Article(id=1236596130197336299, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236596124832821317, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202409218, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1727539200000, receivedDateStr=2024-09-29, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772757092283, onlineDateStr=2026-03-06, pubDate=1748102400000, pubDateStr=2025-05-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772757092283, onlineIssueDateStr=2026-03-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772757092283, creator=13701087609, updateTime=1772757092283, 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=1, endPage=12, ext={EN=ArticleExt(id=1236596130528686339, articleId=1236596130197336299, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Techno-economic analysis and carbon emission prediction for synthetic ammonia system coupling different hydrogen production technologies, columnId=1236596126195970127, journalTitle=Thermal Power Generation, columnName=Special topic on new power generation technology, runingTitle=null, highlight=null, articleAbstract=

In the context of “carbon peak” and “carbon neutrality”, using renewable electricity to electrolyze water to produce hydrogen and synthesize ammonia can not only consume renewable energy and solve the problem of hydrogen storage and transportation, but also promote the green transformation of the conventional ammonia synthesis process. To investigate the effect of different hydrogen production schemes on technical and economic performance of the synthetic ammonia system, the system thermal and economic performance of three hydrogen production schemes, including proton exchange membrane electrolyzer hydrogen production, proton exchange membrane electrolyzer and alkaline water electrolyzer hydrogen production in a 1:1 ratio, and alkaline water electrolyzer hydrogen production, are compared and analyzed. The hot and cold integration of the synthetic ammonia system with coordinated hydrogen production by proton exchange membrane electrolyzer and alkaline water electrolyzer is analyzed by combining pinch analysis with mathematical programming. The results show that, the system exergy efficiencies of the above three hydrogen production schemes are 60.3%, 56.1% and 52.5%, respectively, and the carbon emissions of ammonia also increase due to the increase in net power consumption of the system. Benefiting from alkaline water electrolyzer’s mature hydrogen production process, the alkaline water electrolyzer hydrogen production scheme has the shortest investment payback period of 6.4 years, while the proton exchange membrane electrolyzer hydrogen production scheme has the longest investment payback period of 12.8 years. The thermal integration analysis of the synthetic ammonia system for the coordinated hydrogen production of proton exchange membrane electrolyzer and alkaline water electrolyzer shows that the low-temperature waste heat below 100 ℃ in the system is released to the environment via cold utilities. In addition, increasing the operating temperature of the electrolyzer is beneficial to improving thermal performance of the system, while lowering electricity price and increasing the annual operating hours of the system will help to improve the economic performance of the system.

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“双碳”背景下,利用可再生电力电解水制氢合成氨,不仅可以消纳可再生能源,解决氢能储运难题,也促进传统合成氨工艺的绿色转型。为了探究不同制氢方案对合成氨系统技术经济性的影响,对比分析了质子交换膜电解槽制氢、质子交换膜电解槽和碱液电解槽制氢比例为1:1以及碱液电解槽制氢3种制氢方案的系统热力性能和经济性能的表现,并利用夹点分析和数学规划相结合的方法,分析了质子交换膜电解槽和碱液电解槽协同制氢合成氨系统的冷热物流集成情况。结果表明:上述3种制氢方案的系统㶲效率依次为60.3%、56.1%和52.5%,而氨的碳排放也因系统净耗电量的增加而增加;受益于碱液电解槽成熟的制氢工艺,碱液电解槽制氢方案的投资回收期最短,为6.4年,质子交换膜电解槽制氢方案投资回收期最长,达到了12.8年;质子交换膜电解槽和碱液电解槽协同制氢的合成氨系统热集成分析表明,系统中低于100 ℃的低温余热可经过冷公用工程排向环境;此外,提升电解槽运行温度,有利于改善系统的热力性能,而降低电价、提升系统年运行时长有助于改善系统的经济性。

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张汉飞(1986),男,博士,讲师,主要研究方向为先进能量系统集成优化技术,
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杜逸云(1989),女,博士,高级工程师,主要研究方向为氢能及绿电转化技术,

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杜逸云(1989),女,博士,高级工程师,主要研究方向为氢能及绿电转化技术,

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杜逸云(1989),女,博士,高级工程师,主要研究方向为氢能及绿电转化技术,

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figureFileBig=Dtki9GRpnTtoTKafhDcUzQ==, tableContent=null), ArticleFig(id=1236610620095778864, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=图10, caption=运行时长对合成氨系统经济性的影响, figureFileSmall=QIOv1QPHehWMlpdhibeMdQ==, figureFileBig=Dtki9GRpnTtoTKafhDcUzQ==, tableContent=null), ArticleFig(id=1236610620209025084, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.1, caption=

Parameters of the PEMEC model

, figureFileSmall=null, figureFileBig=null, tableContent=
项目数值
λm22
αa2
αc0.5
j0,a/(A·cm–2)10–7
j0,c/(A·cm–2)0.5
δm/μm178
), ArticleFig(id=1236610620309688388, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表1, caption=

PEMEC模型参数

, figureFileSmall=null, figureFileBig=null, tableContent=
项目数值
λm22
αa2
αc0.5
j0,a/(A·cm–2)10–7
j0,c/(A·cm–2)0.5
δm/μm178
), ArticleFig(id=1236610620431323209, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.2, caption=

Parameters of the AWE model

, figureFileSmall=null, figureFileBig=null, tableContent=
项目数值
r1/(Ω·m2)4.451 53×10–5
r2/(Ω·m2·℃–1)6.888 74×10–9
d1/(Ω·m2)–3.129 96×10–6
d2/(Ω·m2·MPa–1)4.471 37×10–8
s/V0.338 24
t1/(m2·A–1)–0.015 39
t2/(m2·℃·A–1)2.001 81
t3/(m2·℃·A–1)15.241 78
f11/(A2·m–4)478 645.74
f12/(A2·m–4·℃–1)–2 953.15
f211.039 6
f22/℃–1–0.001 04
), ArticleFig(id=1236610620544569425, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表2, caption=

