Article(id=1324806228748152976, tenantId=1146029695717560320, journalId=1205116786560364546, issueId=1324806227083002341, articleNumber=null, orderNo=null, doi=10.16236/j.cnki.nrjxb.202506061, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1740499200000, receivedDateStr=2025-02-26, revisedDate=1748793600000, revisedDateStr=2025-06-02, acceptedDate=null, acceptedDateStr=null, onlineDate=1793788018642, onlineDateStr=2026-11-04, pubDate=1764000000000, pubDateStr=2025-11-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793788018642, onlineIssueDateStr=2026-11-04, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793788018642, creator=13701087609, updateTime=1793788018642, updator=13701087609, issue=Issue{id=1324806227083002341, tenantId=1146029695717560320, journalId=1205116786560364546, year='2025', volume='43', issue='6', pageStart='481', pageEnd='568', issueExtLink='null', onlineDate='null', pubDate='1764000000000', pubDateStr='2025-11-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1793788018246, creator='13701087609', updateTime=1793959617886, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1325525968575812368, tenantId=1146029695717560320, journalId=1205116786560364546, issueId=1324806227083002341, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1325525968575812369, tenantId=1146029695717560320, journalId=1205116786560364546, issueId=1324806227083002341, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=549, endPage=558, ext={EN=ArticleExt(id=1324806228915925137, articleId=1324806228748152976, tenantId=1146029695717560320, journalId=1205116786560364546, language=EN, title=Experimental and mechanistic study of high-efficiency two-phase solvents for carbon capture in marine diesel engines, columnId=null, journalTitle=Transactions of CSICE, columnName=null, runingTitle=null, highlight=null, articleAbstract=

The extensive emission of carbon dioxide,leading to global warming,has attracted widespread attention. Excessive energy consumption for regeneration has become the main reason limiting the application of carbon capture systems(CCS) on ships. In this study,tailored to the specific needs of marine diesel engines,a novel two-phase absorption system,3-methylaminopropylamine-sulfolane-water(MAPA-SFL-H2O) was constructed. Experiments were conducted using simulated ship exhaust with a gas flow rate of 1000mL/min. The absorption,desorption,and cycling performance of the two-phase absorbent were investigated under various conditions,including different absorbent composition ratios,absorption temperatures(30—60℃),CO2 volume fraction(3%—5%),and impurity gases(SO2 and NO),using a bubbling device and titration setup. The results indicate that the absorption rate of the MAPA-SFL-H2O two-phase absorbent under the different CO2 volume fraction conditions of ship exhaust is higher than that of monoethanolamine(MEA). When the mass ratio of the absorbents is 3: 3:4,the system exhibites its optimal performance. Compared to MEA of equal mass,the cyclic load is increased by 72.3%,while the energy consumption for regeneration is reduced by 28.4 %. Carbon-13 nuclear magnetic resonance(13CNMR) detection results show that the primary amine groups in MAPA are the main CO2 carrier,and the secondary amine groups are involved in proton transfer. The phase change of the absorbent is influenced by the CO2 load. An increase in CO2 load promotes the precipitation of SFL to form a lean phase,which facilitates two-phase separation and significantly reduces the energy consumption for regeneration.

, authors=Song Zhou, Zhaoshan Huang, Hongyuan Xi, Ze Hao, Taiyu You, authorsList=Song Zhou, Zhaoshan Huang, Hongyuan Xi, Ze Hao, Taiyu You, authorCompany=null, correspAuthors=Hongyuan Xi, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1324806233634517172, articleId=1324806228748152976, tenantId=1146029695717560320, journalId=1205116786560364546, language=CN, title=船舶柴油机碳捕集用高效双相溶剂的试验与机理研究, columnId=null, journalTitle=内燃机学报, columnName=, runingTitle=null, highlight=null, articleAbstract=

CO2大量排放所导致的全球变暖效应,已经引起了广泛关注.再生能耗过高成为限制船舶碳捕集系统(CCS)应用的主要原因.针对船舶柴油机特殊需求,构建了3-甲氨基丙胺-环丁砜-水(MAPA-SFL-H2O)新型两相吸收体系.试验模拟船舶废气,气体流量为1000mL/min,在不同吸收剂组分比例、吸收温度(30~60℃)、CO2体积分数(3%~5%)以及杂质气体(SO2和NO)等条件下使用鼓泡装置和滴定装置研究两相吸收剂的吸收、解吸和循环性能.结果表明:MAPA-SFL-H2O两相吸收剂在船舶尾气不同CO2体积分数条件下的吸收速率高于乙醇胺(MEA),在吸收剂质量比为3:3:4时性能最佳,循环负载相较同质量的MEA提高72.3%,再生能耗降低28.4%.碳-13核磁共振(13CNMR)检测显示,MAPA的伯胺基团是主要CO2载体,仲胺基团参与质子转移.吸收剂的相变受CO2负载影响,负载升高使SFL析出形成贫相,促进分相,显著降低再生能耗.

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周松,博士,教授,.

