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In order to study the rejuvenating effect difference of rejuvenation fluid on water tree ageing cable when different catalysts were combined with siloxane, we selected a methyl phenyl dimethoxy siloxane (PMDMS) and a long-chain siloxane, tetraisopropyl titanate (TIPT) and long-chain benzene sulfonic acid two catalysts to prepare four rejuvenation fluids with different formula. Water tree aged cables were rejuvenated by injecting the rejuvenation fluid and conducted second ageing, and their electrical properties and microstructure changes were analyzed by the power frequency breakdown test, water tree morphology observation, and FTIR test. The results show that four kinds of rejuvenation fluids can inhibit the growth of water tree, and the breakdown voltage of the water tree aged sample is improved. The rejuvenation fluid composed of long-chain siloxane and long-chain benzene sulfonic acid has the highest retention rate in the insulation layer, and the rejuvenating effect is the best. The rejuvenation fluid composed of PMDMS and long-chain benzene sulfonic acid has the lowest retention rate in the insulation layer, and the rejuvenating effect is the worst. It is proved that when the diffusion speed of siloxane and catalyst in insulation layer matches, the retention rate of the siloxane can be improved, and the long-term rejuvenating effect can be enhanced.

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为了研究不同催化剂与硅氧烷配合时,修复液对水树老化电缆修复效果的差异,选取甲基苯基二甲氧基硅烷(PMDMS)和一种长链硅烷,以及钛酸四异丙酯(TIPT)和长链苯磺酸两种催化剂,配制了4种不同配方的修复液,对水树老化电缆进行注入修复和二次老化,并通过工频击穿试验、水树形貌观测和傅里叶红外光谱测试分析短电缆试样绝缘的电气性能和微观结构变化。结果表明:4种配方的修复液均能抑制水树的生长,提高水树老化试样的击穿电压;长链硅烷搭配长链苯磺酸的修复液在绝缘层中的留存率最高,修复效果最佳;PMDMS搭配长链苯磺酸的修复液在绝缘层中的留存率最低,修复效果最差;最终证明当硅氧烷与催化剂在绝缘层中扩散速度相匹配时能够提高硅氧烷的留存率,增强修复液的长期修复效果。

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王利(1981-),男(汉族),辽宁海城人,高级工程师,主要从事核电厂电气的系统设计及电力设备状态监测的研究。

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王利(1981-),男(汉族),辽宁海城人,高级工程师,主要从事核电厂电气的系统设计及电力设备状态监测的研究。

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王利(1981-),男(汉族),辽宁海城人,高级工程师,主要从事核电厂电气的系统设计及电力设备状态监测的研究。

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修复液组分
硅氧烷催化剂
APMDMSTIPT
BPMDMS长链苯磺酸
C长链硅氧烷TIPT
D长链硅氧烷长链苯磺酸
), ArticleFig(id=1245084036155159367, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241799378998984933, language=CN, label=表1, caption=

各组修复液配方

, figureFileSmall=null, figureFileBig=null, tableContent=
修复液组分
硅氧烷催化剂
APMDMSTIPT
BPMDMS长链苯磺酸
C长链硅氧烷TIPT
D长链硅氧烷长链苯磺酸
), ArticleFig(id=1245084036251628365, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241799378998984933, language=EN, label=Tab.2, caption=Comparison of C-Si bond absorption peak strength for each sample, figureFileSmall=null, figureFileBig=null, tableContent=
组别校正峰高/(cm-1)(C-Si)/(-CH2-)相对强度/%
1 259(C-Si)2 917(-CH2-)
A0.0800.8958.94
B0.0370.8934.14
C0.0460.8925.10
D0.0960.88310.88
), ArticleFig(id=1245084036331320144, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241799378998984933, language=CN, label=表2, caption=

