Foundation): 中国电力工程顾问集团有限公司重大科技专项资助项目(GSKJ3-J02-2021)

作者(Author): 林海周,吴大卫,范永春,罗必雄,裴爱国,方梦祥
LIN Haizhou,WU Dawei,FAN Yongchun,LUO Bixiong,PEI Aiguo,FANG Mengxiang

DOI: 10.13226/j.issn.1006-6772.RM23040101

参考文献(References)：

• [1] 蔡博峰，李琦，张贤.中国二氧化碳捕集利用与封存 (CCUS) 年度报告 (2021):中国CCUS 路径研究[R].北京：生态环境部环境规划院 ,中国科学院武汉岩土力学研究所 ,中国 21世纪议程管理中心，2021.
• [2] 陆诗建，贡玉萍，刘玲，等.有机胺CO2吸收技术研究现状与发展方向 [J].洁净煤技术，2022,28(9):44-54.LU Shijian,GONG Yuping,LIU Ling,et al.Research status and future development direction of CO2 absorption technology for organic amine [J].Clean Coal Technology,2022,28(9):44-54.
• [3] 林海周，杨晖，罗海中，等.烟气二氧化碳捕集胺类吸收剂研究进展[J].南方能源建设，2019,6(1):8-14.LIN Haizhou,YANG Hui,LUO Haizhong,et al.Research progress of amine absorbents for CO2 capture in flue gas [J].Southern Energy Construction,2019,6 (1):8-14.
• [4] 林海周，裴爱国，方梦祥.燃煤电厂烟气二氧化碳胺法捕集工艺改进研究进展[J].化工进展，2018,37(12):4874-4886.LIN Haizhou,PEI Aiguo,FANG Mengxiang.Progress of research on process modifications for amine solvent-based post combustion CO2 capture from coal-fired power plant [J].Chemical Industry and Engineering Progress,2018,37 (12):4874-4886.
• [5] 涂智芳，魏建文，周小斌.固-液相变二氧化碳吸收剂的研究进展[J].洁净煤技术，2022,28(9):122-132.TU Zhifang,WEI Jianwen,ZHOU Xiaobin.Research progress on carbon dioxide capture using solid.liquid phase.change absorbents[J].Clean Coal Technology,2022,28(9):122-132.
• [6] ZHUANG Q,CLEMENTS B,DAI J,et al.Ten years of research on phase separation absorbents for carbon capture:Achievements and next steps[J].International Journal of Greenhouse Gas Control,2016,52:449-460.
• [7] 张政，刘彪，覃显业，等.相变溶剂吸收CO2研究进展[J].材料导报，2014(21):94-99.ZHANG Zheng,LIU Biao,QIN Xianye,et al.Progress in CO2 capture using phase change solvents [J].Materials Reports,2014 (21):94-99.
• [8] RAYNAL L,BRIOT P,DREILLARD M,et al.Evaluation of the DMX process for industrial pilot demonstration:Methodology and results[J].Energy Procedia,2014,63:6298-6309.
• [9] WANG L,ZHANG Y,WANG R,et al.Advanced monoethanolamine absorption using sulfolane as a phase splitter for CO2 capture[J].Environmental Science & Technology,2018,52(24):14556-14563.
• [10] 王涛，刘飞，方梦祥，等.两相吸收剂捕集二氧化碳技术研究进展[J].中国电机工程学报，2021,41(4):1186-1196,1525.WANG Tao,LIU Fei,FANG Mengxiang,et al.Research progress in biphasic solvent for CO2 capture technology[J].Proceedings of the CSEE,2021,41(4):1186-1196,1525.
• [11] 徐志成，王淑娟，陈昌和.BDA/DEEA两相吸收剂吸收CO2的研究[J].工程热物理学报，2013,34(5):993-997.XU Zhicheng,WANG Shujuan,CHEN Changhe.CO2 absorption by BDA/DEEA biphasic solvents [J].Journal of Engineering Thermophysics,2013,34 (5):993-997.
• [12] YE Q,WANG X,LU Y.Screening and evaluation of novel biphasic solvents for energy-efficient post-combustion CO2 capture[J].International Journal of Greenhouse Gas Control,2015,39:205-214.
