Article(id=1172620564444361385, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172620559834821232, articleNumber=1009-2617(2024)01-0029-05, orderNo=null, doi=10.13355/j.cnki.sfyj.2024.01.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1691424000000, receivedDateStr=2023-08-08, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1757504128800, onlineDateStr=2025-09-10, pubDate=1708358400000, pubDateStr=2024-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757504128800, onlineIssueDateStr=2025-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757504128800, creator=13701087609, updateTime=1757504128800, updator=13701087609, issue=Issue{id=1172620559834821232, tenantId=1146029695717560320, journalId=1146120122248306696, year='2024', volume='43', issue='1', pageStart='1', pageEnd='111', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1757504127699, creator=13701087609, updateTime=1758625263309, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1177322943446135256, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172620559834821232, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1177322943446135257, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172620559834821232, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=29, endPage=33, ext={EN=ArticleExt(id=1172620564796682926, articleId=1172620564444361385, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Extraction of Vanadium from Vanadium Tailing Slag with Titanium Dioxide Waste Acid, columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

In order to realize the high value utilization of solid and liquid wastes, extraction of vanadium from vanadium tailings with titanium dioxide waste acid was studied. The effects of leaching temperature, leaching time, solid mass to liquid volume ratio, waste acid concentration and other technological parameters on vanadium leaching rate were investigated by orthogonal experiments, and the optimal leaching conditions were determined. In order to further improve the vanadium leaching rate, the appropriate amount of leaching aid (fluorite) and oxidant (hydrogen peroxide) was discussed. The results show that the order of influence of the process parameters on vanadium leaching rate is leaching temperature> leaching time> solid mass to liquid volume ratio> titanium dioxide waste acid concentration. Under the optimum conditions of temperature of 80 ℃, leaching time of 2 h, solid mass to liquid volume ratio of 1∶5 and waste acid concentration of 5%, the vanadium leaching rate is about 53%. After adding 7% fluorite and 5% hydrogen peroxide, the vanadium leaching rate can be increased to 71.09%.

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李军(1986—),男,博士,副研究员,主要研究方向为钒钛资源综合利用。

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李军(1986—),男,博士,副研究员,主要研究方向为钒钛资源综合利用。

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李军(1986—),男,博士,副研究员,主要研究方向为钒钛资源综合利用。

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a—放大100倍;b—放大500倍;c—放大2 000倍;d—放大10 000倍。

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∑Fe TiO2 V2O5 MnO SiO2 Al2O3 CaO MgO Cr2O3
32.80 12.90 2.08 7.84 14.40 3.20 2.50 3.57 2.24
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提钒尾渣的主要化学成分 %

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∑Fe TiO2 V2O5 MnO SiO2 Al2O3 CaO MgO Cr2O3
32.80 12.90 2.08 7.84 14.40 3.20 2.50 3.57 2.24
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+40目 40~60目 60~100目 100~150目 150~200目 -200目
7.8 6.0 20.6 25.2 1.6 38.8
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提钒尾渣的粒度分布 %

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+40目 40~60目 60~100目 100~150目 150~200目 -200目
7.8 6.0 20.6 25.2 1.6 38.8
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H2SO4 FeSO4 TiOSO4 Al2(SO4)3
18~22 5~8 1~2 2~3
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钛白废酸的主要化学组成 %

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H2SO4 FeSO4 TiOSO4 Al2(SO4)3
18~22 5~8 1~2 2~3
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试验编号 A
浸出温度/℃
B
浸出时间/h
C
固液质量体积比
D
钛白废酸浓度/%
钒浸出率/%
1 25 3 1∶7 20 37.98
2 25 2 1∶3 10 38.17
3 25 1 1∶5 5 36.92
4 60 3 1∶3 5 45.47
5 60 2 1∶5 20 45.92
6 60 1 1∶7 10 33.41
7 80 3 1∶5 10 53.95
8 80 2 1∶7 5 53.55
9 80 1 1∶3 20 45.41
k1 37.69 45.80 41.65 43.10
k2 41.60 45.88 43.02 41.84
k3 50.97 38.58 45.60 45.31
极差 13.28 7.30 3.95 3.47
极差占比/% 47.40 26.00 14.10 12.40
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正交试验因素、水平及结果