各组试样的C-Si吸收峰强度对比

, figureFileSmall=null, figureFileBig=null, tableContent=
组别校正峰高/(cm-1)(C-Si)/(-CH2-)相对强度/%
1 259(C-Si)2 917(-CH2-)
A0.0800.8958.94
B0.0370.8934.14
C0.0460.8925.10
D0.0960.88310.88
), ArticleFig(id=1245084036423594838, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241799378998984933, language=EN, label=Tab.3, caption=Breakdown voltage at 63.2% of each sample, figureFileSmall=null, figureFileBig=null, tableContent=
项目

E组(第一次

老化)

A组(第二次老化)B组(第二次老化)C组(第二次老化)D组(第二次老化)E组(第二次老化)

击穿电压

/kV

31.121.627.522.524.528.918.0

下降幅度

/%

基准30.511.627.721.27.042.1
), ArticleFig(id=1245084036503286620, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241799378998984933, language=CN, label=表3, caption=

各组试样的63.2%击穿电压

, figureFileSmall=null, figureFileBig=null, tableContent=
项目

E组(第一次

老化)

A组(第二次老化)B组(第二次老化)C组(第二次老化)D组(第二次老化)E组(第二次老化)

击穿电压

/kV

31.121.627.522.524.528.918.0

下降幅度

/%

基准30.511.627.721.27.042.1
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催化剂对硅氧烷修复水树老化电缆长期效果的影响
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王利 , 李剑波 , 罗定南
绝缘材料 | 绝缘技术 2021,54(9): 73-78
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绝缘材料 | 绝缘技术 2021, 54(9): 73-78
催化剂对硅氧烷修复水树老化电缆长期效果的影响
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王利, 李剑波, 罗定南
作者信息
  • 中广核研究院有限公司,广东 深圳 518124
  • 王利(1981-),男(汉族),辽宁海城人,高级工程师,主要从事核电厂电气的系统设计及电力设备状态监测的研究。

Influence of Catalyst on Long-term Performance of Siloxane Rejuvenating Water Tree Aged Cable
Li WANG, Jianbo LI, Dingnan LUO
Affiliations
  • China Nuclear Power Technology Research Institute, Shenzhen 518124, China
出版时间: 2021-09-20 doi: 10.16790/j.cnki.1009-9239.im.2021.09.012
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为了研究不同催化剂与硅氧烷配合时,修复液对水树老化电缆修复效果的差异,选取甲基苯基二甲氧基硅烷(PMDMS)和一种长链硅烷,以及钛酸四异丙酯(TIPT)和长链苯磺酸两种催化剂,配制了4种不同配方的修复液,对水树老化电缆进行注入修复和二次老化,并通过工频击穿试验、水树形貌观测和傅里叶红外光谱测试分析短电缆试样绝缘的电气性能和微观结构变化。结果表明:4种配方的修复液均能抑制水树的生长,提高水树老化试样的击穿电压;长链硅烷搭配长链苯磺酸的修复液在绝缘层中的留存率最高,修复效果最佳;PMDMS搭配长链苯磺酸的修复液在绝缘层中的留存率最低,修复效果最差;最终证明当硅氧烷与催化剂在绝缘层中扩散速度相匹配时能够提高硅氧烷的留存率,增强修复液的长期修复效果。

交联聚乙烯电缆  /  水树老化  /  硅氧烷修复液  /  催化剂  /  长期性

In order to study the rejuvenating effect difference of rejuvenation fluid on water tree ageing cable when different catalysts were combined with siloxane, we selected a methyl phenyl dimethoxy siloxane (PMDMS) and a long-chain siloxane, tetraisopropyl titanate (TIPT) and long-chain benzene sulfonic acid two catalysts to prepare four rejuvenation fluids with different formula. Water tree aged cables were rejuvenated by injecting the rejuvenation fluid and conducted second ageing, and their electrical properties and microstructure changes were analyzed by the power frequency breakdown test, water tree morphology observation, and FTIR test. The results show that four kinds of rejuvenation fluids can inhibit the growth of water tree, and the breakdown voltage of the water tree aged sample is improved. The rejuvenation fluid composed of long-chain siloxane and long-chain benzene sulfonic acid has the highest retention rate in the insulation layer, and the rejuvenating effect is the best. The rejuvenation fluid composed of PMDMS and long-chain benzene sulfonic acid has the lowest retention rate in the insulation layer, and the rejuvenating effect is the worst. It is proved that when the diffusion speed of siloxane and catalyst in insulation layer matches, the retention rate of the siloxane can be improved, and the long-term rejuvenating effect can be enhanced.