AWE模型的参数

, figureFileSmall=null, figureFileBig=null, tableContent=
项目数值
r1/(Ω·m2)4.451 53×10–5
r2/(Ω·m2·℃–1)6.888 74×10–9
d1/(Ω·m2)–3.129 96×10–6
d2/(Ω·m2·MPa–1)4.471 37×10–8
s/V0.338 24
t1/(m2·A–1)–0.015 39
t2/(m2·℃·A–1)2.001 81
t3/(m2·℃·A–1)15.241 78
f11/(A2·m–4)478 645.74
f12/(A2·m–4·℃–1)–2 953.15
f211.039 6
f22/℃–1–0.001 04
), ArticleFig(id=1236610620641038420, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.3, caption=

Validation of the ammonia synthesis model

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项目模拟值工业值误差/%
氢气和氮气摩尔比2.993.000.30
氨合成塔运行温度/℃460~470449~4782.45~1.46
氨合成塔运行压力/MPa13.4~14.213.7~14.02.20~1.43
氮气转化率/%30.931.10.64
纯氨的质量分数/%99.899.90.10
), ArticleFig(id=1236610620758478939, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表3, caption=

合成氨模型的验证

, figureFileSmall=null, figureFileBig=null, tableContent=
项目模拟值工业值误差/%
氢气和氮气摩尔比2.993.000.30
氨合成塔运行温度/℃460~470449~4782.45~1.46
氨合成塔运行压力/MPa13.4~14.213.7~14.02.20~1.43
氮气转化率/%30.931.10.64
纯氨的质量分数/%99.899.90.10
), ArticleFig(id=1236610620880113762, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.4, caption=

Design parameters of the synthetic ammonia system

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项目数值
合成氨压力/MPa20
氨合成塔运行温度/℃450~500
PEMEC运行温度/℃80
PEMEC运行压力/MPa1.5
AWE运行温度/℃85
AWE运行压力/MPa0.7
氨冷冻单元制冷系数2.14
空分装置产生每吨O2的能耗/(kW·h)160
泵的等熵效率/%70
压缩机等熵效率/%80
), ArticleFig(id=1236610620993359975, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表4, caption=

合成氨系统设计参数

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项目数值
合成氨压力/MPa20
氨合成塔运行温度/℃450~500
PEMEC运行温度/℃80
PEMEC运行压力/MPa1.5
AWE运行温度/℃85
AWE运行压力/MPa0.7
氨冷冻单元制冷系数2.14
空分装置产生每吨O2的能耗/(kW·h)160
泵的等熵效率/%70
压缩机等熵效率/%80
), ArticleFig(id=1236610621127577708, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.5, caption=

Economic evaluation parameters of the synthetic ammonia system

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项目数值
合成氨系统寿命/a25
氨产量/(t·h–1)22.5
利率/%5
氨价/(元·t–1)4 500
年运行小时数/h8 000
电价/(元·(kW·h)–1)0.3
PEMEC投资成本/(元·kW–1)7 200
PEEMC寿命/h60 000
AWE投资成本/(元·kW–1)1 600
AWE寿命/a10
), ArticleFig(id=1236610621245018225, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表5, caption=

合成氨系统经济性评估参数

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项目数值
合成氨系统寿命/a25
氨产量/(t·h–1)22.5
利率/%5
氨价/(元·t–1)4 500
年运行小时数/h8 000
电价/(元·(kW·h)–1)0.3
PEMEC投资成本/(元·kW–1)7 200
PEEMC寿命/h60 000
AWE投资成本/(元·kW–1)1 600
AWE寿命/a10
), ArticleFig(id=1236610621366653048, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.6, caption=

Energy balance table of the synthetic ammonia system for different hydrogen production schemes

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项目方案1方案2方案3
PEMEC耗电/MW2001000
AWE耗电/MW0114.43228.87
空分装置耗电/MW0.740.740.74
辅机设备耗电/MW12.6513.3814.31
朗肯循环发电/MW8.38.38.3
净耗电/MW205.09220.25235.42
氨低位热值/MW116.11116.11116.11
能量效率/%56.652.749.3
㶲效率/%60.356.152.5
氨生产成本/(元·t–1)4 275.13 807.73 331.9
投资回收期/a12.89.96.4
风电制氢合成氨系统单位质量氨碳排放量/kg0.1090.1170.125
光伏制氢合成氨系统单位质量氨碳排放量/kg0.3200.3430.367
), ArticleFig(id=1236610621450539134, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表6, caption=

不同制氢方案的合成氨系统能量平衡

, figureFileSmall=null, figureFileBig=null, tableContent=
项目方案1方案2方案3
PEMEC耗电/MW2001000
AWE耗电/MW0114.43228.87
空分装置耗电/MW0.740.740.74
辅机设备耗电/MW12.6513.3814.31
朗肯循环发电/MW8.38.38.3
净耗电/MW205.09220.25235.42
氨低位热值/MW116.11116.11116.11
能量效率/%56.652.749.3
㶲效率/%60.356.152.5
氨生产成本/(元·t–1)4 275.13 807.73 331.9
投资回收期/a12.89.96.4
风电制氢合成氨系统单位质量氨碳排放量/kg0.1090.1170.125
光伏制氢合成氨系统单位质量氨碳排放量/kg0.3200.3430.367
), ArticleFig(id=1236610621576368261, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=EN, label=Tab.7, caption=