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席鸿远,博士,助理研究员,.
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figureFileBig=zHanZaKCloWEzls22KxN8g==, tableContent=null), ArticleFig(id=1325514545749439339, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1324806228748152976, language=CN, label=图15, caption=吸收剂质量比为3∶3∶4时吸收过程NMR检测结果, figureFileSmall=zmv/zgtLY7EgohsWFn0AGQ==, figureFileBig=zHanZaKCloWEzls22KxN8g==, tableContent=null), ArticleFig(id=1325514545829131116, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1324806228748152976, language=EN, label=Fig.16, caption=detection results after phase separation with the absorbent mass ratio of 3∶3∶4, figureFileSmall=WhPYKHccBTXJrFf8kz1m4w==, figureFileBig=ZytjF2QdZMCHBHddFOuksQ==, tableContent=null), ArticleFig(id=1325514545908822893, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1324806228748152976, language=CN, label=图16, caption=吸收剂质量比为3∶3∶4时分相后检测结果, figureFileSmall=WhPYKHccBTXJrFf8kz1m4w==, figureFileBig=ZytjF2QdZMCHBHddFOuksQ==, tableContent=null), 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Parameters of reagents

, figureFileSmall=null, figureFileBig=null, tableContent=
参数化学式质量分数%生产厂家
3-甲氨基丙胺C4H12N299上海阿拉丁有限公司
1-正丙醇C3H8O99上海阿拉丁有限公司
1-正丁醇C4H10O99上海阿拉丁有限公司
1-正戊醇C5H12O99上海阿拉丁有限公司
环丁砜C4H8O2S99上海阿拉丁有限公司
), ArticleFig(id=1325514546210812785, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1324806228748152976, language=CN, label=表1, caption=

试剂参数

, figureFileSmall=null, figureFileBig=null, tableContent=
参数化学式质量分数%生产厂家
3-甲氨基丙胺C4H12N299上海阿拉丁有限公司
1-正丙醇C3H8O99上海阿拉丁有限公司
1-正丁醇C4H10O99上海阿拉丁有限公司
1-正戊醇C5H12O99上海阿拉丁有限公司
环丁砜C4H8O2S99上海阿拉丁有限公司
), ArticleFig(id=1325514546294698866, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1324806228748152976, language=EN, label=Tab.2, caption=

Parameters of gases

, figureFileSmall=null, figureFileBig=null, tableContent=
参数化学式质量分数%生产厂家
二氧化碳CO299哈尔滨黎明煤气有限公司
氮气N299哈尔滨黎明煤气有限公司
), ArticleFig(id=1325514546378584947, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1324806228748152976, language=CN, label=表2, caption=

气体参数

, figureFileSmall=null, figureFileBig=null, tableContent=
参数化学式质量分数%生产厂家
二氧化碳CO299哈尔滨黎明煤气有限公司
氮气N299哈尔滨黎明煤气有限公司
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船舶柴油机碳捕集用高效双相溶剂的试验与机理研究
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周松 , 黄照珊 , 席鸿远 , 郝泽 , 游泰宇
内燃机学报 | 2025,43(6): 549-558
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内燃机学报 | 2025 , 43 (6) : 549 -558
船舶柴油机碳捕集用高效双相溶剂的试验与机理研究
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周松 , 黄照珊, 席鸿远 , 郝泽, 游泰宇
作者信息
  • 哈尔滨工程大学动力与能源工程学院,哈尔滨 150001
通讯作者:
席鸿远,博士,助理研究员,.
作者简介:

周松,博士,教授,.

Experimental and mechanistic study of high-efficiency two-phase solvents for carbon capture in marine diesel engines
Song Zhou , Zhaoshan Huang, Hongyuan Xi , Ze Hao, Taiyu You
Affiliations
  • Department of Power and Energy Engineering,Harbin Engineering University,Harbin 150001,China
出版时间: 2025-11-25 doi: 10.16236/j.cnki.nrjxb.202506061
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CO2大量排放所导致的全球变暖效应,已经引起了广泛关注.再生能耗过高成为限制船舶碳捕集系统(CCS)应用的主要原因.针对船舶柴油机特殊需求,构建了3-甲氨基丙胺-环丁砜-水(MAPA-SFL-H2O)新型两相吸收体系.试验模拟船舶废气,气体流量为1000mL/min,在不同吸收剂组分比例、吸收温度(30~60℃)、CO2体积分数(3%~5%)以及杂质气体(SO2和NO)等条件下使用鼓泡装置和滴定装置研究两相吸收剂的吸收、解吸和循环性能.结果表明:MAPA-SFL-H2O两相吸收剂在船舶尾气不同CO2体积分数条件下的吸收速率高于乙醇胺(MEA),在吸收剂质量比为3:3:4时性能最佳,循环负载相较同质量的MEA提高72.3%,再生能耗降低28.4%.碳-13核磁共振(13CNMR)检测显示,MAPA的伯胺基团是主要CO2载体,仲胺基团参与质子转移.吸收剂的相变受CO2负载影响,负载升高使SFL析出形成贫相,促进分相,显著降低再生能耗.

