Article(id=1236596128637047349, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236596124832821317, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202409206, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1725638400000, receivedDateStr=2024-09-07, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772757091912, onlineDateStr=2026-03-06, pubDate=1748102400000, pubDateStr=2025-05-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772757091912, onlineIssueDateStr=2026-03-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772757091912, creator=13701087609, updateTime=1772757091912, updator=13701087609, issue=Issue{id=1236596124832821317, tenantId=1146029695717560320, journalId=1210938733613449225, year='2025', volume='54', issue='5', pageStart='1', pageEnd='162', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=0, articleOrder=1, issueType=-1, specialIssue=null, createTime=1772757091004, creator=13701087609, updateTime=1772757664851, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236598531780309922, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236596124832821317, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236598531780309923, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236596124832821317, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=44, endPage=53, ext={EN=ArticleExt(id=1236596129006146104, articleId=1236596128637047349, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Performance study of CO2 zero emission SOFC/GT/ORC hybrid power system integrated with chemical chain hydrogen production, columnId=1236596126195970127, journalTitle=Thermal Power Generation, columnName=Special topic on new power generation technology, runingTitle=null, highlight=null, articleAbstract=

A novel type of integrated chemical chain hydrogen production CO2 zero emission solid oxide fuel cell/gas turbine/organic Rankine cycle hybrid power system is proposed, which achieves efficient power generation while efficiently separating and capturing CO2. The system uses methane as fuel and generates hydrogen gas through chemical chain reactions to enter the fuel cell, avoiding carbon accumulation inside the cell. The anode outlet circuit of the cell is connected to the chemical chain, and the gas from the fuel reactor outlet and the cathode outlet of the cell enters the gas turbine to do work. The exhaust waste heat is recovered and utilized by the organic Rankine cycle system, further improving the system efficiency. A complete system model was established and thermodynamic performance analysis was conducted on the system, obtaining the variation laws of system performance with fuel flow rate, fuel utilization rate, battery working temperature, and system working pressure. The results showed that the comprehensive energy utilization efficiency of the system could reach over 74.10%, the electrical efficiency could reach over 62.42%, and the exergy efficiency could reach 57.73%. Sensitivity analysis showed that the system performance reached its optimum when the system working pressure reached 7×105 Pa.

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提出一种新型集成化学链制氢的CO2零排放固体氧化物燃料电池/燃气轮机/有机朗肯循环混合动力系统,在实现高效发电的同时,高效分离捕集CO2。系统以甲烷为燃料,通过化学链反应产生氢气进入燃料电池,避免了电池内部积碳现象发生,电池阳极出口回路至化学链,燃料反应器出口与电池阴极出口气体进入燃气轮机做功,排气余热被有机朗肯循环系统回收利用,进一步提高系统效率;并建立了系统模型并进行热力学性能分析,得到系统性能随燃料流量、燃料利用率、电池工作温度及系统工作压力的变化规律。结果表明:系统综合能源利用效率可达74.10%以上,电效率可达62.42%以上,㶲效率达到57.73%;敏感性分析表明,系统工作压力达到7×105 Pa时,系统性能达到最优。

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段立强(1973),男,博士,教授、博导,主要研究方向为分布式能量系统,燃料电池复合动力系统、太阳能-化石燃料多能互补动力系统,
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佟勇婧(1995),女,博士,工程师,主要研究方向为天然气与新能源融合技术,

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佟勇婧(1995),女,博士,工程师,主要研究方向为天然气与新能源融合技术,

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佟勇婧(1995),女,博士,工程师,主要研究方向为天然气与新能源融合技术,