XLPE cable  /  water tree ageing  /  siloxane rejuvenation liquid  /  catalyst  /  long-term effect
王利, 李剑波, 罗定南. 催化剂对硅氧烷修复水树老化电缆长期效果的影响. 绝缘材料, 2021 , 54 (9) : 73 -78 . DOI: 10.16790/j.cnki.1009-9239.im.2021.09.012
Li WANG, Jianbo LI, Dingnan LUO. Influence of Catalyst on Long-term Performance of Siloxane Rejuvenating Water Tree Aged Cable[J]. Insulating Materials, 2021 , 54 (9) : 73 -78 . DOI: 10.16790/j.cnki.1009-9239.im.2021.09.012
交联聚乙烯(cross-linked polyethylene,XLPE)电缆已成为城市配电网的重要输电载体,而树枝老化一直是其绝缘击穿的主要原因之一[1-2]。我国早期的入地电缆防水性能不佳,易发生水树老化,随着运行年限的增加,“老龄化”问题日益凸显。虽然随着制造工艺的进步,新入地电缆外层密封性和绝缘抗水树性有所增强,但在某些地区地下电缆长期处于潮湿环境或浸泡在积水中,水分仍可能从外护套、中间接头或电缆终端等途径入侵,进而使绝缘受潮,并在电场作用下发展成水树缺陷,甚至引发电树,危害电缆运行安全[3-4]
相较于直接更换老化电缆,使用注入式修复技术延长电缆运行寿命具有更高的经济效应[5],其主要原理是通过压力将修复液从缆芯间隙注入电缆内部,随后修复液会逐渐扩散至绝缘层中,并发生水解-缩合反应,消耗水分并填充微孔缺陷,从而阻碍水分再次入侵,并减少由于微孔造成的局部高场区,减缓绝缘劣化。这项技术在国外已有30多年的商业化运行经验,成功修复电缆超过24 000 km[6];而该技术在国内经过近十年的发展,也开始逐渐走向工程应用[7]
硅氧烷修复技术问世以来,国内外学者进行了大量研究,文献[8]在修复液中加入扩散速度更快的水反应性硅氧烷,使其优先进入导体屏蔽层和绝缘层消除水分,增强短期修复效果,但其添加量需要控制在一定范围内;文献[9]通过增大注入压力的方式加速修复液的扩散,不仅有效缩短了注入时间,还增强了短期修复效果,但压力过大可能会造成电缆损伤;文献[10]在修复液中加入抗氧化剂等添加剂,增强了修复液的综合性能和中长期修复效果。然而,当前的研究大多数都聚焦于硅氧烷(主要成分)、注入技术和功能添加剂上,只有较少文献提及催化剂的改进,文献[11]利用钛酸脂类催化剂水解反应生成纳米颗粒的特性增强了修复后电缆的抗局部放电能力,但本质上相当于另一种形式的添加剂;文献[12]报道了模型电缆中催化剂对硅氧烷留存率的影响,但未通过试验研究修复后试样的电气性能和理化性能。在实际中,硅氧烷的聚合反应必须有催化剂参与,因此任一组分(硅氧烷或催化剂)的提前流失都将减少聚合反应的发生,降低修复液的留存率,并最终使修复效果远低于预期。因此,有必要探究催化剂与硅氧烷扩散速率的匹配对修复效果的具体影响。
本研究在国内外研究的基础上,选取不同分子量的硅氧烷和催化剂配置4种不同配方的修复液,对短电缆试样进行加速水树老化与注入修复试验,通过理化性能与电气性能测试,分析不同催化剂对修复液修复效果的影响,尤其关注硅氧烷在绝缘层中的留存率。