船舶柴油机  /  碳捕集  /  3-甲氨基丙胺  /  两相吸收剂

The extensive emission of carbon dioxide,leading to global warming,has attracted widespread attention. Excessive energy consumption for regeneration has become the main reason limiting the application of carbon capture systems(CCS) on ships. In this study,tailored to the specific needs of marine diesel engines,a novel two-phase absorption system,3-methylaminopropylamine-sulfolane-water(MAPA-SFL-H2O) was constructed. Experiments were conducted using simulated ship exhaust with a gas flow rate of 1000mL/min. The absorption,desorption,and cycling performance of the two-phase absorbent were investigated under various conditions,including different absorbent composition ratios,absorption temperatures(30—60℃),CO2 volume fraction(3%—5%),and impurity gases(SO2 and NO),using a bubbling device and titration setup. The results indicate that the absorption rate of the MAPA-SFL-H2O two-phase absorbent under the different CO2 volume fraction conditions of ship exhaust is higher than that of monoethanolamine(MEA). When the mass ratio of the absorbents is 3: 3:4,the system exhibites its optimal performance. Compared to MEA of equal mass,the cyclic load is increased by 72.3%,while the energy consumption for regeneration is reduced by 28.4 %. Carbon-13 nuclear magnetic resonance(13CNMR) detection results show that the primary amine groups in MAPA are the main CO2 carrier,and the secondary amine groups are involved in proton transfer. The phase change of the absorbent is influenced by the CO2 load. An increase in CO2 load promotes the precipitation of SFL to form a lean phase,which facilitates two-phase separation and significantly reduces the energy consumption for regeneration.