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IEEE, 1996., articleTitle=The Westinghouse solid oxide fuel cell program-a status report, refAbstract=null), Reference(id=1236610630082417049, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, doi=null, pmid=null, pmcid=null, year=2020, volume=40, issue=4, pageStart=5, pageEnd=null, url=null, language=null, rfNumber=[20], rfOrder=24, authorNames=张建亮, journalName=煤气与热力, refType=null, unstructuredReference=张建亮. 中温余热热源有机朗肯循环工质比较[J]. 煤气与热力, 2020, 40(4): 5., articleTitle=中温余热热源有机朗肯循环工质比较, refAbstract=null), Reference(id=1236610630187274652, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, doi=null, pmid=null, pmcid=null, year=2020, volume=40, issue=4, pageStart=5, pageEnd=null, url=null, language=null, rfNumber=[20], rfOrder=25, authorNames=ZHANG Jianliang, journalName=Gas & Heat, refType=null, unstructuredReference=ZHANG Jianliang. 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Journal of Power Sources, 2002, 103(2): 188-200., articleTitle=Energy and exergy analysis of simple solid-oxide fuel-cell power systems, refAbstract=null), Reference(id=1236610630447321509, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, doi=null, pmid=null, pmcid=null, year=2020, volume=223, issue=1, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[23], rfOrder=28, authorNames=ZHAO H, ZHAO Z, WANG H, journalName=Energy Conversion and Management, refType=null, unstructuredReference=ZHAO H, ZHAO Z, WANG H. Thermodynamic performance study of the CLHG/SOFC combined cycle system with CO2 recovery[J]. Energy Conversion and Management, 2020, 223(1): 113319., articleTitle=Thermodynamic performance study of the CLHG/SOFC combined cycle system with CO2 recovery, refAbstract=null)], funds=[Fund(id=1236610627301593426, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, awardId=2023-KLKJ-10, language=EN, fundingSource=Scientific Research and Technology Development Project of PetroChina Kunlun Gas Co., Ltd(2023-KLKJ-10), fundOrder=null, country=null), Fund(id=1236610627456782680, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, awardId=2023-KLKJ-10, language=CN, fundingSource=中石油昆仑燃气有限公司科学研究与技术开发项目(2023-KLKJ-10), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1236610618724242408, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, xref=1., ext=[AuthorCompanyExt(id=1236610618736825322, tenantId=1146029695717560320, journalId=1210938733613449225, 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figureFileBig=YQWyP6Rbnn6x4K4hTu5BKw==, tableContent=null), ArticleFig(id=1236610624583684355, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=图5, caption=燃料利用率对系统各部分功率影响, figureFileSmall=B0gBrjW95NYZpjmNoD377Q==, figureFileBig=YQWyP6Rbnn6x4K4hTu5BKw==, tableContent=null), ArticleFig(id=1236610624692736261, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=EN, label=Fig.6, caption=The effect of fuel utilization rate on the net output power and efficiency of the system, figureFileSmall=995O8tabK1NCKPUr7N7GVA==, figureFileBig=pXKIlSq5TCH+4t47a+fnYQ==, tableContent=null), ArticleFig(id=1236610624810176778, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=图6, caption=燃料利用率对系统净输出功率以及效率影响, figureFileSmall=995O8tabK1NCKPUr7N7GVA==, figureFileBig=pXKIlSq5TCH+4t47a+fnYQ==, tableContent=null), 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caption=系统工作压力对系统净输出功率以及效率影响, figureFileSmall=GuSoIk5cCHucm6J7EMZMNA==, figureFileBig=WfivX+izAhnSHB9K3FG1/w==, tableContent=null), ArticleFig(id=1236610626060079400, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=EN, label=Tab.1, caption=

Main design parameters of the system

, figureFileSmall=null, figureFileBig=null, tableContent=
参数数值
环境温度/℃25
环境压力/Pa1.013 15×105
燃料流量/(kmol·h–1)1
DC-AC转换效率/%95[9]
空气压缩机等熵效率/%82[10]
燃料压缩机等熵效率/%82[10]
燃气轮机等熵效率/%75
R141b膨胀机等熵效率/%75
工质泵效率/%80
空气反应器进气温度/℃544
MgAl2O4流量/(kmol·h–1)6[11]
Fe2O3流量/(kmol·h-1)4[11]
SOFC热损失/%2
SOFC工作压力/Pa5×105
SOFC工作温度/℃910
燃料利用率/%85
电池活化面积/m296.1
), ArticleFig(id=1236610626169131307, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=表1, caption=

系统主要设计参数

, figureFileSmall=null, figureFileBig=null, tableContent=
参数数值
环境温度/℃25
环境压力/Pa1.013 15×105
燃料流量/(kmol·h–1)1
DC-AC转换效率/%95[9]
空气压缩机等熵效率/%82[10]
燃料压缩机等熵效率/%82[10]
燃气轮机等熵效率/%75
R141b膨胀机等熵效率/%75
工质泵效率/%80
空气反应器进气温度/℃544
MgAl2O4流量/(kmol·h–1)6[11]
Fe2O3流量/(kmol·h-1)4[11]
SOFC热损失/%2
SOFC工作压力/Pa5×105
SOFC工作温度/℃910
燃料利用率/%85
电池活化面积/m296.1
), ArticleFig(id=1236610626290766127, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=EN, label=Tab.2, caption=

Calculation results of CLHG

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物流项目模拟值参考值[11]误差/%
FR出口流(1)压力/Pa2×1062×1060
温度/℃7137231.380
流量/(kmol·h–1)330
摩尔分数CO20.330.330
H2O0.6700.6700.015
SR出口流(2)压力/Pa2×1062×1060
温度/℃7177271.380
流量/(kmol·h–1)6.556.550
摩尔分数H2O0.592 90.593 80.152
H20.407 00.406 00.197
AR出口流(3)压力/Pa2×1062×1060
温度/℃8808800
流量/(kmol·h–1)2.5302.5380.052
), ArticleFig(id=1236610626404012341, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=表2, caption=

CLHG计算结果

, figureFileSmall=null, figureFileBig=null, tableContent=
物流项目模拟值参考值[11]误差/%
FR出口流(1)压力/Pa2×1062×1060
温度/℃7137231.380
流量/(kmol·h–1)330
摩尔分数CO20.330.330
H2O0.6700.6700.015
SR出口流(2)压力/Pa2×1062×1060
温度/℃7177271.380
流量/(kmol·h–1)6.556.550
摩尔分数H2O0.592 90.593 80.152
H20.407 00.406 00.197
AR出口流(3)压力/Pa2×1062×1060
温度/℃8808800
流量/(kmol·h–1)2.5302.5380.052
), ArticleFig(id=1236610626525647159, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=EN, label=Tab.3, caption=