Stream information of the ammonia system

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部件入口温度/℃出口温度/℃热负荷/kW
AWE氢气冷却器87.635.0432.6
电解槽入口换热器86.185.0999.3
PEMEC氢气冷却器81.235.0379.7
电解槽入口换热器80.780.01 493.4
深冷空分单元5号多级压缩机间冷器1215.035.01 002.3
5号多级压缩机间冷器2215.035.01 014.0
合成氨单元6号多级压缩机间冷器1121.635.01 923.3
6号多级压缩机间冷器2122.435.01 954.5
6号多级压缩机间冷器3122.635.01 983.1
6号多级压缩机间冷器4123.035.02 028.0
8号换热器36.5182.011 195.4
9号换热器182.0305.03 932.0
10号换热器496.035.037 013.8
11号换热器–5.035.02 205.3
12号换热器1 000.0115.03 039.2
系统废气燃烧锅炉1 000.01 000.0823.5
冷公用工程5.015.029 001.0
余热锅炉蒸发器129.0324.87 280.0
蒸发器2324.8324.86 393.4
蒸发器3324.8574.84 601.7
再热器1484.1534.0644.1
再热器2109.4109.42 722.1
凝汽器157.633.0251.1
凝汽器233.133.012 974.2
补充水25.028.067.7
), ArticleFig(id=1236610621706391689, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236596130197336299, language=CN, label=表7, caption=

合成氨系统流股信息

, figureFileSmall=null, figureFileBig=null, tableContent=
部件入口温度/℃出口温度/℃热负荷/kW
AWE氢气冷却器87.635.0432.6
电解槽入口换热器86.185.0999.3
PEMEC氢气冷却器81.235.0379.7
电解槽入口换热器80.780.01 493.4
深冷空分单元5号多级压缩机间冷器1215.035.01 002.3
5号多级压缩机间冷器2215.035.01 014.0
合成氨单元6号多级压缩机间冷器1121.635.01 923.3
6号多级压缩机间冷器2122.435.01 954.5
6号多级压缩机间冷器3122.635.01 983.1
6号多级压缩机间冷器4123.035.02 028.0
8号换热器36.5182.011 195.4
9号换热器182.0305.03 932.0
10号换热器496.035.037 013.8
11号换热器–5.035.02 205.3
12号换热器1 000.0115.03 039.2
系统废气燃烧锅炉1 000.01 000.0823.5
冷公用工程5.015.029 001.0
余热锅炉蒸发器129.0324.87 280.0
蒸发器2324.8324.86 393.4
蒸发器3324.8574.84 601.7
再热器1484.1534.0644.1
再热器2109.4109.42 722.1
凝汽器157.633.0251.1
凝汽器233.133.012 974.2
补充水25.028.067.7
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耦合不同制氢技术的合成氨系统技术经济性分析及碳排放评估
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杜逸云 1 , 刘路尧 2 , 陈越 3 , 于吉庆 3 , 张馨艺 1 , 张栋顺 1 , 刘先海 4 , 李标 1 , 王桂楠 3 , 张汉飞 2
热力发电 | 新型发电技术专题 2025,54(5): 1-12
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热力发电 | 新型发电技术专题 2025, 54(5): 1-12
耦合不同制氢技术的合成氨系统技术经济性分析及碳排放评估
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杜逸云1 , 刘路尧2, 陈越3, 于吉庆3, 张馨艺1, 张栋顺1, 刘先海4, 李标1, 王桂楠3, 张汉飞2
作者信息
  • 1.国核电力规划设计研究院有限公司,北京 100095
  • 2.华北电力大学能源动力与机械工程学院,北京 102206
  • 3.吉林电力股份有限公司,吉林 长春 130022
  • 4.大安吉电绿氢能源有限公司,吉林 白城 131312
  • 杜逸云(1989),女,博士,高级工程师,主要研究方向为氢能及绿电转化技术,

通讯作者:

张汉飞(1986),男,博士,讲师,主要研究方向为先进能量系统集成优化技术,
Techno-economic analysis and carbon emission prediction for synthetic ammonia system coupling different hydrogen production technologies
Yiyun DU1 , Luyao LIU2, Yue CHEN3, Jiqing YU3, Xinyi ZHANG1, Dongshun ZHANG1, Xianhai LIU4, Biao LI1, Guinan WANG3, Hanfei ZHANG2
Affiliations
  • 1.State Nuclear Electric Power Planning Design & Research Institute Co., Ltd., Beijing 100095, China
  • 2.School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China
  • 3.Jilin Electric Power Co., Ltd., Changchun 130022, China
  • 4.Daan Jilin Electric Power Green Hydrogen Energy Co., Ltd., Baicheng 131312, China
出版时间: 2025-05-25 doi: 10.19666/j.rlfd.202409218
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“双碳”背景下,利用可再生电力电解水制氢合成氨,不仅可以消纳可再生能源,解决氢能储运难题,也促进传统合成氨工艺的绿色转型。为了探究不同制氢方案对合成氨系统技术经济性的影响,对比分析了质子交换膜电解槽制氢、质子交换膜电解槽和碱液电解槽制氢比例为1:1以及碱液电解槽制氢3种制氢方案的系统热力性能和经济性能的表现,并利用夹点分析和数学规划相结合的方法,分析了质子交换膜电解槽和碱液电解槽协同制氢合成氨系统的冷热物流集成情况。结果表明:上述3种制氢方案的系统㶲效率依次为60.3%、56.1%和52.5%,而氨的碳排放也因系统净耗电量的增加而增加;受益于碱液电解槽成熟的制氢工艺,碱液电解槽制氢方案的投资回收期最短,为6.4年,质子交换膜电解槽制氢方案投资回收期最长,达到了12.8年;质子交换膜电解槽和碱液电解槽协同制氢的合成氨系统热集成分析表明,系统中低于100 ℃的低温余热可经过冷公用工程排向环境;此外,提升电解槽运行温度,有利于改善系统的热力性能,而降低电价、提升系统年运行时长有助于改善系统的经济性。