marine diesel engine  /  carbon capture  /  3-methylaminopropylamine(MAPA)  /  two-phase absorbent
周松, 黄照珊, 席鸿远, 郝泽, 游泰宇. 船舶柴油机碳捕集用高效双相溶剂的试验与机理研究. 内燃机学报, 2025 , 43 (6) : 549 -558 . DOI: 10.16236/j.cnki.nrjxb.202506061
Song Zhou, Zhaoshan Huang, Hongyuan Xi, Ze Hao, Taiyu You. Experimental and mechanistic study of high-efficiency two-phase solvents for carbon capture in marine diesel engines[J]. Transactions of CSICE, 2025 , 43 (6) : 549 -558 . DOI: 10.16236/j.cnki.nrjxb.202506061
近年来,温室气体(GHG)排放持续升高引发的全球变暖问题已经引起了广泛关注[1-2],CO2是导致全球变暖的主要因素,其对全球供暖失衡的贡献占比为66%[3].在众多GHG排放源中,交通运输行业占据了重要位置,其中海运承担了全球90%的贸易运输任务[4].海运业每年排放的CO2约为1.0×1012kg,占全球GHG排放总量的3%[5].根据预测,到2050年,船舶GHG排放可能比2012年增加250%,其中CO2排放将增至1.6×1012kg[6].因此,海洋环境保护委员会(MEPC)通过了国际海事组织(IMO)的初步战略计划[7],即到2050年,船舶GHG排放比2008年至少减少50%.此外,MEPC在2023年7月修订了GHG减排战略,要求不考虑国情的条件下在2050年实现近零排放[8],实现这一强制措施对航运业是一项颇具挑战的目标.
提升船舶柴油机能效可减少单位运输量的碳排放,但仅靠这一措施不足以达到接近零排放的目标.使用零碳或碳中性燃料能够大幅度地降低碳排放,但需配套基础设施并对发动机进行改造,目前无法实现广泛应用.碳捕集系统(CCS)在陆基已有实际应用且较为成熟[9],CCS适用于CO2低分压的情况,能够满足船舶减排战略[10].MEPC已经认识到船上CCS在减少GHG排放方面的潜力,考虑将其纳入IMO法规[11].在CCS技术中,一般先应用CO2分离捕集技术从船舶排放的废气中提取CO2,然后对其进行压缩液化并存储,最终卸载至专业设施进行处理或封存.在已经发展的CO2分离捕集技术中,常见的方法有化学吸收法、吸附分离法、膜分离法和低温蒸馏法[12].采用乙醇胺(MEA)等有机胺的化学吸收法是当前应用最广泛且技术最成熟的CO2捕集方法.然而,高能耗的再生过程是限制该技术进一步推广使用的主要原因[13].MEA吸收剂的再生过程需要消耗的能量占整个碳捕集操作成本的60%~80%[14].由于船舶运行的经济性和可利用空间等因素限制,低能耗、高捕集效率的CO2捕集技术才是实现船舶尾气CO2减排的急需技术.
在CO2捕集技术的研究中,相变吸收剂(PCAs)因其在吸收CO2后能够发生相变分层的特性而受到关注;这种特性可显著减少吸收液的再生体积,进而降低能耗[15].被用作碳捕集的胺吸收剂种类较多,3-甲氨基丙胺(MAPA)作为一种含有伯胺和仲胺基团的二胺类吸收剂,因其高吸收速率和单个胺基上的高CO2负载能力而备受关注[16].研究[17]表明,MAPA-甲基二乙醇胺(MEDA)再生速率比同质量分数的MEA溶剂提高了46%,且循环负载达到了31.29mg/kg,MAPA在相变溶剂中有助于降低再生能耗.此外,MAPA适用于低分压CO2捕集,更适用于船舶发动机低分压CO2的处理[18].目前,关于胺混合分相剂形成两相吸收剂的研究主要针对高分压的CO2进行处理,适用于船舶柴油机尾气低分压CO2捕集的两相吸收剂研究则较少.
综合考虑船舶空间有限、成本控制以及船舶废气中CO2低分压特性等特殊应用条件,笔者提出了一种适用于船舶尾气不同CO2体积分数条件下的低解吸能耗、高捕集效率和高速分相的两相吸收剂.结合实际应用场景,通过吸收试验筛选和复配得到了MAPA-环丁砜(SFL)-H2O两相吸收剂,使用鼓泡装置和滴定装置研究两相吸收剂的吸收、解吸和循环性能,以及不同试验条件(吸收温度、CO2体积分数)对吸收剂性能的影响,通过碳-13核磁共振(13CNMR)谱分析了分相后贫、富相构成及控制吸收剂相变的主要因素,以期为船舶碳捕集的吸收剂开发提供参考.
表1为试验用试剂信息,表2为试验用气体参数.
两相吸收剂筛选过程使用的有机溶剂质量分数为30%,随后与质量分数为30%的MAPA复配,其余为水,共50g.溶剂筛选过程的气体流量为1000mL/min,鼓泡120min(体积分数20%的CO2和80%的N2).在单轮吸收试验和循环吸收试验中使用体积分数为5%的CO2和95%的N2,吸收温度为40℃.当CO2出口体积分数为4.6%时停止吸收试验.在每次吸收试验结束和开始时使用纯N2对整个吸收系统进行吹扫.图1为吸收试验台架示意.
在吸收过程中,废气中的N2经过反应器时并不会与吸收剂发生反应,因而N2在反应器进/出口的流量保持不变,变化的仅为CO2或其他与吸收剂发生反应的气体组分.CO2吸收速率、出/入口气体摩尔流量计算式可表示为
