Article(id=1198266576135877103, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1198266568997175650, articleNumber=1009-5438(2023)02-0069-04, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1673366400000, receivedDateStr=2023-01-11, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1763618614467, onlineDateStr=2025-11-20, pubDate=1682352000000, pubDateStr=2023-04-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763618614467, onlineIssueDateStr=2025-11-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763618614467, creator=13701087609, updateTime=1763618614467, updator=13701087609, issue=Issue{id=1198266568997175650, tenantId=1146029695717560320, journalId=1185652524569653253, year='2023', volume='49', issue='2', pageStart='1', pageEnd='98', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763618612765, creator=13701087609, updateTime=1763619383107, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1198269800108618470, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1198266568997175650, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1198269800108618471, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1198266568997175650, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=69, endPage=72, ext={EN=ArticleExt(id=1198266576366563824, articleId=1198266576135877103, tenantId=1146029695717560320, journalId=1185652524569653253, language=EN, title=Applications of Double-layer Selective Catalytic Reduction (SCR) Denitration Catalyst in Compressor-turbine Unit with Low Heating Values, columnId=1187100786392711543, journalTitle=Science & Technology of Baotou Steel, columnName=Equipment and Automation, runingTitle=null, highlight=null, articleAbstract=

The maximum concentration of nitrogen oxide emissions in the flue gas of four compressor-turbine units with low heating values using blast furnace and coke oven gas in a steel enterprise is about 250 mg/m3, which could not meet the requirements of limiting values for ultra-low emissions of the steel industry, so the denitration modification is needed. Three different denitration modification schemes are proposed based on studying frequently-used flue gas denitration technologies at home and abroad. The modification scheme of built-in double-layer SCR catalyst in waste heat boiler is finally implemented by comparing such factors as the technology maturity, use risks and operating economy as well as the expected effects are achieved. This study could provide the feasible and effective technical methods for the compressor-turbine unit with low heating values and more nitrogen oxides while without prepared denitration space on site in our country.

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某钢铁企业4台使用高炉煤气、焦炉煤气的低热值燃气轮机组烟气氮氧化物排放最高浓度约为250 mg/m3,不满足钢铁行业超低排放限值要求,需要进行脱硝改造。在研究国内外常用的烟气脱硝技术基础上,提出了3种不同的脱硝改造方案。通过对比技术成熟度、使用风险、运行经济性等因素最终实施了余热锅炉内置双层SCR催化剂的改造方案并达到预期效果。本研究可为我国未预留脱硝空间且氮氧化物较高的低热值燃气轮机组提供现场可行且有效的技术方法。

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孟晓敏(1986-),男,山西省代县人,高级工程师,现从事热能与动力工程方面的运行、设备研究工作。

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孟晓敏(1986-),男,山西省代县人,高级工程师,现从事热能与动力工程方面的运行、设备研究工作。

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孟晓敏(1986-),男,山西省代县人,高级工程师,现从事热能与动力工程方面的运行、设备研究工作。

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烟气量
/(t·h-1)
排烟温度
/℃
烟气最高NOx浓度
/(mg·m-3)
烟气含氧量
/%
1 346.8 130~170 250 ≤15
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1#—4#燃气轮机组脱硝改造前烟气参数

, figureFileSmall=null, figureFileBig=null, tableContent=
烟气量
/(t·h-1)
排烟温度
/℃
烟气最高NOx浓度
/(mg·m-3)
烟气含氧量
/%
1 346.8 130~170 250 ≤15
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技术类型 适用温度/℃ 脱硝效率/% 缺点
SCR 150~450 90~95 需使用催化剂
SNCR 850~1 100 30~60 脱硝效率低下
活性焦法 120~160 70~80 投资与运行费用高,存在较大安全风险
氧化吸收法 <60 50~80 运行费较高,有二次污染,效率较低,适用于湿法改造
络合吸收法 <60 50~70 运行费较高,络合剂再生困难,适用于湿法改造
固定床法 120~450 40~75 不宜处理较高浓度氮氧化物废气
), ArticleFig(id=1198266579067695684, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=CN, label=表2, caption=