• [13] PINTO D D D,KNUUTILA H,FYTIANOS G,et al.CO2 post combustion capture with a phase change solvent.Pilot plant campaign[J].International Journal of Greenhouse Gas Control,2014,31:153-164.
• [14] PINTO D D D,ZAIDY S A H,HARTONO A,et al.Evaluation of a phase change solvent for CO2 capture:Absorption and desorption tests[J].International Journal of Greenhouse Gas Control,2014,28:318-327.
• [15] 刘飞.胺基两相吸收剂捕集二氧化碳机理研究[D].杭州：浙江大学，2020.
• [16] 刘练波，方梦祥，许世森，等.DMAC/DETA复配水溶液两相吸收剂吸收CO2的行为研究[J].中国电机工程学报，2021,41(18):6284-6292.LIU Lianbo,FANG Mengxiang,XU Shisen,et al.CO2 Absorption behavior by DMAC/DETA biphasic absorbent[J].Proceedings of the CSEE,2021,41 (18):6284-6292.
• [17] ZHANG S,SHEN Y,SHAO P,et al.Kinetics,thermodynamics,and mechanism of a novel biphasic solvent for CO2 capture from flue gas[J].Environmental Science & Technology,2018,52(6):3660-3668.
• [18] ZHOU X,JING G,LV B,et al.Low-viscosity and efficient regeneration of carbon dioxide capture using a biphasic solvent regulated by 2-amino-2-methyl-1-propanol[J].Applied Energy,2019,235:379-390.
• [19] WANG R,LIU S,WANG L,et al.Superior energy-saving splitter in monoethanolamine-based biphasic solvents for CO2 capture from coal-fired flue gas[J].Applied Energy,2019,242:302-310.
• [20] 沈丽.新型相变吸收剂AEP/正丙醇水溶液捕集二氧化碳传质—反应动力学[D].杭州：浙江大学，2021.
• [21] LI X,LIU J,JIANG W,et al.Low energy-consuming CO2 capture by phase change absorbents of amine/alcohol/H2O[J].Separation and Purification Technology,2021,275:119181.
• [22] WANG R,YANG Y,WANG M,et al.Energy efficient diethylenetriamine-1-propanol biphasic solvent for CO2 capture:Experimental and theoretical study[J].Applied Energy,2021,290:116768.
• [23] YANG F,JIN X,FANG J,et al.Development of CO2 phase change absorbents by means of the cosolvent effect[J].Green Chemistry,2018,20(10):2328-2336.
• [24] WANG N,PENG Z,GAO H,et al.New insight and evaluation of secondary Amine/N-butanol biphasic solutions for CO2 capture:Equilibrium solubility,phase separation behavior,absorption rate,desorption rate,energy consumption and ion species[J].Chemical Engineering Journal,2022,431:133912.
• [25] WANG R,ZHAO H,QI C,et al.Novel tertiary amine-based biphasic solvent for energy-efficient CO2 capture with low corrosivity[J].Energy,2022,260:125045.
• [26] LV J,LIU S,LING H,et al.Development of a promising biphasic absorbent for postcombustion CO2 capture:Sulfolane+2-(Methylamino)ethanol + H2O[J].Industrial & Engineering Chemistry Research,2020,59(32):14496-14506.
• [27] LUO W,GUO D,ZHENG J,et al.CO2 absorption using biphasic solvent:Blends of diethylenetriamine,sulfolane,and water[J].International Journal of Greenhouse Gas Control,2016,53:141-148.
• [28] LIU F,FANG M,YI N,et al.Research on Alkanolamine-based physical-chemical solutions as biphasic solvents for CO2 capture[J].Energy & Fuels,2019,33(11):11389-11398.
• [29] WANG L,LIU S,WANG R,et al.Regulating phase separation behavior of a DEEA-TETA biphasic solvent using sulfolane for energy-saving CO2 capture[J].Environmental Science & Technology,2019,53(21):12873-12881.
• [30] WANG B,CHEN X,YU G.A new biphasic system of TEPA/DGME/Water for capturing CO2[J].Separation and Purification Technology,2022,294:121173.