为了研究不同催化剂与硅氧烷组合得到的修复液的修复效果,配置4种不同配方的修复液进行后续试验,各修复液配方如表1所示。4种试剂中,甲基苯基二甲氧基硅烷(PMDMS)和钛酸四异丙酯(TIPT)已有较多相关研究[13-14],长链硅氧烷和长链苯磺酸为新型试剂,其分子体积更大,且含有长烷基链,与脂肪族XLPE分子的相容性更高[15]
为了获得老化试样,先进行加速水树老化试验,选取的电缆型号为YJLV223×95, 8.7/10 kV,生产厂家为尚炜股份有限公司。截取长度为500 mm的短电缆试样,去除外护套,两端分别剥除150 mm半导电层并用砂纸将绝缘打磨光滑,防止沿面放电,为了方便试验接线,在一端剥除10 mm的绝缘层,露出缆芯。电缆中部长度为200 mm的一段为加速水树老化区,用钢针(曲率半径为(2.5±0.5)μm)等间距((10±1)mm)地扎出上下两排针孔缺陷,深度为3 mm。最后在水树老化区域套上热缩管,并热封两端用于储存NaCl溶液。
图1所示,采用水针电极法对短电缆试样进行加速水树老化,NaCl溶液浓度为1.8 mol/L,缆芯处施加7.5 kV、400 Hz的高频高压信号,外半导电层通过铜电极接地[16]
上述短电缆试样老化21天后得到第一次老化试样,分为A、B、C、D、E 5组,分别用表1中不同配方的修复液进行注入式修复,其中E组为对照组,不注入修复液。注入方法如图2所示,连接装置后,施加0.2 MPa的压力使修复液从前端适配器流入缆芯,注通后,使用阀门密封后端出口,保持气压4 h,使修复液快速扩散至绝缘层中。
修复完毕后,将5组试样置于60℃烘箱中,加快修复液向绝缘层的扩散速度,并定期向热缩管中添加NaCl溶液,确保水解-缩合反应的进行。恒温放置5天后,将试样再次进行加速水树老化21天,验证各配方的长期效果,所得试样为第二次老化试样。需要注意的是,在整个加速老化试验和修复试验中,始终保持两排针孔处于水平方向上,尽量避免因重力等因素导致的周向差异[14,17]
使用转轮式切片机平行于短电缆样本的针孔缺陷切取厚度约为200 μm的扇形薄片,并将其置于90℃的亚甲基蓝溶液中恒温染色30 min,随后通过Mshot-MP41型光学显微镜观察各组样本的水树生长情况。
用切片机沿垂直于绝缘层的方向,切取厚度约为200 μm,包含针孔缺陷的薄片,用Nicolet is50型傅里叶红外光谱仪的衰减全反射组件在距离绝缘层内侧2 mm处取点检测。
采用逐级升压法对试样进行工频击穿电压测试,初始电压选择12 kV,每次升高1 kV,每级电压保持1 min,升压过程中发生击穿则将击穿电压记为(前一级电压+0.5)kV,高压端为针电极,沿针孔缺陷垂直扎入相同深度,接地端为电缆缆芯。
为了观察水树生长情况,分别对老化前后的短电缆试样进行取样,观察其内部水树微观形貌,结果如图3所示。E组试样在第一次加速老化21天后,其绝缘层内的针尖附近已经出现较明显的水树缺陷,如图3(a)所示。而对比图3(b)(f)可以看出,未进行处理的E组和经过修复的A、B、C、D组试样,在第二次加速老化21天后,水树长度均有不同程度的增长。