氮氧化物末端控制技术使用条件对比

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技术类型 适用温度/℃ 脱硝效率/% 缺点
SCR 150~450 90~95 需使用催化剂
SNCR 850~1 100 30~60 脱硝效率低下
活性焦法 120~160 70~80 投资与运行费用高,存在较大安全风险
氧化吸收法 <60 50~80 运行费较高,有二次污染,效率较低,适用于湿法改造
络合吸收法 <60 50~70 运行费较高,络合剂再生困难,适用于湿法改造
固定床法 120~450 40~75 不宜处理较高浓度氮氧化物废气
), ArticleFig(id=1198266579130610246, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
工况 区间1 区间2
冬季100%负荷 444 244
夏季100%负荷 453 239
冬季50%负荷 380 219
夏季50%负荷 416 213
), ArticleFig(id=1198266579206107720, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=CN, label=表3, caption=

1#、2#燃气轮机组余热锅炉检修空间烟气温度℃

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工况 区间1 区间2
冬季100%负荷 444 244
夏季100%负荷 453 239
冬季50%负荷 380 219
夏季50%负荷 416 213
), ArticleFig(id=1198266579269022282, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
工况 区间3 区间4
冬季100%负荷 297 228
夏季100%负荷 297 230
冬季50%负荷 258 213
夏季50%负荷 257 217
), ArticleFig(id=1198266579361296972, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=CN, label=表4, caption=

3#、4#燃气轮机组余热锅炉检修空间烟气温度℃

, figureFileSmall=null, figureFileBig=null, tableContent=
工况 区间3 区间4
冬季100%负荷 297 228
夏季100%负荷 297 230
冬季50%负荷 258 213
夏季50%负荷 257 217
), ArticleFig(id=1198266579461960269, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
时间 入口氮氧化物浓度小时均值 出口氮氧化物浓度小时均值
1# 2# 3# 4# 1# 2# 3# 4#
19:00 181.39 183.42 205.33 208.36 41.81 38.42 41.15 41.83
20:00 213.76 221.83 230.59 231.67 43.74 38.86 47.85 46.48
21:00 243.25 245.39 218.88 217.56 49.92 35.95 33.73 43.41
22:00 154.14 149.53 187.89 183.86 46.98 31.99 44.56 45.14
23:00 183.38 179.42 205.33 213.48 39.26 42.62 37.21 37.53
), ArticleFig(id=1198266579550040654, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266576135877103, language=CN, label=表5, caption=

1#—4#燃气轮机组氮氧化物出入口浓度对比mg/m3

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时间 入口氮氧化物浓度小时均值 出口氮氧化物浓度小时均值
1# 2# 3# 4# 1# 2# 3# 4#
19:00 181.39 183.42 205.33 208.36 41.81 38.42 41.15 41.83
20:00 213.76 221.83 230.59 231.67 43.74 38.86 47.85 46.48
21:00 243.25 245.39 218.88 217.56 49.92 35.95 33.73 43.41
22:00 154.14 149.53 187.89 183.86 46.98 31.99 44.56 45.14
23:00 183.38 179.42 205.33 213.48 39.26 42.62 37.21 37.53
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双层SCR脱硝催化剂在低热值燃气轮机组的应用
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孟晓敏 , 李平 , 武建国 , 张俊峰 , 连伟
包钢科技 | 设备与自动化 2023,49(2): 69-72
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包钢科技 | 设备与自动化 2023, 49(2): 69-72
双层SCR脱硝催化剂在低热值燃气轮机组的应用
全屏
孟晓敏, 李平, 武建国, 张俊峰, 连伟
作者信息
  • 内蒙古包钢钢联股份有限公司动供总厂,内蒙古 包头 014010
  • 孟晓敏(1986-),男,山西省代县人,高级工程师,现从事热能与动力工程方面的运行、设备研究工作。

Applications of Double-layer Selective Catalytic Reduction (SCR) Denitration Catalyst in Compressor-turbine Unit with Low Heating Values
Xiao-min Meng, Ping Li, Jian-guo Wu, Jun-feng Zhang, Wei Lian
Affiliations
  • Power Supply General Plant of Inner Mongolia Baotou Steel Union Co. , Ltd. , Baotou 014010, Inner Mongolia Autonomous Region, China
出版时间: 2023-04-25
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某钢铁企业4台使用高炉煤气、焦炉煤气的低热值燃气轮机组烟气氮氧化物排放最高浓度约为250 mg/m3,不满足钢铁行业超低排放限值要求,需要进行脱硝改造。在研究国内外常用的烟气脱硝技术基础上,提出了3种不同的脱硝改造方案。通过对比技术成熟度、使用风险、运行经济性等因素最终实施了余热锅炉内置双层SCR催化剂的改造方案并达到预期效果。本研究可为我国未预留脱硝空间且氮氧化物较高的低热值燃气轮机组提供现场可行且有效的技术方法。

