赵敏楠,张佳音,张新妙,徐恒,栾金义,陆丁香,赵鹏宇,陈湘泽,武振康
ZHAO Minnan,ZHANG Jiayin,ZHANG Xinmiao,XU Heng,LUAN Jinyi,LU Dingxiang,ZHAO Pengyu,CHEN Xiangze,WU Zhenkang

• 1:中国矿业大学(北京)化学与环境工程学院
• 2:中石化(北京)化工研究院有限公司

摘要(Abstract)：

碳捕集转化一体化工艺能利用CO_2转化过程同步实现CO_2富液再生，有望降低碳捕集转化整体成本。为评价生物甲烷化与碳捕集耦合的可行性，首先，在填料塔中考察了以4.2 g/L NaHCO_3、6 g/L Na_2CO_3、微生物营养液配制的弱碱性吸收剂(pH=10)对模拟烟气中CO_2的吸收性能；其次，在厌氧瓶内利用生物甲烷化过程对CO_2富液开展5个周期的循环再生试验。结果表明，填料塔气体流量≤1.0 L/min时，随液体流量增加，所有试验组CO_2去除率逐渐上升并能稳定在80%以上，该填料塔液体流量宜≤0.9 L/min;不同气体流量(0.4～1.2 L/min)下填料塔体积总传质系数基本稳定在17～19 mol/(h·kPa·m~3);CO_2吸收导致吸收液中NaHCO_3增加、Na_2CO_3减少，二者变量比值在1.2～1.9。气体流量为0.6 L/min、液体流量为0.7 L/min时，在维持80%以上CO_2去除率的前提下，该弱碱性吸收剂可循环使用6次，此时活性组分CO_3~(2-)利用率达89.5%,形成的CO_2富液中总无机碳量为0.127 mol/L,pH为8.82,能为生物甲烷化微生物提供适宜的生长环境。CO_2富液循环生物再生试验表明，每次再生后的吸收剂CO_2吸收量基本稳定在69.6～78.6 mmol/L,且再生期间CH_4产生过程具有良好的重复性；再生试验后，Firmicutes、Actinobacteriota等耐碱性门水平细菌得到一定富集；氢营养型产甲烷菌在再生前后古菌属中占比均接近99%,但再生试验期间弱碱性环境导致Methanobrevibacter相对丰度降低了19.5%,unclassified＿f＿Methanobacteriaceae增加了18.7%。初步证实了碳捕集耦合生物甲烷化工艺的可行性。
It is expected that integrated carbon capture and conversion(iCCC) will reduce the overall cost of carbon capture & conversion by leveraging the CO_2 conversion process to simultaneously regenerate CO_2-rich solutions. To assess the feasibility of coupling biomethanation and carbon capture, the absorption performance of a slightly alkaline absorbent(pH=10) prepared with 4.2 g/L NaHCO_3, 6 g/L Na_2CO_3 and a microbial nutrient solution for CO_2 in simulated flue gas in a packed column was investigated. Second, the CO_2-rich solution was subjected to a five-cycle regeneration experiment using the biomethanation process in anaerobic bottles. The results show that in the flow-through mode, when the gas flow rate of packed column is ≤1.0 L/min, with the increase of liquid flow rate, CO_2 removal rates of all experimental groups gradually increase and can be stabilized above 80%, and the liquid flow rate of this packed column is suitable to be ≤ 0.9 L/min. Overall volumetric mass transfer coefficients of the packed column at different gas flow rates(0.4-1.2 L/min) are generally stable between 17-19 mol/(h·kPa·m~3). As a result of CO_2 absorption, NaHCO_3 in the absorption solution increases and Na_2CO_3 decreases, with a ratio between 1.2 and 1.9. Under the condition that the CO_2 removal rate is greater than 80%, the slightly alkaline absorbent can be recycled 6 times at a gas flow rate of 0.6 L/min and liquid flow rate of 0.7 L/min. The utilization rate of the active component CO_3~(2-) reaches 89.5%, and the total inorganic carbon(TIC) of the formed CO_2-rich solution is 0.127 mol/L at a pH of 8.82, creating an environment conducive to the growth of biomethanation microorganisms. The results of the cyclic experiments on the bio-regeneration of the CO_2-rich solution reveal that the absorbed CO_2 of the absorbent is basically stable in the range of 69.6-78.6 mmol/L after each regeneration and the CH_4 production is reproducible during the regeneration process. As a result of the regeneration experiment, alkali-resistant bacteria at the phylum level, such as Firmicutes and Actinobacteriota, are somewhat enriched. Approximately 99% of archaeal genera are dominated by hydrogenotrophic methanogens before and after regeneration, but the slightly alkaline environment during regeneration results in a 19.5% decrease in the relative abundance of Methanobrevibacter and a 18.7% increase in the relative abundance of unclassified＿ f＿Methanobacteriaceae, respectively. In conclusion, the above experimental results indicate the feasibility of biomethanation combined with carbon capture.