Verification of SOFC simulation

, figureFileSmall=null, figureFileBig=null, tableContent=
参数模拟值文献值[20]文献值[19]
VSOFC/V0.690.700.70
i/(mA·cm2)179.08180.00178.00
TSOFC/℃830.85847.00834.00
ηSOFC/%51.9550.0052.00
), ArticleFig(id=1236610626605338939, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=表3, caption=

SOFC验证结果

, figureFileSmall=null, figureFileBig=null, tableContent=
参数模拟值文献值[20]文献值[19]
VSOFC/V0.690.700.70
i/(mA·cm2)179.08180.00178.00
TSOFC/℃830.85847.00834.00
ηSOFC/%51.9550.0052.00
), ArticleFig(id=1236610626802471233, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=EN, label=Tab.4, caption=

Output power and efficiency of the system under rated operating conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
参数数值
总输入能量/kW222.95
WSOFC/kW100.32
WGT1/kW9.48
WGT2/kW71.69
WGT3/kW11.70
WAC1/kW6.86
WAC2/kW40.66
WFC/kW1.62
WP/kW0.44
WCOMP/kW4.44
QH/kW26.05
输出电功/kW139.16
总输出能量/kW165.21
ηe/%62.42
ηt/%74.10
CO2捕获率/%100.00
), ArticleFig(id=1236610626911523140, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=表4, caption=

系统额定工况下输出功率和效率

, figureFileSmall=null, figureFileBig=null, tableContent=
参数数值
总输入能量/kW222.95
WSOFC/kW100.32
WGT1/kW9.48
WGT2/kW71.69
WGT3/kW11.70
WAC1/kW6.86
WAC2/kW40.66
WFC/kW1.62
WP/kW0.44
WCOMP/kW4.44
QH/kW26.05
输出电功/kW139.16
总输出能量/kW165.21
ηe/%62.42
ηt/%74.10
CO2捕获率/%100.00
), ArticleFig(id=1236610627003797833, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=EN, label=Tab.5, caption=

Exergy balance of the system under rated operating conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
参数数值
输入㶲/kW247.65
电㶲/kW139.16
热量㶲/kW3.80
输出㶲共计/kW142.96
㶲损/kW104.69
㶲效率/%57.73
设备㶲损/kW㶲损率/%
CLHG39.1137.36
SOFC23.4822.43
预热器6.175.89
热交换器11.208.98
冷凝器3.052.91
空气压缩机10.790.76
空气压缩机24.684.47
燃料压缩机0.210.20
燃气轮机10.920.88
燃气轮机28.438.05
燃气轮机33.323.17
P0.090.09
二氧化碳压缩机0.590.55
冷却器1.121.07
排气3.343.19
合计104.69100.00
), ArticleFig(id=1236610627087683917, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596128637047349, language=CN, label=表5, caption=

系统额定工况下㶲平衡

, figureFileSmall=null, figureFileBig=null, tableContent=
参数数值
输入㶲/kW247.65
电㶲/kW139.16
热量㶲/kW3.80
输出㶲共计/kW142.96
㶲损/kW104.69
㶲效率/%57.73
设备㶲损/kW㶲损率/%
CLHG39.1137.36
SOFC23.4822.43
预热器6.175.89
热交换器11.208.98
冷凝器3.052.91
空气压缩机10.790.76
空气压缩机24.684.47
燃料压缩机0.210.20
燃气轮机10.920.88
燃气轮机28.438.05
燃气轮机33.323.17
P0.090.09
二氧化碳压缩机0.590.55
冷却器1.121.07
排气3.343.19
合计104.69100.00
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集成化学链制氢的CO2零排放SOFC/GT/ORC混合动力系统性能
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佟勇婧 1 , 王军 1 , 池立勋 1 , 程思昱 2 , 段立强 2 , 张汉飞 2 , 王秋实 2 , 王浩博 3 , 黄龑 1
热力发电 | 新型发电技术专题 2025,54(5): 44-53
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热力发电 | 新型发电技术专题 2025, 54(5): 44-53
集成化学链制氢的CO2零排放SOFC/GT/ORC混合动力系统性能
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佟勇婧1 , 王军1, 池立勋1, 程思昱2, 段立强2 , 张汉飞2, 王秋实2, 王浩博3, 黄龑1
作者信息
  • 1.中国石油天然气股份有限公司规划总院,北京 100000
  • 2.华北电力大学能源动力与机械工程学院,北京 100000
  • 3.中石油昆仑燃气有限公司,北京 100000
  • 佟勇婧(1995),女,博士,工程师,主要研究方向为天然气与新能源融合技术,

通讯作者:

段立强(1973),男,博士,教授、博导,主要研究方向为分布式能量系统,燃料电池复合动力系统、太阳能-化石燃料多能互补动力系统,
Performance study of CO2 zero emission SOFC/GT/ORC hybrid power system integrated with chemical chain hydrogen production
Yongjing TONG1 , Jun WANG1, Lixun CHI1, Siyu CHENG2, Liqiang DUAN2 , Hanfei ZHANG2, Qiushi WANG2, Haobo WANG3, Yan HUANG1
Affiliations
  • 1.PetroChina Planning and Engineering Institute, Beijing 100000, China
  • 2.School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 100000, China
  • 3.PetroChina Kunlun Gas Co., Ltd., Beijing 100000, China
出版时间: 2025-05-25 doi: 10.19666/j.rlfd.202409206
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提出一种新型集成化学链制氢的CO2零排放固体氧化物燃料电池/燃气轮机/有机朗肯循环混合动力系统,在实现高效发电的同时,高效分离捕集CO2。系统以甲烷为燃料,通过化学链反应产生氢气进入燃料电池,避免了电池内部积碳现象发生,电池阳极出口回路至化学链,燃料反应器出口与电池阴极出口气体进入燃气轮机做功,排气余热被有机朗肯循环系统回收利用,进一步提高系统效率;并建立了系统模型并进行热力学性能分析,得到系统性能随燃料流量、燃料利用率、电池工作温度及系统工作压力的变化规律。结果表明:系统综合能源利用效率可达74.10%以上,电效率可达62.42%以上,㶲效率达到57.73%;敏感性分析表明,系统工作压力达到7×105 Pa时,系统性能达到最优。

固体氧化物燃料电池  /  化学链制氢  /  分布式发电系统  /  热力学性能

A novel type of integrated chemical chain hydrogen production CO2 zero emission solid oxide fuel cell/gas turbine/organic Rankine cycle hybrid power system is proposed, which achieves efficient power generation while efficiently separating and capturing CO2. The system uses methane as fuel and generates hydrogen gas through chemical chain reactions to enter the fuel cell, avoiding carbon accumulation inside the cell. The anode outlet circuit of the cell is connected to the chemical chain, and the gas from the fuel reactor outlet and the cathode outlet of the cell enters the gas turbine to do work. The exhaust waste heat is recovered and utilized by the organic Rankine cycle system, further improving the system efficiency. A complete system model was established and thermodynamic performance analysis was conducted on the system, obtaining the variation laws of system performance with fuel flow rate, fuel utilization rate, battery working temperature, and system working pressure. The results showed that the comprehensive energy utilization efficiency of the system could reach over 74.10%, the electrical efficiency could reach over 62.42%, and the exergy efficiency could reach 57.73%. Sensitivity analysis showed that the system performance reached its optimum when the system working pressure reached 7×105 Pa.