燃气轮机组  /  余热锅炉  /  脱硝  /  超低排放

The maximum concentration of nitrogen oxide emissions in the flue gas of four compressor-turbine units with low heating values using blast furnace and coke oven gas in a steel enterprise is about 250 mg/m3, which could not meet the requirements of limiting values for ultra-low emissions of the steel industry, so the denitration modification is needed. Three different denitration modification schemes are proposed based on studying frequently-used flue gas denitration technologies at home and abroad. The modification scheme of built-in double-layer SCR catalyst in waste heat boiler is finally implemented by comparing such factors as the technology maturity, use risks and operating economy as well as the expected effects are achieved. This study could provide the feasible and effective technical methods for the compressor-turbine unit with low heating values and more nitrogen oxides while without prepared denitration space on site in our country.

compressor-turbine unit  /  waste heat boiler  /  denitration  /  ultra-low emissions
孟晓敏, 李平, 武建国, 张俊峰, 连伟. 双层SCR脱硝催化剂在低热值燃气轮机组的应用. 包钢科技, 2023 , 49 (2) : 69 -72 .
Xiao-min Meng, Ping Li, Jian-guo Wu, Jun-feng Zhang, Wei Lian. Applications of Double-layer Selective Catalytic Reduction (SCR) Denitration Catalyst in Compressor-turbine Unit with Low Heating Values[J]. Science & Technology of Baotou Steel, 2023 , 49 (2) : 69 -72 .
近年来随着燃煤电厂污染控制成效的显现,钢铁行业已经成为我国工业部门最大的污染物排放来源。实施钢铁行业超低排放改造是打赢蓝天保卫战的重要措施,也是钢铁行业高质量发展、绿色发展的主要推力,是未来一段时间内大气质量改善的关键点和难点之一。2019年4月,中华人民共和国生态环境部等五部委联合发布了环大气〔2019〕35号文件《关于推进实施钢铁行业超低排放的意见》,要求2025年底前,重点区域钢铁企业超低排放改造基本完成,以气体为燃料的燃气轮机组烟气排放限值为NOx浓度不大于50 mg/m3,SO2浓度不大于35 mg/m3,颗粒物浓度不大于5 mg/m3(以下简称超低排放)。国内某钢铁企业1#—4#燃气轮机组烟气NOx排放浓度不满足超低排放限值要求,需实施脱硝改造。
1#—4#燃气轮机组额定功率为150 MW,采用三菱M701S(DA)型燃机,主要设备包括轴流式压缩机、多筒燃烧室和轴流式透平机。M701S(DA)燃机在国内外有多年的成功运行经验。机组使用燃料为低热值的高炉煤气及焦炉煤气,两种煤气混合后在燃烧室内燃烧后产生高温气流送入透平机做功后进入余热锅炉。