质子交换膜电解槽  /  碱液电解槽  /  绿氨  /  夹点分析

In the context of “carbon peak” and “carbon neutrality”, using renewable electricity to electrolyze water to produce hydrogen and synthesize ammonia can not only consume renewable energy and solve the problem of hydrogen storage and transportation, but also promote the green transformation of the conventional ammonia synthesis process. To investigate the effect of different hydrogen production schemes on technical and economic performance of the synthetic ammonia system, the system thermal and economic performance of three hydrogen production schemes, including proton exchange membrane electrolyzer hydrogen production, proton exchange membrane electrolyzer and alkaline water electrolyzer hydrogen production in a 1:1 ratio, and alkaline water electrolyzer hydrogen production, are compared and analyzed. The hot and cold integration of the synthetic ammonia system with coordinated hydrogen production by proton exchange membrane electrolyzer and alkaline water electrolyzer is analyzed by combining pinch analysis with mathematical programming. The results show that, the system exergy efficiencies of the above three hydrogen production schemes are 60.3%, 56.1% and 52.5%, respectively, and the carbon emissions of ammonia also increase due to the increase in net power consumption of the system. Benefiting from alkaline water electrolyzer’s mature hydrogen production process, the alkaline water electrolyzer hydrogen production scheme has the shortest investment payback period of 6.4 years, while the proton exchange membrane electrolyzer hydrogen production scheme has the longest investment payback period of 12.8 years. The thermal integration analysis of the synthetic ammonia system for the coordinated hydrogen production of proton exchange membrane electrolyzer and alkaline water electrolyzer shows that the low-temperature waste heat below 100 ℃ in the system is released to the environment via cold utilities. In addition, increasing the operating temperature of the electrolyzer is beneficial to improving thermal performance of the system, while lowering electricity price and increasing the annual operating hours of the system will help to improve the economic performance of the system.