rabs(t)=qCO2, in−qCO2, out
qCO2, out=[QN2/(1−CCO2, out)×CCO2, out]/(Vm×60)
qCO2, in=QCO2,inVm×60
式中:rabs(t)为t时刻吸收剂对CO2的吸收速率;qCO2, in为吸收试验反应器入口CO2气体摩尔流量;qCO2, out为反应器出口CO2气体摩尔流量;CCO2, out为气体检测仪记录的CO2体积分数;Vm为气体摩尔体积,取值为24.7L/mol(温度为25℃、压力为0.1MPa);QN2和QCO2,in分别为N2和CO2的质量流量.
0~t时刻内吸收剂对CO2的负载可表示为
R(t)=∑t=0n[rabs(t)×Δt]
R′(t)=1n×∑t=0n[rabs(t)×Δt]
式中:R(t)为0~t时刻内吸收剂CO2负载;R′(t)为0~t时刻内吸收剂CO2相对负载;n为吸收剂溶质物质的量;Δt为气体检测仪数据间隔时间.
在解吸试验中,反应器内通过磁力转子(转速为1000r/min)增强扰动以提高解吸效率.富液在120℃下加热解吸,释放CO2.富液负载经滴定测定,解吸过程中每30min取样一次,每次取2.0mL样品,其中1.5mL进行滴定分析.先向样品瓶中加入0.5mL样品,用去离子水清洗滴管3次并合并清洗液以避免残留;随后在锥形瓶中加入过量稀盐酸进行滴定,以3次结果平均值计算解吸容量.解吸结束后取最终样品,并将贫液与新鲜吸收剂混合用于后续循环吸收试验.
采用布鲁克400MHz核磁共振仪对分子进行NMR分析.同时以质量比m(MAPA)∶m(SFL)∶m(H2O)为3∶3∶4配制吸收剂共100g,吸收温度设为40℃,气体流量为1000mL/min,通入体积分数为5%的CO2和N2混合气.对分相前负载CO2全部吸收剂及分相后吸收剂贫相和富相分别进行取样检测.在吸收试验中,分别在0、10、20、40和60min的时间点采集样本进行分析.为实现信号锁定,将样品溶解于氘水(D2O)再进行检测.
再生能耗主要包含加热吸收剂到解吸温度的显热(Qsen)、解吸CO2过程的反应热(Qreac)、再生过程蒸发气体带走的汽化潜热(Qlatent)及热损失(Qlose)共4部分.由于热损失在解吸过程的能耗占比小于5%,可忽略此部分能量,再生能耗组成[19]可表示为
Qregen=Qsen+Qlatent+Qreac
Qsen=(cpmsolΔT)/mCO2
Qreac=−ΔHreacMCO2
Qlatent=ΔmwHvapΔmCO2
式中:cp为吸收剂富液的定压比热容;msol为吸收剂富液质量;ΔT为吸收剂贫、富液体温差,取值为10K;mCO2为吸收剂吸收CO2的质量;ΔHreac为反应焓,笔者使用的反应焓数据参见文献[20];MCO2为CO2摩尔质量,其值为44g/mol;Δmw为蒸发的水蒸汽物质的量;Hvap为水的蒸发潜热;ΔmCO2为富液解吸量.
在相变吸收剂的筛选和复配试验中所用分相剂的相关参数见表1,MAPA分别和不同分相剂复配后再通入体积分数为5%的CO2,直到试验达到平衡.图2为4种有机溶剂的负载.1-丁醇、1-丙醇和1-戊醇复配吸收剂的CO2负载分别为1.00、0.98和0.97mol/mol,而SFL复配的吸收剂负载为0.87mol/ mol.3种醇复配得到的吸收剂CO2负载差值小,但均高于SFL.醇类会与有机胺和CO2发生反应使吸收剂整体负载升高,反应方程如反应R(1)所示[21].此外,3种醇形成的富相占比与SFL不同,3种醇的富相占比由高到低依次为1-丙醇(33%)、1-戊醇(30%)和1-丁醇(27%),SFL作为分相剂的富相占比为79%,比例显著高于其他3种醇,其原因是负载CO2后,SFL复配吸收剂的产物和水都集中在上相,而3种醇的复配吸收剂产物都在上相,水集中在下相,表明SFL作为双相溶剂的分相剂形成的富相黏度低于3种醇的黏度.
ROH+CO2+R1R2NH⇌    R1R2NH2++ROCOO−
图3为4种相变吸收剂的饱和蒸气压.由于3种醇会参与吸收反应,在试验过程中,3种醇在负载后吸收剂损失较高;此外,3种醇的饱和蒸气压随温度的升高而升高,而温度对SFL的饱和蒸气压影响较小.这是由于其化学结构稳定、分子间作用力较弱且对温度变化敏感性低.SFL的环丁烷环和硫原子构成的分子结构提供了高热稳定性和化学稳定性,减少了分子间的不稳定相互作用,从而维持了较低且稳定的蒸气压.饱和蒸气压越高则吸收剂的物理蒸发也越高,SFL的饱和蒸气压始终维持在较低水平,作为分相剂的的吸收剂损失也较少.MAPA-SFL-H2O的吸收剂在化学稳定性上更优,不易降解;而传统吸收剂MEA在长期运行中可能因氧化等化学反应而产生降解,导致吸收剂损失[22],因而笔者最终选定SFL作为有机溶剂.