1#、2#燃气轮机组配套的立式余热锅炉由无锡华光锅炉股份有限公司生产制造,型号为UG-M701S(DA)-R,3#、4#燃气轮机组配套的卧式余热锅炉由杭州锅炉有限公司生产制造,型号为NG-M701D-R1。余热锅炉主要设备包括烟道、本体受热面、高低压汽包、给水泵、除氧器、管道、出口烟道、主烟囱等。燃机排出的烟气通过进口烟道进入锅炉本体,依次纵向冲刷各受热模块,再经出口烟道由主烟囱排出。
脱硝改造前,1#—4#燃气轮机组没有任何环保设备,根据2021—2022年烟气检测数据,大部分时段各台燃气轮机氮氧化物排放浓度约为100~150 mg/m3左右,存在较多250 mg/m3左右的极限值,烟气参数详见表1
根据NOx生成机理,燃料燃烧过程中所产生的NOx量与燃料燃烧方式、燃烧温度、空气过剩系数以及烟气在炉膛停留时间等因素密切相关。燃料燃烧产生NOx的主要机理有燃料型、热力型和快速型三种。快速型NOx是碳氢化合物燃料燃烧时,如果燃料浓度较大,在反应区附近会快速生成NOx。因燃气轮机的过剩空气量较大,快速型NOx生成量很少,可以忽略不计。燃气轮机的主要燃料是高炉煤气,几乎不含氮化合物,燃料燃烧时,不产生烃,燃烧过程中不存在氮化合物在燃烧过程中热分解而又接着氧化生产NOx的现象,因此烟气中燃料型NOx生成量也很低。从燃气轮机燃烧原理分析,燃烧室温度约在1 500 ℃左右,处于热力型NOx快速生成的区间,燃气轮机组烟气中的NOx以NO为主[1],NO2的浓度非常低,但进入大气环境后,NO会逐渐转化成为NO2。综上所述,燃气轮机燃烧产生的NOx以热力型为主。
1#—4#燃气轮机在设计安装之初已经采用了低氮燃烧技术,由于国内尚无针对三菱M701S(DA)型燃机的燃烧器低氮改造升级方案,需采用烟气脱硝技术。目前国内外常用的烟气脱硝技术主要包括选择性催化还原法(SCR)、选择性非催化还原法(SNCR)、活性焦法、氧化吸收法、络合吸收法、固定床干法等。对以上几项技术的使用条件进行对比,见表2
1#—4#燃气轮机组烟气氮氧化物最大排放浓度约为250 mg/m3,若要实现超低排放脱硝效率需稳定控制在80%以上。SNCR法、活性焦法、氧化吸收法以及络合吸收法因效率较低且缺点较明显,并不适合。SCR脱硝技术脱硝效率高,设备可靠性高,投资相对适中,运行维护简单,能最大程度满足燃气轮机组的脱硝要求。
选择合适的催化剂反应窗口温度,是烟气SCR脱硝技术的关键。SCR脱硝技术按照温度划分为中高温SCR(反应温度窗口在300~450 ℃)、中低温SCR(反应温度窗口在180~300 ℃)、低温SCR(反应温度窗口在150~180 ℃)、超低温SCR(反应温度窗口小于150 ℃)。1#—4#燃气轮机组余热锅炉入口烟气温度约550 ℃,出口烟气温度一般在130~170 ℃左右,可供选择的脱硝方案有中高温SCR、中低温SCR、超低温SCR技术,逐一对比分析。
方案一:中低温催化还原(外置SCR反应区)方案。外置SCR反应区采用中低温催化剂可以保证足够的催化剂用量,但由于余热锅炉出口温度无法满足中低温催化剂温度要求,需要将余热锅炉出口温度提高至220 ℃左右,常规烟气升温方式有燃气补燃、回转式烟气换热以及混合升温等。1#—4#燃气轮机组烟气量约为105万m3/h,按照温升90 ℃设计,若采用高炉煤气补燃升温,每年消耗能源费用约7 000万元。
方案二:超低温催化还原(外置SCR反应区)方案。超低温SCR技术是采用特殊的催化剂及载体的脱硝技术,外置SCR反应区可以保证足够的催化剂用量,但催化剂及其载体的制作成本较高,与中低温和高温催化剂相比,其售价高出数倍以上。此外,超低温SCR催化剂现阶段技术尚不成熟,寿命偏低,易受水分、二氧化硫等烟气组分影响,应用案例较少。
方案三:中低温/中高温催化还原(内置SCR反应区)方案。1#—4#燃气轮机组余热锅炉内部布置极为紧凑,若对余热锅炉进行改造,开辟最佳温度区间以保证足够的催化剂安装空间,需对现有换热模块管屏进行切割移位并重新焊接,改造施工极其困难,国内尚无改造案例,可以利用现有检修空间安装SCR催化剂。
1#、2#余热锅炉在高压蒸发器下部、低压蒸发器下部各有一个高度为800 mm的检修空间,高压蒸发器下部检修空间(以下简称区间1)、低压蒸发器下部检修空间(以下简称区间2)的运行温度见表3。1#、2#余热锅炉安装两层SCR催化剂,理论上两层催化剂可保证脱硝效率达到80%以上,实现超低排放。