solid oxide fuel cell  /  chemical chain hydrogen production  /  distributed power generation system  /  thermodynamic performance
佟勇婧, 王军, 池立勋, 程思昱, 段立强, 张汉飞, 王秋实, 王浩博, 黄龑. 集成化学链制氢的CO2零排放SOFC/GT/ORC混合动力系统性能. 热力发电, 2025 , 54 (5) : 44 -53 . DOI: 10.19666/j.rlfd.202409206
Yongjing TONG, Jun WANG, Lixun CHI, Siyu CHENG, Liqiang DUAN, Hanfei ZHANG, Qiushi WANG, Haobo WANG, Yan HUANG. Performance study of CO2 zero emission SOFC/GT/ORC hybrid power system integrated with chemical chain hydrogen production[J]. Thermal Power Generation, 2025 , 54 (5) : 44 -53 . DOI: 10.19666/j.rlfd.202409206
随着经济不断发展,化石能源需求量日益增加,不仅导致已探明能源储量逐渐减少,还对气候与环境带来了巨大的影响。化石燃料的利用伴随着二氧化碳等温室气体大量排放,导致全球气候变暖。为了应对这一挑战,实现二氧化碳减排和能源的供应平衡,清洁能源的重要性可见一斑。国家积极推进“碳达峰、碳中和”战略,立足能源资源禀赋,分步骤实施“碳达峰、碳中和”,加快规划建设新型能源体系。
氢气作为能源,其无毒、质量轻、能量密度高,燃烧只产生水,可以有效减少碳排放,同时单位质量热值也高于其他种类的燃料,可以直接燃烧供能,也可以为冶金行业提供反应材料和热源,在交通运输、化工生产、建筑行业等多个领域都有广泛的应用潜力,因此氢能开始逐渐受到重视。目前,氢气制备主要通过水分解制氢和碳氢燃料热化学制氢。热分解水是最直接的制氢方式,但是水分解所需的反应温度过高,导致制氢过程中热损失过大,能量转化效率低,对反应器的材料要求也更高。热化学循环水分解制氢相较于直接水分解降低了反应温度,但温度仍较高,效率也在50%以下。目前,应用较多的是甲烷水蒸气重整制氢[1]。为了满足能源需求与环境要求,高效率制氢技术至关重要。
德国科学家Richter等人[2]在近年首次提出了一种用于分离提纯CO2的新型燃烧技术,即化学链燃烧(chemical looping combustion,CLC),该技术通过载氧体把传统燃烧分为2个气固反应,以晶格氧的形式代替空气中的氧分子,并通过载氧体的循环完成整个燃烧过程,是一种与传统燃烧方式不同的近乎于零排放、高效环保的燃烧方式。化学链制氢(chemical looping hydrogen generation,CLHG)技术拥有系统简化、“碳集中”捕集的优势,引起了极大关注。氢气可为固体氧化物燃料电池(solid oxide fuel cell,SOFC)提供燃料,化学链制氢系统可以回收固体氧化物燃料电池的余热,以实现天然气的高效清洁利用。传统的甲烷重整制氢反应温度高、能耗高、碳排放高,为了实现氢气的高效清洁制备,需要新的制氢方案。化学链制氢作为一种低能耗、碳捕集方面的优势,逐渐进入研究视野。化学链制氢的研究中大致可以分成3个层面:化学链燃烧反应器的设计,对载氧体性能的分析与研究,化学链燃烧与其他技术相耦合的系统研究。可采用Aspen Plus等相关软件对其进行建模、仿真和计算[3]。王晓佳等[4]对以Fe2O3为载氧体的甲烷化学链燃烧系统进行建模和计算,探究铁基载氧体的反应机理,研究反应器各项参数对载氧体性能的影响,并分析化学链燃烧系统的反应效率。Xiao等人[5]针对以Fe2O3为载氧体的固体燃料进行化学链燃烧实验,主要研究铁基载氧体在不同温度条件下的反应活性与循环情况,结果表明,CO2转化率在反应温度超过900 ℃时可达90%以上,在反应温度小于850 ℃时仅在75%以下,同时通过扫瞄式电子显微镜(SEM)分析可以得出,铁基载氧体会随循环次数的增加出现逐渐烧结的现象。化学链制氢系统与先进能源系统相耦合的研究也在不断进行,如燃料电池、太阳能及燃气轮机等与化学链燃烧相结合,不但扩展了化学链燃烧的应用范围,同时实现了不同技术之间的互补,得到更高的节能减排率、经济性和燃料转化率。Wang等人[6]提出了一种集太阳能和CLC于一体的冷热电联供(combined cooling heating and power,CCHP)系统,该系统实现了CO2的分离,且无能耗损失。Fan等人[7]将CLC与混合燃料CCHP系统相结合,在生物质比例较大时达到负排放的目标,仿真结果表明,该系统降低了CLC捕集CO2的能量成本。工业生产过程中会产生大量中低温余热(温度在350 ℃以下的为低温余热,温度在350~650 ℃的为中温余热),合理回收和利用中低温余热不仅有助于缓解我国能源短缺,还能减少工业生产造成的环境污染。在中低温余热回收利用中,有机朗肯循环(organic Rankine cycle,ORC)发电技术对热源温度具有广泛的适应性,因而受到广泛重视。
本文提出了一种新型集成CLHG的CO2零排放SOFC/GT/ORC混合动力系统,建立了整个系统模型并对系统性能进行灵敏度分析,得到了系统性能随燃料流量、燃料利用率、SOFC工作温度及系统工作压力的变化规律。
本文提出的集成CLHG的CO2零排放SOFC/ GT/ORC混合动力系统如图1所示。该系统中甲烷进入化学链制氢CLHG系统进行反应产生氢气,氢气作为燃料气进入固体氧化物燃料电池SOFC发生电化学反应,避免了传统SOFC/GT系统中甲烷直接进入SOFC所引起的积碳现象;燃料不与氧气直接接触,有效减少了氮氧化物的产生,提高了安全性能[8];阳极出口排气完全回流至CLHG中的蒸汽反应器,以提高系统效率,同时可以取消SOFC的预重整与后燃室,产生的余热由ORC进行回收,同时,燃料反应器(FR)出口的气体在换热后经过四级压缩成液体进行储存,便于运输及利用,在系统高效发电的同时可以实现CO2的高效分离与捕集。
