徐冬,黄艳,宋俊朝,史晓宏,王涛,曾伟强,张帅,李水飞,方梦祥,高翔
XU Dong,HUANG Yan,SONG Junchao,SHI Xiaohong,WANG Tao,ZENG Weiqiang,ZHANG Shuai,LI Shuifei,FANG Mengxiang,GAO Xiang

• 1:国家能源集团新能源技术研究院有限公司
• 2:国能锦界能源有限责任公司
• 3:浙江大学能源高效清洁利用全国重点实验室
• 4:浙江大学浙江省清洁能源与碳中和重点实验室

摘要(Abstract)：

在如今温室效应日益严重背景下，化学吸收法作为当前最具应用前景的燃煤烟气脱碳技术，受国内外广泛关注，开发低再生能耗、高稳定、易工程化应用的吸收剂是目前研究热点。提出了以高容量、低能耗三级胺为吸收剂主剂，高动力学一级胺和高稳定环状胺为辅剂吸收剂方案；并形成了从实验室配方遴选、百标方时中试工艺匹配到每年万吨级规模工业装置运行优化的工程化开发体系。通过鼓泡吸收试验与吸收-再生循环试验对吸收剂进行快速筛选，初筛获得一种性能好的吸收剂配方，通过200 m~3/h中试与万吨级工业装置测试优化运行参数并完成工业验证。测试结果表明，开发的CEU型吸收剂CO_2脱除率达90%,最优再生热耗达2.42 GJ/t CO_2,在工业装置上完成了>700 h稳定运行。
With the increasingly serious greenhouse effect, chemical absorption method, as the most promising technology for decarbonization of coal-fired flue gas, has received wide attentionof China and abroad. The development of absorbents with low energy consumption, high stability and easy engineering application is a research hotspot at present. An absorbent scheme was proposed with high capacity and low energy consumption tertiary amine as the main absorbent, high kinetic primary amine and high stable cyclic amine as the auxiliary agent. An engineering development system has been formed, ranging from the selection of laboratory formula, the matching of 100 standard square meters per hour pilot energy-saving process to the optimization of the operation of 10 000 standard square meters per hour scale industrial devices. Through the quick screening of absorbents was carried out through bubbling absorption experiment and absorption-regeneration cycle experiment, and an absorbent formula with excellent performance was obtained through primary screening. Further, the energy-saving process was optimized and its operation stability was verified through the test of 200 m~3/h pilot plant and 10 000 tons of industrial plant. The test results show that the CO_2 removal rate of the CEU type absorbent developed in this study reaches 90%, and the optimal energy consumption reaches 2.42 GJ/t CO_2, and it has completed 700 hours of stable operation on the industrial device.

关键词(KeyWords)： 碳捕集;化学吸收;工程化开发;混合胺;燃煤烟气
carbon capture;chemical absorption;engineering development;mixed amine;coal-fired flue gas

Abstract:

Keywords:

基金项目(Foundation): 国家重点研发计划资助项目(2022YFB4101700);; 中央高校基本科研业务费专项资助项目(2022ZFJH004);; 国家能源集团2022年度科技创新资助项目(GJNY-22-99)

作者(Author): 徐冬,黄艳,宋俊朝,史晓宏,王涛,曾伟强,张帅,李水飞,方梦祥,高翔
XU Dong,HUANG Yan,SONG Junchao,SHI Xiaohong,WANG Tao,ZENG Weiqiang,ZHANG Shuai,LI Shuifei,FANG Mengxiang,GAO Xiang