3#、4#燃气轮机组余热锅炉在高压省煤器前、低压过热器前各有一个宽度为800 mm的检修空间,高压省煤器前检修空间(以下简称区间3)、低压过热器前检修空间(以下简称区间4)的运行温度见表4。3#、4#余热锅炉安装两层SCR催化剂,理论上两层催化剂可保证脱硝效率达到80%以上,可实现超低排放。
方案一工艺路线理论上可行,但是结合该能源消耗与场地条件,实现十分困难不可采用。方案二鉴于技术成熟度、使用风险、经济性较差等因素不可采用。方案三需要牺牲检修空间,但结合调研数据、图纸设计资料、现场实地占用情况以及目前各项治理技术的成熟度、投资和运行经济性等因素考虑是目前可采用最合理的工艺路线。催化剂选择比表面积相对较大的纹板式催化剂,吸收剂选择20%浓度的氨水。
中低温/中高温SCR方案实施后,1#—4#燃气轮机组烟气氮氧化物达到超低排放限值要求,脱硝效率达到80%以上。1#、2#余热锅炉采用下进上出的结构形式,3#、4#余热锅炉采用水平进出的结构形式。
4台机组改造完成后脱硝效率均可以达到80%以上,烟气氮氧化物排放浓度满足钢铁行业超低排放限值要求,达到预期效果。表5为2023年7月17日19:00—23:00四台燃机出入口氮氧化物浓度小时均值对比。
余热锅炉加装烟气脱硝装置后,系统阻力约增加1 300 Pa。有计算表明[2],每增加1 kPa的烟气阻力会使燃气轮机的效率下降0.8%。此外SCR催化剂主要是以TiO2为载体,V2O5-WO3或V2O5-MoO3为催化活性成分,此类型的催化剂对SO2向SO3的转化有明显的促进作用[3]。脱硝系统NH3与SO3反应产生硫酸氢氨(NH4HSO4),在140~240 ℃之间由液态转化为固态,NH4HSO4具有极强的吸附性和黏性。四台燃气轮机组中使用的中低温催化剂温度为210~240 ℃,NH4HSO4会附着在受热面及催化剂的表面,造成系统阻力进一步增大,催化剂活性下降,机组发电效率降低。为避免系统阻力过大影响机组运行的经济性及稳定性,建议布置烟气再生系统,根据实际情况每季度或每半年运行一次。1#—4#燃气轮机组余热锅炉布置烟气再生系统较为困难,没有布置烟气再生系统。
余热锅炉在检修空间安装催化剂后,各检修空间已不足400 mm,对余热锅炉日后维护有较大影响。催化剂及受热面检修时需要将部分催化剂模块拆除后才能进行,造成检修工期延长、维护成本升高等一系列问题。
SCR投运后,其反应生成氮气和水,对锅炉烟气量而言,属微量反应,因此烟气成分变化不大。氨水工艺需抽取喷氨格栅前的锅炉热烟气作为氨水蒸发热源,在蒸发器中气化后经喷氨格栅喷入锅炉,此过程中仅氨水蒸发消耗一部分热能,锅炉内部无热交换,蒸发氨水对锅炉整体烟气温度下降微乎其微,烟气温度降低约0.1~0.2 ℃。
(1)某钢铁企业1#—4#燃气轮机组经双层SCR脱硝改造后,烟气氮氧化物排放浓度满足超低排放要求,此改造方案适用于未预留脱硝空间且氮氧化物较高的低热值燃气轮机组。
(2)燃气轮机组脱硝改造后具有一定的环境效益,对当地的大气环境改善具有积极意义,具有良好的社会效益。
参考文献 引证文献
排序方式:
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金维平. 燃料型NOx的生成机理及控制措施[J]. 中国科技信息, 2005(22):17.
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焦树建. 燃气-蒸汽联合循环[M]. 北京: 机械工业出版社, 2000.
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刘宇, 单广波, 闰松, 等. 燃煤锅炉烟气中SO3的生成、危害及控制技术研究进展[J]. 大气污染防治, 2005, 18(4):65-68.
2023年第49卷第2期
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  • 接收时间:2023-01-11
  • 首发时间:2025-11-20
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
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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