关键词(KeyWords)： 碳捕集转化一体化;吸收剂;CO_2富液;生物再生;生物甲烷化
integrated carbon capture and conversion(iCCC);absorbent;CO_2-rich solution;bio-regeneration;biomethanation

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金青年科学基金资助项目(51908547)

作者(Author): 赵敏楠,张佳音,张新妙,徐恒,栾金义,陆丁香,赵鹏宇,陈湘泽,武振康
ZHAO Minnan,ZHANG Jiayin,ZHANG Xinmiao,XU Heng,LUAN Jinyi,LU Dingxiang,ZHAO Pengyu,CHEN Xiangze,WU Zhenkang

DOI: 10.13226/j.issn.1006-6772.KD23121401

参考文献(References)：

• [1] 阳平坚，彭栓，王静，等.碳捕集、利用和封存(CCUS)技术发展现状及应用展望[J/OL].中国环境科学：1-15(2023-08-16)[2024-01-09].https://doi.org/10.19674/j.cnki.issn1000-6923.20230815.001.YANG Pingjian,PENG Shuan,WANG Jing,et al.Carbon Capture,Utilization and Storage (CCUS) technology development status and application prospects[J/OL].China Environmental Science:1-15(2023-08-16)[2024-01-09].https://doi.org/10.19674/j.cnki.issn1000-6923.20230815.001.
• [2] 国家统计局.中华人民共和国2022年国民经济和社会发展统计公报[J].中国统计，2023(3):12-29.
• [3] 刘克峰，刘陶然，蔡勇，等.二氧化碳捕集技术研究和工程示范进展[J/OL].化工进展：1-15(2023-11-03)[2024-01-09].https://doi.org/10.16085/j.issn.1000-6613.2023-0730.LIU Kefeng,LIU Taoran,CAI Yong,et al.Progress in research and engineering demonstration of CO2 capture technology[J/OL].Chemical Industry and Engineering Progress:1-15(2023-11-03)[2024-01-09].https://doi.org/10.16085/j.issn.1000-6613.2023-0730.
• [4] 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.
• [5] 余歌.混合吸收剂的沼气CO2化学吸收—再生特性研究[D].武汉：华中农业大学，2018.
• [6] 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.
• [7] FU Hongchen,YOU Fei,LI Hongru,et al.CO2 capture and in situ catalytic transformation[J].Frontiers in Chemistry,2019,7:525.
• [8] 纪龙，曾鸣.燃煤电厂CO2捕集与利用技术综述[J].煤炭工程，2014,46(3):90-92.JI Long,ZENG Ming.Review oncapture and utilization technology of carbon dioxide in coal-firea power plant[J].Coal Engineering,2014,46(3):90-92.
• [9] 陈云飞.CO2-钒酸盐电转化碳/钒基材料基础研究[D].北京：北京科技大学，2022.
• [10] 谢美连.新型“化学吸收-微藻转化”耦合的CO2再利用系统及优化[D].天津：天津大学，2018.
• [11] CHOI W,KIM G,LEE K.Influence of the CO2 absorbent monoethanolamine on growth and carbon fixation by the green alga Scenedesmus sp[J].Bioresource Technology,2012,120:295-299.
• [12] 邱依婷.基于废水资源化利用的“化学吸收-微藻转化”耦合CO2捕集工艺[D].天津：天津大学，2019.
• [13] 苗佳慧，王建城，代雅男，等.潮汐式嗜氢型甲烷化性能及其用于CO2富液再生可行性研究[J/OL].洁净煤技术：1-8(2023-08-17)[2024-01-09].http://kns.cnki.net/kcms/detail/11.3676.TD.20230817.0840.002.html.MIAO Jiahui,WANG Jiancheng,DAI Yanan,et al.Performance of tidal hydrogenotrophic methanation and its feasibility forregenerating CO2-loaded solutions[J/OL].Clean Coal Technology:1-8(2023-08-17)[2024-01-09].http://kns.cnki.net/kcms/detail/11.3676.TD.20230817.0840.002.html.
• [14] XU H,MIAO J,WANG J,et al.Integrated CO2 capture and co-nversion via H2-driven CO2 biomethanation:Cyclic performance and microbial community response[J].Bioresource Technology,2023,393:130055.
• [15] 侯海龙，王秀林，侯建国，等.甲烷作为储氢介质产业模式下的关键技术分析[J].现代化工，2023,43(6):12-17.HOU Hailong,WANG Xiulin,HOU Jianguo,et al.Analysis on key technologies under industry mode with methane as hydrogen storage medium[J].Modern Chemical Industry,2023,43(6):12-17.
• [16] IRINI ANGELIDAKI,WENDY SANDERS.Assessment of the anaerobic biodegradability of macropollutants[J].Reviews in Environmntal Science and Biotechnology,2004,3(2):117-129.
• [17] MORITA M,MALVANKAR N S,FRANKS A E,et al.Potential for direct interspecies electron transfer in methanogenic wastewater digester aggregates[J].mBio,2011,2(4):10.1128.
• [18] 徐恒，汪翠萍，颜锟，等.颗粒型厌氧生物膜改善高氢分压下丙酸降解抑制研究[J].中国环境科学，2016,36(5):1435-1441.XU Heng,WANG Cuiping,YAN Kun,et al.Granule-based anaerobic biofilm enhances propionic acid degradation under high H2 partial pressure[J].China Environmental Science,2016,36(5):1435-1441.