图4统计了各组试样水树的平均长度,其中横坐标E(1)表示第一次老化E组试样,E(2)、A(2)、B(2)、 C(2)、D(2)分别表示第二次老化E、A、B、C、D组试样。从图4可以看出,第一次老化E组试样的水树平均长度为157.80 μm;经过第二次老化后,未修复E组的水树长度增长最明显,达到了283.74 μm,与第一次老化E组试样相比增加了79.8%;而A、B、C、D组试样的水树平均长度分别为224.50、259.50、254.60、193.80 μm,与第一次老化E组试样相比,水树平均长度分别增加了42.3%、64.4%、61.3%和22.8%。可见,4种配方的修复液均具有抑制水树生长的作用,修复液D的效果最优,修复液A次之,修复液C和修复液B较差。这是因为在注入修复液并保持恒温使其充分扩散后,硅氧烷能够发生水解反应消除绝缘内部的水分,并填充水树区域的微观孔洞,一方面缓和缺陷处的电场畸变,另一方面阻碍水分再次入侵,从而抑制水树生长[7]。此外,硅氧烷单体的分子体积较小,容易流失,若在催化剂的作用下发生水解-缩合反应,则能生成低聚物,增长分子链段,减缓迁移速率。观察4种配方可以发现,修复液B的PMDMS(硅氧烷)分子体积小于长链苯磺酸(催化剂),修复液C的TIPT(催化剂)分子体积小于长链硅氧烷(硅氧烷),容易造成硅氧烷或催化剂的先一步流失,使水解-缩合反应难以发生,从而减弱修复效果。
为了研究硅氧烷在电缆中的留存情况,在第一次和第二次加速水树老化后分别对各组电缆取样进行红外光谱检测,并通过波数为1 259 cm-1处的C-Si吸收峰强度判断硅氧烷的含量[14]图5为各组试样的C-Si峰观测结果,为了消除薄片厚度的影响,纵坐标进行了归一化处理。从图5可以看出,未进行修复的第一次老化和第二次老化E组试样可能由于电缆制造工艺引入了相关物质,在1 259 cm-1处也有微弱的吸收峰,但基本可以忽略,而经过修复的4组试样,其C-Si峰均有明显的增强。
采用内标法定量分析试样绝缘层内硅氧烷的含量,内标峰选取2 917 cm-1处的亚甲基(-CH2-)伸缩振动峰[18-19],4组修复试样在1 259 cm-1处的校正峰高和相对强度如表2所示。由表2可知,各试样C-Si特征峰的相对强度从高到低依次为D组(10.88%)、A组(8.94%)、C组(5.10%)、B组(4.14%),这与水树长度统计中各修复液抑制水树生长效果的排序结果相对应,证明硅氧烷在绝缘层中的留存量是抑制水树生长的关键因素之一。此外,A组试样的C-Si特征峰相对强度约为B组试样的两倍,D组试样的C-Si特征峰相对强度约为C组试样的两倍,表明硅氧烷与催化剂扩散速度的不匹配会使大部分硅氧烷流失,成为无效部分,不同配方若要达到相同的修复效果,则需注入更多的修复液,导致注入修复技术的成本上升,经济效益大幅降低。
为了研究各组试样的击穿电压变化情况,采用逐级升压法对试样进行工频击穿电压测试,并对击穿电压测试结果进行Weibull分布处理,结果如图6所示,并取击穿概率为63.2%时对应的特征击穿电压列于表3中。从图6表3可以看出,新电缆的击穿电压为31.1 kV,经过第一次老化和第二次老化的E组试样,其击穿电压相比新电缆试样的击穿电压分别下降了30.5%和42.1%,下降幅度较大;而经过修复的4组试样的击穿电压均大于未修复试样(E组),相比新电缆试样的击穿电压下降幅度从低到高依次为D组(7.0%)、A组(11.6%)、C组(21.2%)、B组(27.7%),总体表现出较优异的抗击穿性能,并且硅氧烷留存量较高的D组和A组修复效果最佳。
修复液的主要有效成分是硅氧烷,分子内一般至少含有两个烷氧基(RO-)与硅原子(Si)相连,组成能够发生水解-缩合反应的Si-OR结构。以试剂PMDMS为例,单体扩散进入绝缘层后,若有水分存在,将发生如图7(a)所示的水解反应,达到预期消除水分的作用,同时生成一种硅醇和副产物甲醇(CH3OH),甲醇极易挥发流失。而该硅醇可以继续水解,生成硅烷二醇(仅当环境非常潮湿时),或可与自身及PMDMS中的Si-OCH3作用,发生聚合反应生成二聚体,图7(b)为PMDMS与硅醇的聚合反应。二聚体的分子体积更大,扩散更缓慢,更不容易流失,若能够占据水树微孔,一方面能够减少绝缘层内的自由体积区,阻碍水分入侵,并缓解缺陷处的电场畸变[20],另一方面,即使水分再次侵入,水解性基团Si-OCH3也将再次与之反应,从而抑制水树的生长。二聚体可以进一步缩合成为三聚体、四聚体等,但是随着分子体积的增大,反应速度会相应减缓,并且XLPE基体内的空间阻碍也会抑制反应的进行,因此聚合度难达到较高的程度。