proton exchange membrane electrolyzer  /  alkaline water electrolyzer  /  green ammonia  /  pinch analysis
杜逸云, 刘路尧, 陈越, 于吉庆, 张馨艺, 张栋顺, 刘先海, 李标, 王桂楠, 张汉飞. 耦合不同制氢技术的合成氨系统技术经济性分析及碳排放评估. 热力发电, 2025 , 54 (5) : 1 -12 . DOI: 10.19666/j.rlfd.202409218
Yiyun DU, Luyao LIU, Yue CHEN, Jiqing YU, Xinyi ZHANG, Dongshun ZHANG, Xianhai LIU, Biao LI, Guinan WANG, Hanfei ZHANG. Techno-economic analysis and carbon emission prediction for synthetic ammonia system coupling different hydrogen production technologies[J]. Thermal Power Generation, 2025 , 54 (5) : 1 -12 . DOI: 10.19666/j.rlfd.202409218
“双碳”目标的提出,推动了我国可再生能源的快速发展,但其波动性和随机性,限制了高比例可再生能源并入电网[1]。氢作为我国绿色能源发展的重要载体,其长距离储运以及安全性问题尚未有效解决[2-3]。而氨作为极具潜力的无碳燃料,具有储能密度高、易液化及储运成本低的优点,但传统合成氨工艺严重依赖化石能源,其中煤制氨和天然气制氨的单位质量氨碳排放分别高达4.19 kg和2.356 kg[4]。在此背景下,利用可再生电力制氢合成氨,既可解决氢气低成本储运的难题,又能减少合成氨工艺的碳排放。国际上,阿联酋阿布扎比的哈里发地区的绿氢-合成氨项目最高能够产生4万吨绿氢用于生产绿氨。在国内,以国能、国电投、吉电股份、中国氢能、明拓集团等为代表的企业正在积极布局风光制氢合成氨一体化项目,如吉林大安风光制氢合成氨示范项目。相比电化学、光催化、等离子体等温和条件合成氨工艺,采用电解水制氢及哈伯-博世法合成绿氨的技术路线,被认为最有可能实现绿氨产业化的技术路线[5]
电解水制氢技术主要包括质子交换膜电解槽(proton exchange membrane electrolyzer,PEMEC)、碱液电解槽(alkaline water electrolyzer,AWE)以及固体氧化物电解槽(solid oxide electrolyzer,SOEC)。其中,SOEC作为高温电解槽,制氢效率高,可与CO2共电解产生合成气(CO和H2),但高温运行限制了其负荷响应能力;PEMEC和AWE作为低温电解槽,AWE具有技术成熟、投资成本低等优势,但启动时间较长,负荷调节能力较差[6-7],适用于稳定电力供应下的大规模制氢;PEMEC则具有电流密度高、启动时间短和动态响应能力强的优点[8],但其寿命短、投资成本高[9],适用于电力波动大,需快速启停的场所。综上,PEMEC和AWE在负荷响应和经济性两方面存在互补性。同时,黄启帆等[10]采用网络层次分析法验证了PEMEC和AWE协同制氢方案在秒级时间尺度上制氢效率的优越性,在以小时为时间尺度,PEMEC和AWE协同制氢方案的制氢量高于仅由AWE制氢的方案,接近仅由PEMEC制氢的方案。
众多学者探讨了不同绿氨工艺技术路线的可行性。Driscoll等人[11]根据潮汐能功率曲线,利用混合整数线性规划方法探讨了氨的最低平均生产成本。黄靖钟等[12]提出了一种利用核能-碘硫热化学循环制氢合成氨的系统,实现了核热制氢与合成氨工艺的耦合。关于AWE制氢合成氨技术,Devkota等人[13]探讨了利用水电驱动AWE制氢的合成氨系统的技术经济可行性,蒙特卡罗不确定性分析表明氨的最低生产成本为418美元/t。林今等[14]指出近期应发展电网友好型AWE制氢合成氨系统,同时也强调了微电网先进控制技术在发展离网型制氢合成氨系统的必要性。关于PEMEC制氢合成氨系统,Sousa等人[15]的研究表明,由PEMEC制氢的合成氨系统比天然气重整制氢合成氨系统的单位质量氨的耗能多消耗约2 kW·h。此外,Nowicki等人[16]提出了一种利用SOEC制氢和固体电解质氧泵制氮的绿氨系统,系统的能量效率达到了52.12%,单位质量氨能耗为9.94 kW·h。Cinti等人[17]提出了一种利用SOEC制氢和改进的合成氨反应器耦合的绿氨系统,与天然气制氨工艺相比,系统单位质量氨的电耗降至8.30 kW·h。Zhang等人[18]则利用夹点分析的方法,对不同合成氨系统进行了能质集成分析,结果表明,SOEC电解水制氢合成氨系统的效率高达74%,远高于生物质气化制氨(44%)和天然气制氨(61%),同时,也强调了夹点分析方法在化工合成工艺集成设计的必要性。
综上,目前对于绿色合成氨工艺的研究,仅仅关注不同制氢方案对合成氨工艺技术经济性的影响,缺乏PEMEC和AWE协同制氢方案对绿氨工艺在系统级的热集成方案的探讨。在此背景下,本文对比分析了3种制氢方案合成氨系统技术的经济性,并利用夹点分析和数学规划相结合的方法,探讨了PEMEC和AWE协同制氢合成氨系统的系统热集成情况。
图1为低温电解槽制氢合成氨系统。在可再生电力的驱动下,水分子在电解槽的电极上发生电化学反应,分别在阴极和阳极产生氢气和氧气,电解槽产生的气液混合物分别在2号气液分离器和3号气液分离器分离出氢气和氧气,而氢气则被4号换热器冷却;另一方面,来自空分装置的氮气经过5号多级压缩机压缩至与氢气压力一致,并与氢气(流股11)按照3:1的比例混合再次进入6号多级压缩机压缩,随后与来自一级氨分离塔的部分弛放气(流股33)混合进入7号压缩机,加压至氨合成塔的运行压力,8号换热器则用来加热混合气体流股(流股20)至170~190 ℃,以防止进入氨合成塔的冷却流股温度过低。随后混合气体流股(流股21)分为3股,其中第1股流股(流股23)经过9号换热器进一步加热至300 ℃左右,以适应氨合成塔的运行工况,而第2流股(流股26)和第3流股(流股27)则作为间冷气体进入氨合成塔,调节氨合成塔内合成气的温度,提升合成氨过程中氮气的转化率。氨合成塔出口气体经过10号换热器冷却后进入氨冷冻单元,实现氨气的液化,并在一级氨分离塔中实现液氨和氢气、氮气以及其他气体的分离,而产生的弛放气(流股31)一部分(流股34)进入系统废气燃烧锅炉,另一部分(流股32)则与6号多级压缩机出口的混合气体混合重新进入合成氨回路中。最后,一级氨分离塔分离出液氨经过减压阀减压后进入二级氨分离塔进一步分离,得到纯度为99.9%的液氨(流股37),同样,二级氨分离塔排出的弛放气(流股38)送入系统废气燃烧锅炉燃烧产生高温烟气,满足合成氨系统的热需求。