两相吸收剂的贫、富相占比变化直接影响进入解吸塔的富液体积,富相体积减少则单位体积富液中的产物量越高,有利于过程能耗的降低.笔者以吸收剂富相体积为基准,对吸收剂负载(单位为mol/L)进行分析.调整有机溶剂质量占比为10%~40%,吸收剂的贫、富相占比和负载如图4所示.SFL质量比由20%升高到30%和40%,在负载CO2形成两相后的富相占比分别为90%、79%和70%,两相吸收剂负载CO2后的富相占比随SFL质量比升高而降低,贫相占比与之相反,富相占比较小的吸收剂更具有节能潜力;但不同的贫、富相占比可能会对两相吸收剂的捕集性能产生影响.在吸收剂组分质量比m(MAPA):m(SFL):m(H2O)为3∶1∶6的条件下,吸收剂在负载CO2后并没有变为两相,SFL质量占比为10%时,吸收剂富液可以和SFL互溶.随着SFL质量占比的增加,溶液中的相界面变得更加明显.这是因为SFL作为一种极性溶剂,其亲水性和亲油性特性在一定比例下对溶质的溶解度和分配产生显著作用[23].当SFL的质量占比较高时,会增强富相的极性,从而影响CO2在贫相与富相之间的分配平衡,导致溶质更多地分配到富相中,进而影响分相的效率与稳定性.相反,SFL质量占比降低时,贫相的溶解能力可能增强,导致溶质更多地分配到贫相中,因而吸收剂配比中的SFL质量占比是分相的影响因素.
图5为不同吸收剂的负载和吸收速率随时间变化.由图5(a)可知,4种质量比的吸收剂负载约为1.0mol/mol,显著高于同质量分数的MEA负载(0.5mol/mol).吸收剂的最大CO2负载会随着吸收剂中SFL的质量比增加而降低.其中,质量比为3∶1∶6的吸收剂负载最高为1.015mol/mol,质量比为3∶4∶3的吸收剂负载为0.970mol/mol.图5(b)中,在整个吸收过程中两相吸收剂的吸收速率均高于MEA,两相吸收剂SFL质量占比为20%、30%和40%的吸收速率曲线存在拐点,是由于负载升高后反应产物生成量增加,吸收剂中SFL的溶解度下降,析出的SFL聚集在反应器底部,导致吸收剂发生分相形成两相;反应产物富集在上相使富相黏度升高,阻碍了CO2进入液相,减缓了传质速率,导致吸收速率大幅下降,质量比为3∶1∶6的吸收剂和MEA未变为两相,不存在拐点.在相同CO2负载条件下SFL占比的升高还会使吸收剂分相的时间提前,可促进分相,减少分相时间,同时,SFL占比的升高还降低了富相体积,也更有利于再生能耗的降低.综上可知,随着SFL占比增加,体系的吸收速率在负载较高时会出现拐点,这是由于分相和液相黏度增加导致传质效率下降的结果.
吸收剂的解吸性能影响吸收剂的再生能耗.图6为不同质量比条件下两相吸收剂和MEA(m(MEA):m(SFL):m(H2O))为3∶0∶7的解吸效率和解吸容量.质量比为3∶2∶5的吸收剂富液解吸容量最高为0.59mol/mol,3∶3∶4和3∶4∶5两种质量比的吸收剂解吸容量分别为0.50mol/mol和0.44mol/mol,3种相变吸收剂的富液解吸容量均高于MEA的解吸容量(0.35mol/mol).SFL质量占比升高使富相体积减少,同时也降低了吸收剂的解吸容量和解吸效率,MEA吸收剂的解吸效率为71%,高于相变吸收剂,3种质量比的吸收剂富液解吸效率分别为58%、49%和43%.两相吸收剂的解吸效率低于MEA,但是相同质量分数的吸收剂解吸容量高于MEA,表明在船舶航行过程中,所需携带的吸收剂质量可相对减少.
此外,质量比为3∶4∶3的吸收剂在解吸试验后得到的贫液与剩余的贫相混合,不能恢复为单相.说明在此SFL质量比下解吸容量和解吸效率较低,吸收剂中部分氨基甲酸酯没有分解,解吸后的贫液CO2负载较高.此时混合后的吸收剂贫液对SFL的溶解度相对较低,而贫相中的SFL质量高于其他组分,不足以使吸收剂各组分互溶,因而吸收剂仍保持两相,组分吸收剂不具备循环能力.
循环负载代表吸收剂在完成一个循环后的捕集能力,相同质量分数的吸收剂循环负载越高则所需的吸收剂质量越少,在捕集相同质量的CO2时循环负载越高的吸收剂循环次数越少,从而能降低实际应用过程中的系统运行能耗.笔者以质量比为3∶2∶5和3∶3∶4的吸收剂进行循环试验,如图7所示.在吸收过程中,并非所有的MAPA都参与反应,未反应的MAPA会逐渐积累.在解吸过程中,形成的氨基甲酸酯不能完全解吸,导致富液和贫液的负载随循环次数的增加而上升.随循环次数增加,循环负载最终会稳定在一个值.具体而言,吸收剂质量比为3∶2∶5时,循环负载最终稳定为0.64mol/mol;而吸收剂质量比为3∶3∶4时,循环负载最终稳定为0.56mol/ mol.此外,吸收剂配比中环丁砜的质量占比增加会导致循环负载降低.与MEA吸收剂相比,这两种配比的吸收剂循环负载分别提高了96.8%和72.3%.
再生能耗是碳捕集过程中能量消耗主体,直接影响碳捕集系统的整体运行成本.为明确解吸过程中各部分能耗对降低再生能耗的影响,分别计算两种不同质量比吸收剂的反应热、溶剂显热和潜热,并与MEA吸收剂进行对比,如图8所示.MAPA-SFL-H2O双相吸收剂的节能贡献主要来自于显热和潜热,两种富液的反应热均低于MEA,但相差不大,由于吸收剂质量比中SFL的质量升高会导致富相体积及富相中水的质量同时减小,两种质量比吸收剂的显热相较于MEA降低了70%以上,吸收剂显热降低主要原因为富集液体积减小,分相后生成的产物比热低于水.富液体积的减少也降低了潜热,两种质量比的潜热相较于MEA分别降低了17.3%和27.3%.相较于MEA吸收剂的再生能耗(3.80MJ/kg CO2),两种不同质量比的吸收剂都显示出显著的能耗降低.质量比为3∶2∶5的吸收剂再生能耗为3.80MJ/kg CO2,比MEA吸收剂的能耗减少了25.8%;质量比为3∶3∶4的吸收剂再生能耗为2.72MJ/kg CO2,比MEA吸收剂的能耗降低了28.4%.