燃料甲烷(2)经过加压和预热后,在FR中与Fe2O3发生反应,生成的气体(12)进入燃气轮机(GT1)中做功,生成的FeO进入蒸汽反应器(SR)与来自SOFC阳极的排气(20)反应,产生的氢气(11)进入SOFC阳极作为燃料,同时FeO被氧化为Fe3O4进入空气反应器(AR)。空气(1)经过加压和预热后进入AR,与Fe3O4发生反应放出大量热,Fe3O4被氧化为Fe2O3,进入燃料反应器,从而完成一次循环。
空气(1)经过加压和预热后,进入SOFC阴极提供氧气,SOFC阴极排气(19)与空气反应器排气(10)混合进入燃气轮机(GT2)做功,之后对空气进行预热,再进入热交换器2进行热交换,然后排出。部分工质R141b在热交换器1中吸热,另一部分R141b在热交换器2中吸热,之后混合进入燃气轮机(GT3)做功,排气经过冷凝器冷凝,之后被工质泵加压。燃气轮机(GT1)排气对空气和燃料进行预热,然后进入热交换器1进行热交换,完成热交换后,在换热器中冷却,冷凝得到热水,然后进入气液分离器分离,经过四级压缩,分离出纯净的CO2和水。
本文选择嵌入Fortran的Aspen Plus软件对系统进行仿真,从而得到系统性能参数。本文模拟基于质量守恒、能量守恒和化学平衡,基于吉布斯自由能最小化理论计算化学平衡。主要假设如下:1)系统处于稳定运行状态,各组分温度、压力分布均匀;2)电压稳定,忽略设备的压损;3)输入燃料为纯甲烷;4)忽略节流损失等设备损耗;5)SOFC阳极、阴极温度相同,电池出口气体温度与工作温度相同。设计工况下的系统主要参数见表1[9-11]
CLHG子系统主要包括燃料反应器、蒸汽反应器、空气反应器3个反应器,载氧体在3个反应器之间循环,避免了氧气和燃料的直接接触,提高了反应效率。整个CLHG子系统反应过程图2所示[12]
CLHG子系统燃料反应器中的Fe2O3被CH4还原为FeO,主要反应为:
4Fe2O3+CH4=8FeO+2H2O+CO2     ΔH=356.5 kJ/kmol
CLHG子系统蒸汽反应器中,FeO被水氧化为Fe3O4,同时生成氢气,主要反应式为:
8FeO+83H2O=83Fe3O4+83H2       ΔH=199.3 kJ/mol
CLHG子系统空气反应器中,Fe3O4被O2氧化为Fe2O3,主要反应为:
83Fe3O4+23O2=4Fe2O3        ΔH=157.4 kJ/mol
参考Edrisi A等[11]建立CLHG模型,计算得到各物流的温度、压力、流量、成分等参数,并与文献[11]系统进行对比,结果见表2。由表2可以看出,本文所建立的CLHG模型与文献[11]的计算结果最大误差为1.38%,证明本文所建立的CLHG模型是可靠的。
来自蒸汽反应器的氢气直接供给SOFC阳极,与氧离子发生化学反应。空气经过预热后进入SOFC阴极,为化学反应提供氧气。
SOFC阴阳极电化学反应式如下:
  O2+4e=2O2
  H2+O2=H2O+2e
SOFC模型计算主要分为直接法和间接法,区别主要在电压计算上。本文模型采用直接法进行电池的电流、电压、效率等模拟计算。
电流计算式如下:
I=zneF
i=iAcell
式中:I表示电流,A;z表示H2的摩尔流量,mol/s;ne表示化学反应过程中转移的电子数;F为法拉第常数;i表示电流密度,A/m2Acell表示SOFC的活化面积,m2
SOFC电压计算是建模的核心,电压计算公式如下[13-18]
VSOFC=ENernstVohm(Vact,an+Vact,ca)(Vcon,an+Vcon,ca)
式中:Vohm表示欧姆损失,V;Vact,anVact,ca分别表示阳极和阴极的活化极化损失,V;Vcon,anVcon,ca分别表示阳极和阴极的浓差极化损失,V;ENernst表示能斯特电压,V。
其中,能斯特电压一般按照下式计算:
E0=1.2532.451 6×104T
ENernst=E0+RT2Fln(PH2PO20.5PH2O)
式中:E0表示标准电动势,V;T表示电池运行温度,K;R为摩尔气体常数,8.31 J/(mol·K);P表示电池出口分压力,下标表示对应气体,Pa。
欧姆极化损失可以利用下式计算:
ρi=aiexp(biT)
ri=ρiΔiASOFC
Vohm=ISOFCiri
式中:ρi表示SOFC对应元件的电阻率,Ω·m;δi表示电池对应组分的厚度,m;ri表示电池其他元件的电阻,Ω;ASOFC为电池有效反应面积,m2
活化极化损失利用下式计算:
i0,an=γan(PH2P0,an)(PH2OP0,an)exp(Eact,anRT)
i0,ca=γca(PO2P0,ca)0.25exp(Eact,caRT)
Vact,an=RTFln[(iSOFC2i0,an)+(iSOFC2i0,an)2+1]
Vact,ca=RTFln[(iSOFC2i0,ca)+(iSOFC2i0,ca)2+1]
式中:i0,ani0,ca分别表示阳极和阴极交换电流密度,A/m2γanγca分别表示电池阳极和阴极扩散系数,A/m2Vact,anVact,ca分别表示阳极和阴极活化能,J/mol;P0,anP0,ca为阳极和阴极的压力,Pa;Eact,anEact,ca为阳极和阴极的活化能,J/mol。
浓差极化损耗是电极和界面材料迁移引起的电阻。由于固体氧化物燃料电池的工作温度很高,燃料的扩散是一个有效的过程,浓差极化损失相对较小,可以忽略不计。
SOFC的输出功率为:
WSOFC=ISOFCVSOFCηDC-AC
式中:ηDC-AC表示直流转交流电的效率。
SOFC电效率可表示为:
ηSOFC=WSOFCmfuel×QLHV,fuel
式中:mfuel表示燃料质量流量,kg/s;QLHV,fuel表示燃料的低位热值,kJ/kg。
为了证明模型的可靠性,将模型经过计算得到的结果与Westinghouse公司生产的120 kW SOFC实验结果[19-20]进行对比,其结果见表3。从表3可以看出,本文模拟仿真结果与文献[19-20]的实验结果误差较小,最大误差为3.9%,证明该模型是可靠的。
从CLHG及SOFC排出的废气余热由ORC系统和热交换器吸收,用以发电和产生生活热水。本文ORC系统选用R141b作为循环工质,因其环境友好、毒性低、不易燃,作为中温余热有机朗肯循环工质综合考虑比较合适[21]
经过余热回收后的CO2流冷却到30 ℃,水冷凝分离出,经过四级压缩,压缩热被冷却水吸收,最后CO2被压缩到120×105 Pa,变为液态以备远距离输送[22]
所提新系统为动力发电系统,系统的发电效率ηe计算公式为:
ηe=WSOFC+WGTWACWFCWCOMPmfuel×QLHV,fuel
式中:WSOFC为SOFC发电量,kW;WGT表示系统中所有膨胀机的发电量,kW;WAC表示空气压缩机耗功,kW;WFC表示燃料压缩机耗功,kW;WCOMP表示CO2压缩机耗功,kW。
基于热力学第一定律同时考虑系统发电及供热,系统综合利用效率ηt计算公式为:
ηt=WSOFC+WGTWACWFCWCOMP+QHmfuel×QLHV,fuel
式中:QH表示系统供热量,kW。
㶲分析从能量质量角度对系统进行评价[23],系统㶲效率计算为:
ηexe=EinEdEin
式中:Ed表示㶲损失,kW。
部件的㶲损率定义为该部件的㶲损失占系统总㶲损失的大小:
y=EdEd,system
式中:Ed,system表示系统总㶲损失,kW。
本文对集成CLHG的CO2零排放SOFC/GT/ ORC混合动力系统进行研究,分析各关键参数对系统性能影响规律。在额定工况下,系统的输出功率和效率见表4
表4所示,系统发电量为139.16 kW,发电效率为62.42%,系统综合能源利用效率74.10%,同时,本系统可以将CO2完全捕获并加压回收。
系统各部分㶲损及比例见表5。可以看出,在额定工况下,系统的总输入㶲为247.65 kW,总输出㶲为142.96 kW,系统㶲效率为57.73%。系统输出㶲大部分是电㶲,共139.16 kW,输出的热量㶲仅有3.80 kW。系统总㶲损失为104.69 kW,其中,CLHG及SOFC㶲损最大,损失率分别为37.36%和22.43%。这主要是因为在CLHG以及SOFC中发生了复杂的热化学或电化学反应,其余部件的㶲损均较小,㶲损率均超过10%,这表明系统的负荷温度符合能量梯级利用的原则,有效减少了损失。
系统不稳定时,需要额外补充H2,这是因为SOFC不能完全利用H2,阳极出口回流到SR的气体中包含的H2量不满足需求,系统稳定后就不需要额外H2输入。本系统在模型建立最初输入0.67 mol/h氢气,完成循环后系统稳定不需要额外氢气。
燃料流量的变化主要通过影响SOFC的电流密度、电压等参数从而影响系统性能,燃料流量对系统性能影响如图3图4所示。
图3图4所示:当燃料流量从0.5 kmol/h增加到4 kmol/h时,系统净输出电功率从72.32 kW增加到487.95 kW,增加量为415.63 kW;供热量从13.11 kW增加到了103.68 kW,增加量90.59 kW;系统电效率从64.88%降低到了54.71%,降低了10.17百分点;系统㶲效率从59.97%降低到了50.78%,降低了9.19百分点;系统综合能源利用率效率从76.64%降低到了66.34%,降低了10.27%。可以看出,系统综合能源利用效率降低的主要原因是随着燃料流量的增加,净输出功率的增加幅度小于耗功的增加幅度,SOFC的电流密度从74.35 mA/cm2增加到了594.79 mA/cm2,电压从0.795 V降低到0.538 V,SOFC的效率逐渐下降,化学能更多的转化为热能,能量损失随着燃料流量的增加而增加。
燃料利用率表示在燃料电池中,燃料被利用的程度。由于受到材料、热力学、动力学等因素的限制,燃料在反应过程中不可能被完全利用。燃料利用率对系统性能的影响如图5图6所示。
图5所示:当燃料利用率从0.25增加到0.95时,系统净输出电功率从148.14 kW降到132.30 kW,降低了15.84 kW,供热量变化不大,系统电效率从66.45%降低到了59.34%,降低了7.11百分点;系统㶲效率从61.35%降低到了54.96%,降低了6.39百分点;系统综合能源利用效率从78.13%降到了71.03%,降低了7.10百分点。随燃料利用率增加,SOFC输出功率降低,其原因是SOFC阳极回流及额外H2流量的补充,使得在不同燃料利用率下,SOFC实际消耗的H2量相同(即CLHG产生的氢气量),所以电流密度保持148.70 mA/cm2不变。但电压从0.85 V下降到0.67 V,这是因为阳极入口及出口H2量的变化以及阴极进气量的不同,使得SOFC效率降低,化学能更多转换为热能并被燃气轮机及ORC利用,但其发电量的增加率小于SOFC发电量的减少率,因此系统总的发电效率及系统效率降低。燃料利用率降低虽然可以提高系统效率,但会增加系统不稳定时H2的额外补充量,经济效率更低。
温度对SOFC电压影响如图7所示。SOFC工作温度对系统性能的影响如图8图9所示,温度变化范围为800~1 100 ℃。SOFC温度的变化影响阳极和阴极出口气体温度,从阳极回流到CLHG气体温度变化不仅会影响CLHG性能,也会影响SOFC电压。
图7可以看出,随着SOFC工作温度的增加,其电压从0.619 V先增加0.781 V,后减小到0.776 V,在1 050 ℃时SOFC电压达到最大值。