本研究中采用Aspen plus化工模拟软件完成了合成氨工艺的模型搭建。
PEMEC中发生的分解反应如下。
阴极:
2H++2eH2
阳极:
H2O12O2+2H++2e
总反应:
H2OH2+12O2
PEMEC电解水所需的总电压是其开路电压、活化过电压、欧姆过电压以及扩散过电压之和[19]。考虑到扩散过电压远小于其他电压,可忽略不计[20]。PEMEC的电压VPEMEC,cell计算公式如下:
VPEMEC,cell=Vocv+Vact+Vohm
式中:Vocv为电解槽理论工作电压,V;Vact为活化过电压,V;Vohm为欧姆过电压,V。
PEMEC的理论工作电压由能斯特等式计算获得:
Vocv=1.2290.9×103(TPEMEC298)+RTPEMEC2Fln(pH2(0.1pO2)0.5pH2O)
式中:TPEMEC为PEMEC的运行温度,K;R为摩尔气体常数,取8.31 J/(mol·K);F为法拉第常数,取96 485 C/mol;pH2pO2pH2O分别为氢气、氧气和水的分压,MPa。
PEMEC阴阳极的活化过电压计算公式如下:
Vact,a=RTPEMECαaFsinh1(jPEMEC2j0,a)
Vact,c=RTPEMECαcFsinh1(jPEMEC2j0,c)
Vact=Vact,a+Vact,c
式中:Vact,cVact,a分别为PEMEC的阴极和阳极活化过电压,V;jPEMEC为PEMEC的电流密度,A/cm2j0,aj0,c分别为PEMEC阳极和阴极的交换电流密度,A/cm2αaαc分别为PEMEC阳极和阴极的电荷转移系数。
欧姆过电压主要由离子电阻和电子电阻产生,可利用欧姆定律计算[21]
Vohm= jPEMEC(Rion+Rele)
Rion=Δmσm
σm=(0.005139λm32.6)exp[1268(13031TPEMEC)]
式中:RionRele分别为离子电阻和电子电阻,Ω;δm为质子交换膜的厚度,μm;λm为质子交换膜的膜水合率;σm为质子交换膜的电导率,S/m。此外,PEMEC的产氢量nH2,pro、产氧量nO2,pro、水的消耗量nH2O,cons、耗功Wstack,PEMEC以及能量效率ηen,PEMEC的计算公式如下:
nH2,pro=ηFjPEMECAPEMECzFNPEMEC,cell=nH2O,cons
nO2,pro=12nH2,pro
Wstack,PEMEC=jPEMECAPEMECNPEMEC,cellVPEMEC,cell
ηen,PEMEC=nH2,proQLHV,H2Wstack,PEMEC
式中:APEMEC为电解槽的活化面积,m2NPEMEC,cell为电解槽中的单元数;QLHV,H2为氢气的低位热值,kJ/kg。
PEMEC模型相关参数的取值见表1[19]图2为PEMEC模型模拟数据与文献[22]数据的对比。由图2可知,两者具有较好的一致性,验证了PEMEC模型的可靠性。
当电极之间有足够的电位差时,在KOH或NaOH溶液中,AWE将在阴极发生析氢反应,在阳极发生析氧反应,其反应方程式如下。
阴极:
2H2O+2eH2+2OH
阳极:
2OH2e+H2O+0.5O2
总反应:
H2OH2+12O2
AWE实际的工作电压计算公式如下[23]
Vcell = Vrev+[(r1+d1)+r2TAWE+0.1d2pAWE]jAWE+slog[(t1+t2TAWE+t3TAWE2)jAWE+1]
式中:Vrev为水发生分解反应的可逆电压,V;TAWE为电解槽的工作温度,℃;pAWE为电解槽的工作压力,MPa;jAWE为电解槽的电流密度,A/m2r1r2d1d2t1t2t3以及s均为修正系数,体现电解槽工作压力、温度和电流密度对AWE实际工作电压的影响。
同时,利用法拉第效率来评价电解槽产氢的有效性,即实际的氢气产量和理想的氢气产量的比值,同电解槽的极化曲线类似,同样采用经验公式拟合[23-24]
ηF=nH2,pronH2,th=(jAWE       2f11+f12TAWE+jAWE       2)(f21+f22TAWE)
式中:nH2,th为AWE的理论产氢量,mol/s;f11f12f21f22为修正系数,体现电解槽工作温度和电流密度对法拉第效率的影响。
氢气、氧气产量以及电解槽水的消耗量的计算公式如下:
nH2,pro=ηFjAWEAAWEzFNAWE,cell
nO2,pro=12nH2,pro
nH2O,cons=nH2,pro
式中:AAWE为AWE的活化面积,m2NAWE,cell为碱液电解槽中的单元数。
AWE的电耗和能量效率的计算公式如下:
WstackAWE=jAWEAAWENAWE,cellVAWE,cell
ηen,AWE=nH2,proQLHV,H2Wstack,AWE
式中:AAWE为电解槽的活化面积,m2NAWE,cell为电解槽中的单元数。
AWE模型参数的取值见表2,AWE模型与文献[23]的数据对比如图3所示。由图3可知,两者具有较好的一致性,证明了模型的可靠性。
合成氨的反应方程式如下:
N2+3H22NH3
以工业中实际运行的三床间冷氨合成塔为参照对象,利用Aspen plus软件采用Temkin-Pyzhev动力学模型对合成氨系统进行了模拟,合成氨的反应动力学模型如下[25-26]
rNH3=2fρcat(k1pN2(0.1pH2)1.5pNH3-k20.1pNH3(0.1pH2)1.5)
k1=1.79×104e87 090/RT
k2=2.75×1016e19 8464/RT
式中:pN2pH2pNH3分别为氮气、氢气和氨气的分压,MPa;ρcat为催化剂的体积密度,kg/m3T为氨合成塔的温度,K;f为校正因子。合成氨模型与文献[18]的验证结果见表3。由表3可见,误差均小于5%,验证了模型的可靠性。
压缩机的出口温度及耗功的计算公式如下:
Tout=Tin(1+(ε(k1)/k-1)/ηcomp)
Wcomp=m(houthin)
式中:ε为压缩机的压比;k为气体的比热容比;ηcomp为压缩机的等熵效率;houthin分别为压缩机出口和进口流股的比焓,kJ/kg;m为流股的质量流量,kg/s。
系统中泵的等熵效率和耗功的计算公式如下:
ηpump=hout,shinhouthin
Wpump=m(hout-hin)