在吸收剂中,MAPA、SFL和H2O之间不会发生化学反应,可通过合理调整水分、溶剂与吸收剂的比例,确保吸收体系性能的稳定性.实际工程操作中,外排的尾气中水分可以通过除雾器进行处理,吸收剂中的水分变化可通过系统运行过程中吸收剂和水分的补偿模块进行调整,从而保证系统运行性能.
笔者开发的两相吸收剂应用对象为船舶柴油机,船舶尾气中的CO2体积分数较低(3%~6%).为研究MAPA-SFL-H2O吸收剂对低分压CO2的捕获性能,测试了质量比为3∶3∶4吸收剂在不同CO2体积分数下的负载和吸收速率,如图9所示.由图9(a)可知,CO2体积分数的升高不仅会使吸收剂达到试验终点的时间提前,还会使吸收剂的负载有所升高,在4种CO2体积分数条件下的负载分别为0.983、0.996、1.015和1.032mol/mol.CO2分压的升高会使吸收剂在达到平衡时的反应向正向移动.图9(b)中,CO2高体积分数意味着更高的反应速率及相同时间内更多的产物生成量,使吸收剂相变的时间提前,即拐点出现的时间也提前,在分相以后CO2体积分数越高则产物的量在相同时间内生成的越多,所以分相吸收的吸收速率迅速下降,但吸收剂在变为两相后对低分压的CO2仍保持相对较高的吸收速率.
不同吸收剂的最佳操作温度不同,吸收温度会对吸收剂的捕集性能产生影响.在吸收温度为30、40、50和60℃下进行吸收试验,吸收剂的负载和吸收速率如图10所示.在30~50℃的温度范围内,吸收温度的升高会使吸收剂的负载升高,吸收温度为50℃时吸收剂的负载为0.99mol/mol,当吸收温度升高到60℃以后吸收剂的负载降为0.97mol/mol,温度的升高有利于吸收反应的正向进行但却不利于CO2溶解在溶剂中.在分相以前,温度越高则吸收速率越快,分相以后温度越高,吸收速率下降速度越快,温度升高会使吸收剂富相对SFL的溶解度升高,因而吸收剂变为两相的时间也提前.为保证吸收剂的负载和吸收速率,MAPA-SFL-H2O两相吸收剂的最佳吸收温度设在40~50℃范围内.
对于尾气中的SO2和NOx,理论上与CO2同为酸性气体,会和MAPA发生反应从而影响吸收剂的吸收性能.为深入探究杂质气体对吸收剂MAPA的影响,试验分别配制体积分数为0.02%和0.04%的SO2废气.图11示出吸收剂质量比为3∶3∶4时吸收SO2对负载的影响.SO2对吸收剂CO2负载影响并不显著,吸收剂在SO2体积分数为0.02%条件下的负载比SO2体积分数为0.04%条件下的负载高0.96%.
这是由于船舶尾气会经过预处理脱除尾气中绝大部分的SO2,尾气中剩余的SO2体积分数相较于CO2的体积分数几乎可以忽略,因而经过预处理后尾气中的SO2对碳捕集系统吸收过程的影响很小,且尾气中SO2引起的吸收剂捕集能力损失仅需补充少量的新鲜吸收剂便可弥补.此外,在反应器出口的位置几乎检测不到SO2,在此试验条件下吸收剂对SO2也达到较高的脱除效率.
在实际船舶排放的废气中,NOx排放中主要为NO,而O2体积分数为10%~14%,O2能促使NO转化为NO2.因此,试验制备了体积分数为10%的O2模拟废气,并在其中分别加入体积分数为0.05%、0.10%和0.15%的NO,如图12所示.当使用质量比为3∶3∶4的吸收剂时,对NO的脱除效率分别为14.4%、22.0%和27.6%,表明吸收剂对NO的脱除效率没有超过40.0%.可知,随着废气中NO体积分数的增加,吸收剂对NO的脱除效率呈上升趋势.此外,由于船舶尾气中NO体积分数相对较低,因而NO对吸收剂吸收性能的影响并不显著.
吸收剂在负载CO2后变为两相是两相吸收剂降低再生能耗的决定性因素.首先,根据两性离子反应机理探究了吸收剂的CO2吸收反应过程.两性离子反应机理广泛用于描述伯胺、仲胺与CO2反应过程.在两性离子反应的初始阶段,伯胺、仲胺与CO2反应形成两性离子,之后碱性物质参与质子转移过程.由于MAPA分子包含伯胺和仲胺基团,两种胺基基团都能直接与CO2反应形成两种不同两性离子(MAPAH+COOP−、MAPAH+COOS−),见反应R(2)和R(3)所示,同时作为载体参与质子转移生成两种氨基甲酸酯(MAPACOOP−、MAPACOOS−)和两种质子化胺(MAPAHP+、MAPAHS+),见反应R(4)~R(7)[24].
MAPAP+CO2⇌MAPAH+COOP−
MAPAS+CO2⇌MAPAH+COOS−
MAPAH+COOP−+MAPAP⇌  MAPACOOP−+MAPAHP+
MAPAH+COOP−+MAPAS⇌  MAPACOOP−+MAPAHP+
MAPAH+COOS−+MAPAP⇌  MAPACOOS−+MAPAHP+
MAPAH+COOS−+MAPAS⇌  MAPACOOS−+MAPAHS+
MAPA的一个胺基基团参与反应后生成氨基甲酸酯(MAPACOO-)和质子化胺(MAPAH+),之后仍有一个胺基基团可以继续和CO2发生反应,MAPA和CO2的全部反应见反应R(8)~R(11)[24],反应路径如图13所示.
MAPAHP++CO2⇌MAPA(HP+)H+COOS−
MAPAHS++CO2⇌MAPA(HS+)H+COOP−
MAPACOOP-+CO2⇌  MAPA(COOS-)H+COOP-
MAPACOOS-+CO2⇌  MAPA(COOP-)H+COOS-