单体的聚合反应需要在催化剂的作用下进行,因此硅氧烷与催化剂在绝缘层内的扩散速度最好相互匹配,修复液在绝缘层中的扩散示意图如图8所示。修复液从绝缘层内侧开始扩散,若硅氧烷扩散更快(见图8(a)),则先到达绝缘层外侧的硅氧烷单体就难以发生聚合,单体分子体积小,可能在较短时间内从绝缘层流失,使得修复液的实际有效成分减少,长期修复效果下降。本研究选取的4种试剂中,PMDMS的分子体积最小,扩散较快,与催化剂长链苯磺酸配合时,将出现如图8(a)所示的情况,因此硅氧烷留存率相对较低。
当分子量相近的长链硅烷与长链苯磺酸配合时,将出现如图8(b)所示情况,两者的扩散速度相近,虽然绝缘层外侧的催化剂浓度相对内侧有所降低,但仍然能够促使一部分硅氧烷单体发生聚合反应,从而使得该配方的硅氧烷留存率大幅提升,抑制水树生长和提升击穿性能的效果都得到了一定的保证。对于A组和D组而言,D组中的长链硅烷和长链苯磺酸分子体积分别大于A组中的PMDMS和TIPT,修复液整体的扩散迁出速度更慢,并且由于D组配方的两种试剂中均存在长链烷基,与XLPE的相容性更高,溶解度更大[15],能够留存在绝缘层中的修复液更多,因此在发生充分扩散的前提下,D组的性能表现比A组更佳。
(1)4种配方的修复液都能有效地抑制XLPE绝缘中水树的生长并提升击穿电压。其中硅氧烷留存率最高的D组效果最优,A组次之,硅氧烷留存率可以作为衡量长期修复效果的关键指标之一。
(2)硅氧烷与催化剂的扩散速度相互匹配时,硅氧烷在绝缘层中的留存率更高。长链硅烷与长链苯磺酸组合得到的修复液留存率最高,PMDMS和TIPT的组合次之。工程上选择扩散速度相近的硅氧烷和催化剂,能够减少硅氧烷的流失,长期修复效果更佳。
  • 中国广核集团尖峰计划(R-2019ZBSEC005)
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doi: 10.16790/j.cnki.1009-9239.im.2021.09.012
  • 接收时间:2020-12-03
  • 首发时间:2026-03-20
  • 出版时间:2021-09-20
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  • 收稿日期:2020-12-03
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中国广核集团尖峰计划(R-2019ZBSEC005)
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    中广核研究院有限公司,广东 深圳 518124
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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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