式中:ηpump为泵的等熵效率;Wpump为泵的耗功,kW;hout,s为等熵过程中泵出口的理论比焓,kJ/kg。
换热器的能量平衡计算公式如下:
mhot(hhot,inhhot,out)=mcold(hcold,inhcold,out)
式中:hout,inhout,out分别为换热器进、出口热流股的比焓,kJ/kg;hcold,inhcold,out分别为换热器进、出口冷流股的比焓,kJ/kg。
能量效率为输入系统的能量转换为输出的能力,㶲效率则从热力学第二定律的角度反映系统将输入的能量转换为可用能的能力,其定义为系统的输出㶲与输入㶲的比值,故借助系统能量效率ηen,sys和㶲效率ηex,sys评价合成氨系统不同制氢方案热力性能表现[18],忽略了进入电解槽中常温水的㶲及电解槽阳极出口氧气的㶲,其计算公式如下:
ηen,sys=mNH3QLHV,NH3Wnet
ηex,sys=mNH3ExNH3Wnet
式中:mNH3为氨的质量流量,kg/s;QLHV,NH3为氨的低位热值,kJ/kg;Wnet为外界提供给合成氨系统的电量,kW;ExNH3为氨的燃料㶲,kJ/kg。表4为合成氨系统的设计参数[18,23]
选取了氨生产成本和投资回收期为合成氨系统的经济性评价指标[27-28],计算公式如下:
Cdep=Cinvi(i+1)n(i+1)n1
CNH3=Copt+CdepCrev,bypMNH3
Copt=Cut+Celec,buy+Clabor
τ=CinvCrev,NH3+Crev,bypCopt
式中:Cdep为折旧成本,元/a;Cinv为系统的投资成本,元,根据氨合成塔、换热器、压缩机等设备的运行压力、温度以及原材料单价估算[18,28]Copt为系统的运行成本,元;i为年利率;Cut为催化剂、水等公用工程的费用,元;Celec,buy为电力成本,元;Clabor为运行人员的工资,元;n为合成氨系统的寿命,年;CNH3为氨的生产成本,元/t;MNH3为氨的产量,t/a;Crev,byp为副产品氧的收益,元/a;τ为合成氨系统的收益回收期,a;Crev,NH3为氨的收益,元/a。表5为合成氨的经济性评估参数[28-31]
选取单位质量氨的CO2排放量评价不同制氢方案下合成氨路线的碳排放情况,计算公式如下:
CENH3=WiCEresmNH33600
式中:CENH3为单位质量氨的CO2排放量,kg;Wi为系统的电力输入功率,kW·h;CEres为可再生电力的度电CO2排放量,其中风力发电的度电CO2排放量为0.012 kg[4],光伏发电的度电量排放量为0.035 1 kg[4]
合成氨系统中PEMEC和AWE的制氢量的比值定义如下:
R=nPEMEC,H2nAWE,H2
式中:nPEMEC,H2为PEMEC的制氢量,mol/s;nAWE,H2为AWE的制氢量,mol/s。
当合成氨系统的氨产量为22.5 t/h时,PEMEC和AWE不同制氢比例R对合成氨系统技术经济性的影响如图4所示。随着PEMEC制氢比例的降低,合成氨系统的能量效率逐渐减少,主要是因为PEMEC制氢效率(68.6%)高于AWE制氢效率(60.0%),减少了系统的耗电量;经济性方面,PEMEC投资成本高于AWE投资成本,故当PEMEC制氢比例降低后,系统的氨生产成本呈现下降的趋势。考虑到不同地区合成氨系统的可再生电力输入部分的波动性差异,故不同地区的合成氨项目应根据当地风光资源条件对制氢比例进行优化。
本文则选取了仅由PEEMC制氢(方案1)、PEMEC和AWE制氢比例R=1(方案2)以及仅由AWE制氢(方案3)3种制氢方案进行分析,具体见表6
随着合成氨系统氢气来源由仅来自PEMEC变为仅来自AWE,系统的能量效率由56.6%降至49.3%。主要原因是AWE的制氢效率低于PEMEC,当合成氨系统的氨产量不变,即所需的氢气量恒定时,电解槽的耗电功率由200.00 MW升至228.87 MW,同时由于来自AWE的氢气压力低于PEMEC,使得系统辅机设备的耗电功率同步增加,最终导致合成氨系统的净耗电由205.09 MW升至235.42 MW,进而降低了合成氨系统的能量效率。此外,单位质量氨的碳排放也因可再生电力输入的增加同步增加,若合成氨系统的可再生电力仅来自风电,PEMEC制氢的合成氨系统单位质量氨的碳排放最低,为0.109 kg,AWE制氢的合成氨系统单位质量氨的碳排放最高,为0.125 kg。由于光伏组件在制备时,提纯硅耗能较高,所以当可再生电力仅来自光伏时,3种制氢方案单位质量氨的碳排放均高于风电制氢合成氨,分别为0.320、0.343、0.367 kg。
尽管合成氨系统AWE制氢比例的增加不利于提升系统的热力性能,但受益于AWE成熟的制氢工艺,AWE的投资成本远低于PEMEC,进而使得系统的氨生产成本和投资回收期随着AWE制氢比例的增加而有所降低。
当合成氨系统的年氨产量为18万吨/a时,系统在不同制氢方案的初始投资分布直方图如图5所示。
当系统的氢气仅来自PEMEC时,系统初始投资金额达到了58.99亿元,其中PEMEC的投资占比最高,为77.45%,这是导致合成氨系统经济性表现不佳的主要因素,使得系统的氨生产成本为4 275.1元/t,投资回收期为12.8年;而当系统中PEMEC和AWE的制氢比例为1:1时,由于AWE的初投资低,故系统的总投资金额减至41.96亿元,进而使得系统的氨生产成本降至3 807.7元/t,投资回收期为9.9年;当系统的氢气仅来自AWE时,系统的总投资为仅由PEMEC制氢的41.97%,低至24.76亿元,氨生产成本为3 331.9元/t,投资回收期减至6.4年。
研究表明,在电解槽合理的运行温度范围内提升其运行温度有利于提升电解槽的性能表现,此外,应避免因电解槽运行温度过高导致电解槽发生超温和退化[23,32-37]图6为PEMEC运行温度对系统热力性能的影响。由图6可知,当PEMEC的运行温度由55 ℃升至80 ℃时,PEMEC的制氢效率由67.9%升至68.6%,方案1系统的能量效率由56.0%升至56.6%,方案2系统的能量效率由52.3%升至52.5%。这主要是因为电解槽运行温度的提升,降低了PEMEC的开路电压和欧姆电压,从而降低了电解槽的总电压,当通入PEMEC的电流和制氢量不变时,电解槽的单位制氢能耗减少,若氨产量保持不变,系统的耗电量将同步减少,进而改善系统的热力性能。
图7展示了AWE运行温度的变化对系统热力性能的影响。由图7可知:当AWE的运行温度由60 ℃升至85 ℃时,AWE的制氢效率增幅为1.9百分点,方案2系统的能量效率增幅为0.9百分点,方案3系统的能量效率增幅为1.5百分点;与PEMEC类似,主要是因为AWE运行温度的提升,进而降低了电解槽的内阻损失,使得电解槽的单位制氢能耗减少。