为验证MAPA-SFL-H2O和CO2的反应机理,明确影响相变的主要因素,分别对吸收剂质量比为3∶3∶4、未负载CO2及负载后10、20和40min的吸收剂进行13CNMR检测,MAPA-SFL-H2O中物质分子结构如图14所示.
图15为4种样品NMR检测结果.原吸收剂的碳谱检测结果中,此时吸收剂并没有和CO2发生反应,因而碳谱图中共有6个碳信号,其中C1~C4为MAPA分子上的4个碳原子,C7和C8为SFL的碳信号(图14(d)).SFL的两个碳信号化学位移分别为51.0和22.3.
CO2通入10min后在C1~C4附近出现了新的碳信号,即C1'~C4',并且在化学位移为164.7处出现了新的碳信号C5',说明有新的物质产生.新出现的5个碳信号为CO2和MAPA的伯胺基团发生反应生成的伯氨基甲酸酯MAPACOOP−,如反应R(5)所示,在化学位移为164.7处出现的新的碳信号由气体CO2和伯胺基团发生反应进入液相的C原子产生.随着反应的进行,吸收剂中C1~C4碳信号强度不断降低,说明吸收剂中的MAPA随反应进行和产物的生成而被不断消耗,产物MAPACOOP−的生成量随着反应的进行而逐渐升高.反应进行到40min时,在C1~C4附近又出现了新的碳信号,即C1"~4";在化学位移为164.3处检测到新增的碳信号C6",对应于气相CO2与仲胺基团反应生成MAPACOOS−并进入到液相所产生的原子,该过程见反应R(7).虽然在吸收时间为10~40min内吸收剂并未变为两相;但氨基甲酸酯的产生使吸收剂对SFL的溶解度降低,因而C7和C8碳信号的强度降低.
吸收剂和CO2反应60min后吸收剂变为两相,分别对吸收剂的上相和下相进行13CNMR检测,分相结果如图16所示.可知上相物质为MAPACOOP−、MAPACOOS−、MAPA和SFL,其中MAPACOOP−的相对含量最高,下相只有SFL.
由图16可知,MAPA-SFL-H2O两相吸收剂发生相变主要由CO2的负载来控制,没有负载CO2时吸收剂中的MAPA、SFL和水能够互溶,随着CO2不断加载到吸收剂当中,产物的生成量也随之升高,MAPACOOP−和MAPACOOS−不能与SFL互溶,两种氨基甲酸酯的体积分数逐渐增加,而未反应的MAPA的量逐渐减少,导致SFL在吸收剂中的溶解度下降.当达到特定的负载水平时,SFL会从溶液中析出形成贫相.同时,两种氨基甲酸酯和未反应的MAPA在水中富集,形成富相.随着吸收剂负载的增加,析出的SFL作为贫相不会进入解吸塔再生,富相中的SFL体积分数逐渐降低,有利于减少解吸过程中进入解吸塔的富液,进而降低再生能耗[25].MAPA-SFL-H2O与CO2反应的相变过程如图17所示.
(1)与相同质量分数的MEA相比,MAPA-SFL-H2O双相吸收剂在低分压CO2的吸收过程保持高反应速率,在吸收剂质量比为3∶3∶4时循环负载相较于MEA提高72.3%,解吸容量提高40.7%,再生能耗下降28.4%;双相吸收剂在分相前、后的吸收速率表现出不同的特性,在分相之后,当CO2体积分数较低且吸收温度较低时,吸收速率较快;而高CO2体积分数和高吸收温度则会导致吸收剂提前发生分相.
(2)在MAPA和CO2反应的过程中,伯胺基团主要与CO2参加反应,仲胺基团控制质子转移过程;吸收剂的相变主要由CO2负载控制,CO2体积分数升高、SFL配比升高和温度降低会促进相变;分相后,SFL析出,使富液相减少进入解吸塔,汽化潜热降低,从而降低再生能耗.
  • 海洋负排放国家大科学计划资助项目(国函[2023]120号)
  • 国家自然科学基金资助项目(52371367)
  • 中央高校基金资助项目(3072025PT0303)
  • 黑龙江省重点研发计划资助项目(2024ZXDXC03)
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2025年第43卷第6期
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doi: 10.16236/j.cnki.nrjxb.202506061
  • 接收时间:2025-02-26
  • 首发时间:2026-11-04
  • 出版时间:2025-11-25
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  • 收稿日期:2025-02-26
  • 修回日期:2025-06-02
基金
海洋负排放国家大科学计划资助项目(国函[2023]120号)
国家自然科学基金资助项目(52371367)
中央高校基金资助项目(3072025PT0303)
黑龙江省重点研发计划资助项目(2024ZXDXC03)
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    哈尔滨工程大学动力与能源工程学院,哈尔滨 150001

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席鸿远,博士,助理研究员,.
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
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