• [31] 张琪悦，方梦祥，周康，等.燃煤烟气碳捕集两相吸收剂开发及其性能研究[J].热力发电，2023,52(4):24-33.ZHANG Qiyue,FANG Mengxiang,ZHOU Kang,et al.Development and properties of physical solvent phase separation absorbent for coal-fired flue gas[J].Thermal Power Generation,2023,52(4):24-33.
• [32] HU H,FANG M,LIU F,et al.Novel alkanolamine-based biphasic solvent for CO2 capture with low energy consumption and phase change mechanism analysis[J].Applied Energy,2022,324:119570.
• [33] QIU Y,LU H,ZHU Y,et al.Phase-change CO2 absorption using novel 3-dimethylaminopropylamine with primary and tertiary amino groups[J].Industrial & Engineering Chemistry Research,2020,59(19):8902-8910.
• [34] SHEN S,SHI X,LI C,et al.Nonaqueous (amine+glycol ether) solvents for energy-efficient CO2 capture:New insights into phase change behaviors and assessment of capture performance[J].Separation and Purification Technology,2022,300:121908.
• [35] LI X,ZHOU X,WEI J,et al.Reducing the energy penalty and corrosion of carbon dioxide capture using a novel nonaqueous monoethanolamine-based biphasic solvent[J].Separation and Purification Technology,2021,265:118481.
• [36] ZHOU X,LI X,WEI J,et al.Novel nonaqueous liquid-liquid biphasic solvent for energy-efficient carbon dioxide capture with low corrosivity[J].Environmental Science & Technology,2020,54(24):16138-16146.
• [37] LIU F,FANG M,DONG W,et al.Carbon dioxide absorption in aqueous alkanolamine blends for biphasic solvents screening and evaluation[J].Applied Energy,2019,233:468-477.
• [38] ZHOU X,LIU F,LV B,et al.Evaluation of the novel biphasic solvents for CO2 capture:Performance and mechanism[J].International Journal of Greenhouse Gas Control,2017,60:120-128.
• [39] ZHANG W,JIN X,TU W,et al.Development of MEA-based CO2 phase change absorbent[J].Applied Energy,2017,195:316-323.
• [40] LIU S,LING H,LV J,et al.New insights and assessment of primary alkanolamine/sulfolane biphasic solutions for post-combustion CO2 capture:Absorption,desorption,phase separation,and technological process[J].Industrial & Engineering Chemistry Research,2019,58(44):20461-20471.
• [41] BARZAGLI F,MANI F,PERUZZINI M.Novel water-free biphasic absorbents for efficient CO2 capture[J].International Journal of Greenhouse Gas Control,2017,60:100-109.
• [42] 符乐，杨阳，徐文青，等.新型相变有机胺吸收捕集CO2技术研究进展[J/OL].化工进展：1-16[2023-05-01].DOI:10.16085/j.issn.1000-6613.2022-1019.FU Le,YANG Yang,XU Wenqing et al.Research progress in CO2 capture technology using novel biphasicorganic amine absorbent[J].Chemical Industry and Engineering Progress:1-16[2023-05-01].DOI:10.16085/j.issn.1000-6613.2022-1019.
• [43] 黄宇辉，方梦祥，王涛，等.新型MEA-AMP混合胺吸收剂的抗降解剂研究[J].能源工程，2021(5):35-42.HUANG Yuhui,FANG Mengxiang,WANG Tao,et al.Inhibitor for new MEA-AMP blended amine absorbent[J].Energy Engineering,2021(5):35-42.
• [44] 刘飞，祁志福，方梦祥，等.用于烟气二氧化碳捕集的有机胺挥发性研究进展[J].热力发电，2022,51(1):33-43.LIU Fei,QI Zhifu,FANG Mengxiang,et al.Research progress of amine volatility for carbon dioxide capture from flue gas[J].Thermal Power Generation,2022,51(1):33-43.
• [45] 狄闻韬.CO2化学吸收系统胺排放特性及控制研究[D].杭州浙江大学，2022.
• [46] 方梦祥，狄闻韬，易宁彤，等.CO2化学吸收系统污染物排放与控制研究进展 [J].洁净煤技术，2021,27(2):8-16.FANG Mengxiang,DI Wentao,YI Ningtong,et al.Research progress on pollutant emission and control from CO2 chemical absorption system [J].Clean Coal Technology,2021,27(2):8-16.