利用夹点分析的方法,明确合成氨工艺中换热温差最小处,并将合成氨工艺化为2个温度区间,即高于夹点温度和低于夹点温度2部分。当流股温度高于夹点温度时,应选择系统中的冷流股进行冷却,避免引入外界冷源进行冷却;当流股温度低于夹点温度时,应选择系统中的热流股进行加热,避免引入外界热源加热,从而实现系统中不同温度区间内冷热流股的合理匹配。根据合成氨工艺中换热器冷热物流的进出口温度和热负荷(表7),采用夹点分析和数学规划相结合的方法,绘制了合成氨系统在PEMEC和AWE制氢比例为1:1时(方案2)的冷热集成曲线如图8所示。
图8可以发现,由于合成氨过程释放大量的热量,故在低温电解槽制氢合成氨系统无需引入热公用工程满足工艺的热负荷需求,只需引入冷公用工程排除系统余热即可。具体而言,系统冷热物流的换热夹点温度为481.1 ℃,在夹点温度以上时,主要是将余热锅炉出口的高温烟气(1 000 ℃)以及合成氨装置出口高温粗氨合成气(496 ℃)降温至夹点温度,并将热量用于加热过热蒸汽由481.1 ℃升至574.0 ℃;当温度降至夹点温度以下时,同压缩机出口气体一起,分别用于加热余热回收子系统中的主给水,产生饱和蒸汽、过热蒸汽以及用于加热合成氨装置入口的混合气体至合成塔工作温度,保证合成氨反应的顺利进行。最后,当上述热物流温度约低于100 ℃时,这部分低温余热则经过系统的冷公用工程排向环境。
由可再生能源电力驱动的绿色合成氨系统经济性受多种因素影响,本节具体分析了电价、系统年运行时长对系统氨生产成本以及投资回收期的影响。
理想情况下,假设合成氨系统在额定负荷22.5 t/h的年运行时长为8 000 h。图9为电价对合成氨系统的氨生产成本和回收期的影响。图9中合成氨系统3种制氢方案的氨生产成本和回收期均随电价的增长而增加,其中,当电价由0.2元/(kW·h)增长至0.3元/(kW·h),合成氨系统仅由PEMEC制氢时,氨生产成本由3 363.6元/t增加至4 275.1元/t,投资回收期则由9.5年增加至12.8年;系统中PEMEC和AWE氢气比例为1:1时,氨生产成本由2 828.8元/t增加至3 807.7元/t,投资回收期由7年增加至9.9年;若系统仅由AWE制氢时,氨生产成本由2 285.7元/t升至3 331.9元/t,投资回收期由4.3年增加至6.4年。主要是因为综合电价的高低直接影响绿色合成氨系统的运行成本,电价越高,合成氨系统的运行成本越高,投资回收期越长。
图10为系统年运行时长对氨生产成本和投资回收期的影响。由图10可知:当系统年运行时长由5 500 h增加至7 000 h时,3种制氢方案的氨生产成本均呈现下降的趋势,其中PEMEC制氢合成氨系统的氨生产成本降幅最大,由4 939.8元/t降至4 290.6元/t,对应的投资回收期减少了3.6年,而方案2和方案3的氨生产成本的降幅分别为470.9元/t和290.2元/t,投资回收期分别降低了2.8年和1.9年;当系统年运行时长由7 000 h增加至8 000 h时,3种制氢方案的氨生产成本先升高再降低。这主要是由于当系统年运行时长由7 000 h增加至7 500 h,合成氨系统的电解槽发生了更换,增加了系统的初始投资;尽管如此,当系统年运行时长达到8 000 h时,此时系统的经济性表现仍优于系统年运行时长为7 000 h的系统经济性。具体而言,对于3种制氢方案,系统年运行时长为8 000 h比年运行时长7 000 h的氨生产成本分别降低了15.6、31.9、47.0元/t,对应的投资回收期分别减少了0.1、0.2、0.3年。
本文对比分析了合成氨系统3种不同制氢方案的技术经济性,并采用夹点分析和数学规划相结合的方法,对由PEMEC和AWE协同制氢的合成氨系统进行了热集成分析,主要结论如下。
1)PEMEC和AWE制氢比例的提升,有助于改善系统的能量效率,减少单位质量氨的碳排放,但系统的氨生产成本和投资回收期却因PEMEC的投资高于AWE而不断增加。
2)合成氨系统采用PEMEC制氢、PEMEC和AWE协同制氢以及AWE制氢的能量效率分别是56.6%、52.7%和49.3%,对应的氨生产成本分别是4 275.1、3 807.7、3 331.9元/t。
3)提升PEMEC和AWE的运行温度均有利于降低电解槽的单位制氢能耗,进而提升系统的热力性能表现;而降低电价和提升系统运行时长有助于降低系统氨生产成本、减少系统投资回收期。
4)借助夹点分析和数学规划相结合的方法,绘制了PEMEC和AWE协同制氢合成氨系统冷热组合曲线,并分析了合成氨工艺中不同冷热物流集成方案,发现系统中低于100 ℃的余热可通过系统的冷公用工程排向环境。
  • 国家自然科学基金重大项目(52090064)
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doi: 10.19666/j.rlfd.202409218
  • 接收时间:2024-09-29
  • 首发时间:2026-03-06
  • 出版时间:2025-05-25
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  • 收稿日期:2024-09-29
基金
Major Project of National Natural Science Foundation of China(52090064)
国家自然科学基金重大项目(52090064)
作者信息
    1.国核电力规划设计研究院有限公司,北京 100095
    2.华北电力大学能源动力与机械工程学院,北京 102206
    3.吉林电力股份有限公司,吉林 长春 130022
    4.大安吉电绿氢能源有限公司,吉林 白城 131312

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张汉飞(1986),男,博士,讲师,主要研究方向为先进能量系统集成优化技术,
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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
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红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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