图8图9可以看出,随着SOFC工作温度的增加,系统净输出电功率从124.47 kW增加到149.28 kW,增加了24.81 kW,供热量变化不大,系统电效率从55.8%增加到了66.96 %,增加了11.13百分点,系统㶲效率从51.79%增加到了61.81%,增加了10.02百分点,系统效率综合能源利用从67.51%增加到了78.64%,增加了11.13百分点。引起这些变化的主要原因是,随着SOFC工作温度的增加,在温度达到1 050 ℃时,电流密度保持不变,但产生的电压从0.619 V升高到了0.781 V,使得SOFC的输出功率与效率增加,同时,随着SOFC工作温度的增加,WAC2逐渐降低,WGT2也逐渐降低,SOFC阴极入口空气量逐渐减少,出口气体的温度逐渐增加,因此被ORC回收的预热降低,使得WGT3降低,但减少率小于SOFC输出功率的增加率;SOFC工作温度增到1 050 ℃后,SOFC产生的电压降低到0.776 V,输出功率降低,WGT2增加,增加率大于SOFC输出功率的减少率。因此,随着SOFC工作温度的增加,更多的化学能转换成电能,系统效率逐渐增加,但效率的增长速率随着温度的增加而减缓。温度增加对材料提出更高要求,因此需要进一步对经济性进行分析。
系统工作压力对系统性能的影响如图10图11所示,压力的变化范围为3×105~12×105 Pa。
随着系统工作压力的增加,系统的净输出功率及系统电效率、系统综合利用效率先逐渐增加,在工作压力为7×105 Pa时到达各项数值最高点,之后随着工作压力的增加,系统的净输出功率及系统电效率、系统效率逐渐降低。工作压力在3×105~7×105 Pa时,系统净输出电功率从134.60 kW增加到140.02 kW,增加了5.42 kW,供热量变化不大,系统电效率从60.37%增加到了62.80%,增加了2.43百分点,系统㶲效率从55.89%增加到了58.08%,增加了2.19百分点,系统综合能源利用效率从72.06%增加到了74.49%,降低了2.43百分点,在工作压力大于7×105 Pa时,系统净输出电功率从140.02 kW降低到136.03 kW,降低了3.99 kW,供热量变化不大,系统电效率从62.80%降低到了61.01%,降低了1.79百分点,系统㶲效率从58.08%降低到了56.46%,降低了1.62百分点,系统综合能源利用效率从74.49%降低到了72.70%,降低了1.79百分点。随着工作压力的增加,SOFC电流密度不变,产生的电压从0.727 V增加到了0.760 V,输出功率逐渐增加,但随SOFC工作压力的增加,压气机的耗功与燃气轮机输出功也在增加。综合考虑下,系统效率在SOFC工作压力为7×105 Pa时达到最大值,但压力的增加对设备材料提出更高要求,也会带来成本的增加。
本文提出了一种集成CLHG的二氧化碳零排放SOFC/GT/ORC混合动力系统。CLHG过程降低了甲烷的燃料品位,为SOFC提供了氢气,实现了燃料品位的梯级降低。SOFC阳极出口气体完全回流到CLHG,可以高效发电并提供部分热,实现二氧化碳的完全捕集,减少甲烷利用时有害气体的产生,同时由于SOFC直接利用氢气,可以避免积碳。碳捕集过程有效避免了系统的碳排放,与传统的SOFC-GT系统相比对环境影响更小。在额定工况下,本文提出的系统综合能源利用效率可达74.10%,电效率为62.42%,㶲效率为57.73%。本文分析了关键参数如燃料流量、燃料利用率、SOFC工作温度及系统工作压力对系统性能的影响,揭示了系统性能变化规律。
1)系统的综合能源效率、电效率以及㶲效率均随着甲烷流量的增加而减小,这主要是因为在燃料流量增加的过程中热损失也逐渐增大。
2)系统性能随着电池燃料利用率的增加而减小,且减小趋势逐渐增大。
3)系统化学链燃烧过程的㶲损失最大,占总㶲损失的37.36%;其次是SOFC过程,占总㶲损失的22.43%;其余部件㶲损失均较小,表明系统的能量匹配较合理。
4)在本研究系统工作压力范围内,系统综合能源利用效率、电效率、㶲效率先逐渐增加后逐渐下降,并在系统压力为7×105 Pa时达到最大值。
  • 中石油昆仑燃气有限公司科学研究与技术开发项目(2023-KLKJ-10)
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doi: 10.19666/j.rlfd.202409206
  • 接收时间:2024-09-07
  • 首发时间:2026-03-06
  • 出版时间:2025-05-25
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  • 收稿日期:2024-09-07
基金
Scientific Research and Technology Development Project of PetroChina Kunlun Gas Co., Ltd(2023-KLKJ-10)
中石油昆仑燃气有限公司科学研究与技术开发项目(2023-KLKJ-10)
作者信息
    1.中国石油天然气股份有限公司规划总院,北京 100000
    2.华北电力大学能源动力与机械工程学院,北京 100000
    3.中石油昆仑燃气有限公司,北京 100000

通讯作者:

段立强(1973),男,博士,教授、博导,主要研究方向为分布式能量系统,燃料电池复合动力系统、太阳能-化石燃料多能互补动力系统,
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2种不同金属材料的力学参数

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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
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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