• [19] 罗洋，盛宇星，曹宏斌.填料塔中Na2CO3吸收高浓度H2S的传质特性[J].环境工程学报，2014,8(4):1561-1566.LUO Yang,SHENG Yuxing,CAO Hongbin.Mass transfer characteristics of absorption of high concentration of H2S by sodiumcarbonate in packed column[J].Chinese Journal of Environmental Engineering,2014,8(4):1561-1566.
• [20] DA ROSA G M,MORAES L,CARDIAS B B,et al.Chemical absorption and CO2 biofixation via the cultivation of Spirulina in semicontinuous mode with nutrient recycle[J].Bioresource Technology,2015,192:321-327.
• [21] SUN Z,ZHANG D,YAN C,et al.Promotion of microalgal biomass production and efficient use of CO2 from flue gas by monoethanolamine[J].Journal of Chemical Technology & Biotechnology,2015,90(4):730-738.
• [22] 林冠屹，朱春英，付涛涛，等.微通道内MEA/MDEA混合溶液吸收CO2的传质特性[J].化工学报，2018,69(11):4675-4682.LIN Guanyi,ZHU Chunying,FU Yaotao,et al.Mass transfer performance of CO2 absorption into aqueous mixture of monoethanolamine with N-methyldiethanolamine in microchannel[J].CIESC Journal,2018,69(11):4675-4682.
• [23] 王乐萌.新型复配醇胺溶液捕集CO2过程的吸收特性研究[D].北京：华北电力大学，2018.
• [24] 唐忠利，赵行健，刘伯潭，等.规整填料塔中氨水吸收CO2的体积总传质系数[J].化工学报，2012,63(4):1102-1107.TANG Zhongli,ZHAO Xingjian,LIU Botan,et al.Volumetric overall mass transfer coefficients of CO2 absorption into aqua ammoniain structured packed column[J].CIESC Journal,2012,63(4):1102-1107.
• [25] 唐建峰，桑伟，毕逢东，等.多因素对散堆填料吸收塔内有效传质面积的影响[J].石油学报(石油加工),2022,38(5):1148-1154.TANG Jianfeng,SANG Wei,BI Fengdong,et al.Different factors affecting effective mass transfer area of random packing absorption tower[J].Acta Petrolei Sinica(Petroleum Processing Section),2022,38(5):1148-1154.
• [26] GONZáLEZ-LóPEZ C V,ACIéN FERNáNDEZ F G,FERNá-NDEZ-SEVILLA J M,et al.Development of a process for efficient use of CO2 from flue gases in the production of photosynthetic microorganisms[J].Biotechnology and Bioengineering,2012,109(7):1637-1650.
• [27] ZHANG Q,WU Y,LUO J,et al.Enhanced volatile fatty acids production from waste activated sludge with synchronous phosphorus fixation and pathogens inactivation by calcium hypochlorite stimulation[J].Science of the Total Environment,2020,712:136500.
• [28] 李鹏飞.农业秸秆与市政污泥共混厌氧消化的协同作用及强化机制[D].南京：东南大学，2021.
• [29] RIVIERE D,DESVIGNES V,PELLETIER E,et al.Towards the definition of a core of microorganisms involved in anaerobic digestion of sludge[J].The ISME Journal,2009,3(6):700-714.
• [30] JANG H M,KIM J H,HA J H,et al.Bacterial and methanogenic archaeal communities during the single-stage anaerobic digestion of high-strength food wastewater[J].Bioresource Technology,2014,165:174-182.
• [31] WARD L M,BERTRAN E,JOHNSTON D T.Draft genome sequence of Desulfovibrio sulfodismutans ThAc01,a heterotrophic sulfur-disproportionating member of the Desulfobacterota[J].Microbiology Resource Announcements,2020,9(13):e00202-20.
• [32] CHUENCHART W,LOGAN M,LEELAYOUTHAYOTIN C,et al.Enhancement of food waste thermophilic anaerobic digestion through synergistic effect with chicken manure [J].Biomass Bioenergy,2020,136:105541.
• [33] 王艳发.祁连山水合物钻探区冻土甲烷代谢特征及功能微生物研究[D].北京：中国地质大学(北京),2020.
• [34] LI C,HAO L,LYU F,et al.Syntrophic acetate-oxidizing microbial consortia enriched from full-scale mesophilic food waste anaerobic digesters showing high biodiversity and functional redundancy[J].Msystems,2022,7(5):e00339-22.
• [35] JIANG H,HAO W,LI Y,et al.Biological methanation of H2 and CO2 in a continuous stirred tank reactor[J].Journal of Cleaner Production,2022,370:133518.
• [36] WANG Z,WANG S,HU Y,et al.Distinguishing responses of acetoclastic and hydrogenotrophic methanogens to ammonia stress in mesophilic mixed cultures[J].Water Research,2022,224:119029.