DOI: 10.13226/j.issn.1006-6772.LC23120401

参考文献(References)：

• [1] World Resources Institute.World greenhouse gas emissions:2019[EB/OL].(2022-06-23)[2023-12-10].https://www.wri.org/data/world-greenhouse-gas-emissions-2019.
• [2] BRICKETT L,MUNSON R,LITYNSKI J U S.DOE/NETL large pilot-scale testing of advanced carbon capture technologies [J].Fuel,2020,268:117169.
• [3] 何卉，方梦祥，王涛，等.燃煤烟气化学吸收碳捕集系统分析与优化 [J].化工进展，2018,37(6):2406-2412.HE Hui,FANG Mengxiang,WANG Tao,et al.Analysis and optimization of post-combustion CO2 capture system based on chemical absorption [J].Chemical Industry and Engineering Progress,2018,37(6):2406-2412.
• [4] 马双忱，吕玉坤，路通畅，等.填料塔中氨水脱除模拟烟气中CO2的实验研究 [J].中国电机工程学报，2013,33(26):27-32.MA Shuangchen,LYU Yukun,LU Tongchang,et al.Experimental research on CO2 capture from simulated flues gas using ammonia solution in packed towers [J].Proceedings of the CSEE,2013,33(26):27-32.
• [5] 方梦祥，周旭萍，王涛，等.CO2化学吸收剂 [J].化学进展，2015,27(12):1808-1814.FANG Mengxiang,ZHOU Xuping,WANG Tao,et al.Solvent development in CO2 chemical absorption [J].Progress in Chemistry,2015,27(12):1808-1814.
• [6] 谢和平，刘虹，吴刚.中国未来二氧化碳减排技术应向CCU方向发展 [J].中国能源，2012,34(10):15-18.XIE Heping,LIU Hong,WU Gang.China′s carbon dioxide emissions technology should be developed in the direction of CCU [J].Energy of China,2012,34(10):15-18.
• [7] 徐燕洁.用于烟气CO2捕集的双胺类少水吸收剂性能研究 [D].杭州：浙江大学，2021.
• [8] 张新军，徐明海，唐建峰，等.MEA-AEP混合胺液捕集烟气中CO2试验 [J].环境工程，2018,36(1):71-76.ZHANG Xinjun,XU Minghai,TANG Jianfeng,et al.CO2 capture in flue gas experiment by mea-aep mixed amine solutions [J].Environmental Engineering,2018,36(1):71-76.
• [9] AROONWILAS A,VEAWAB A.Characterization andcomparison of the CO2 absorption performance into single and blended alkanolamines in a packed column [J].Industrial & Engineering Chemistry Research,2004,43(9):2228-2237.
• [10] 周旭萍.氨基酸盐和混合CO2吸收剂的综合特性研究 [D].杭州：浙江大学，2016.
• [11] AHMAD Z,KADIR N N A,BAHADORI A,et al.Optimization study on the CO2 and H2S removal in natural gas using primary,secondary,tertiary and mixed amine[C]//AIP conference proceedings.[S.l.]:AIP Publishing,2019.
• [12] NWAOHA C,SAIWAN C,TONTIWACHWUTHIKUL P,et al.Carbon dioxide (CO2) capture:Absorption-desorption capabilities of 2-amino-2-methyl-1-propanol (AMP),piperazine (PZ) and monoethanolamine (MEA) tri-solvent blends [J].Journal of Natural Gas Science and Engineering,2016,33:742-750.
• [13] 董文峰.基于低成本塑料填料和高效板式换热器的CO2化学吸收技术及工艺研究 [D].杭州：浙江大学，2022.
• [14] 刘珍珍.燃煤烟气二氧化碳捕集吸收剂的研究及工艺优化运行模拟 [D].杭州：浙江大学，2021.
• [15] WANG T,JENS K J.Oxidative degradation of AMP/MEA blends for post-combustion CO2 capture [J].Energy Procedia,2013,37:306-313.
• [16] MAZARI S A,ALI B S,JAN B M,et al.Thermal degradation of piperazine and diethanolamine blend for CO2 capture [J].International Journal of Greenhouse Gas Control,2016,47:1-7.
• [17] FREEMAN S A,DAVIS J,ROCHELLE G T.Degradation of aqueous piperazine in carbon dioxide capture[J].International Journal of Greenhouse Gas Control,2010,4(5):756-761.
• [18] ROCHELLE G T.Thermal degradation of amines for CO2 capture [J].Current Opinion in Chemical Engineering,2012,1(2):183-190.
• [19] 高涵，郭亚平，褚联峰，等.四乙烯五胺活化N-甲基二乙醇胺溶液吸收CO2 [J].化学工程，2011,39(9):30-33,65.GAO Han,GUO Yaping,CHU Lianfeng,et al.Absorption of CO2 into solution of N-methyldiethanolamine activated by tetraethylenetetramine [J].Chemical Engineering (China),2011,39(9):30-33,65.
• [20] HUEFFER S,SCHWAB P,FISCHER K,et al.Method for producing polyalkenyl succinimide products,novel polyalkenylsuccinimide products with improved properties,intermediate products:U.S.Patent 8263535[P].2012-09-11.
• [21] YU K,CURCIC I,GABRIEL J,et al.Apology:Recent advances in CO2 capture and utilization [J].ChemSusChem,2010,3(6):644.
• [22] FREDRIKSEN S B,JENS K J.Oxidative degradation of aqueous amine solutions of MEA,AMP,MDEA,pz:A review [J].Energy Procedia,2013,37:1770-1777.
• [23] 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.
• [24] LIU F,QI Z,FANG M,et al.Pilot test of water-lean solvent of 2-(ethylamino) ethanol,1-methyl-2-pyrrolidinone,and water for post-combustion CO2 capture[J].Chemical Engineering Journal,2023,459:141634.
• [25] 雷轩邈，王甫，朱先会，等.胺法碳捕集胺的降解与抑制方式研究进展[J].高校化学工程学报，2021,35(6):966-978.LEI XuaNmiao,WANG Fu,ZHU Xianhui,et al.Review on degradation and inhibition of amine from amine carbon capture processes [J].Journal of Chemical Engineering of Chinese Universities,2021,35(6):966-978.