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试验编号 A
浸出温度/℃
B
浸出时间/h
C
固液质量体积比
D
钛白废酸浓度/%
钒浸出率/%
1 25 3 1∶7 20 37.98
2 25 2 1∶3 10 38.17
3 25 1 1∶5 5 36.92
4 60 3 1∶3 5 45.47
5 60 2 1∶5 20 45.92
6 60 1 1∶7 10 33.41
7 80 3 1∶5 10 53.95
8 80 2 1∶7 5 53.55
9 80 1 1∶3 20 45.41
k1 37.69 45.80 41.65 43.10
k2 41.60 45.88 43.02 41.84
k3 50.97 38.58 45.60 45.31
极差 13.28 7.30 3.95 3.47
极差占比/% 47.40 26.00 14.10 12.40
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试验编号 滤渣质量/g 滤渣中w(V2O5)/% 钒浸出率/%
10 38.7 1.010 51.57
11 38.5 0.998 53.14
12 38.6 0.986 53.81
平均 38.6 0.998 52.84
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验证试验结果

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试验编号 滤渣质量/g 滤渣中w(V2O5)/% 钒浸出率/%
10 38.7 1.010 51.57
11 38.5 0.998 53.14
12 38.6 0.986 53.81
平均 38.6 0.998 52.84
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项目 成本单价 耗量/t 费用/(元·t-1)
钛白废酸原料费 0元/t 5 0
含钒尾渣原料费 100元/t 1 100
水费 3.16元/t 0.5 1.58
电费 0.37元/(kW·h) 500 185
人工费 80
折旧费 18.7
合计 385.28
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经济效益评估分析结果

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项目 成本单价 耗量/t 费用/(元·t-1)
钛白废酸原料费 0元/t 5 0
含钒尾渣原料费 100元/t 1 100
水费 3.16元/t 0.5 1.58
电费 0.37元/(kW·h) 500 185
人工费 80
折旧费 18.7
合计 385.28
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用钛白废酸从提钒尾渣中提钒试验研究
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李军 1, 2 , 吴恩辉 1, 2 , 徐众 1, 2 , 侯静 1, 2 , 彭文静 1, 2 , 李宏 1, 2
湿法冶金 | 试验研究 2024,43(1): 29-33
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湿法冶金 | 试验研究 2024, 43(1): 29-33
用钛白废酸从提钒尾渣中提钒试验研究
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李军1, 2, 吴恩辉1, 2, 徐众1, 2, 侯静1, 2, 彭文静1, 2, 李宏1, 2
作者信息
  • 1 攀枝花学院 钒钛学院, 四川 攀枝花 617000
  • 2 钒钛资源综合利用四川省重点实验室, 四川 攀枝花 617000
  • 李军(1986—),男,博士,副研究员,主要研究方向为钒钛资源综合利用。

Extraction of Vanadium from Vanadium Tailing Slag with Titanium Dioxide Waste Acid
Jun LI1, 2, Enhui WU1, 2, Zhong XU1, 2, Jing HOU1, 2, Wenjing PENG1, 2, Hong LI1, 2
Affiliations
  • 1 College of Vanadium and Titanium, Panzhihua University, Panzhihua 617000, China
  • 2 Vanadium and Titanium Resources Comprehensive Utilization Key Laboratory of Sichuan Province, Panzhihua 617000, China
出版时间: 2024-02-20 doi: 10.13355/j.cnki.sfyj.2024.01.005
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为实现固体和液体废弃物的高值化利用,研究了用钛白废酸从提钒尾渣中提取钒。通过正交试验考察了浸出温度、浸出时间、固液质量体积比、钛白废酸浓度等工艺参数对钒浸出率的影响,优化了浸出条件。为进一步提高钒浸出率,探讨了助浸剂(萤石)和氧化剂(双氧水)的适宜添加量。结果表明:各工艺参数对钒浸出率的影响顺序为浸出温度>浸出时间>固液质量体积比>钛白废酸浓度;在温度80 ℃、浸出时间2 h、固液质量体积比1∶5、废酸浓度5%优化试验条件下,钒浸出率为53%左右;加入7%萤石和5%双氧水后,钒浸出率可提高至71.09%。
钛白废酸  /  提钒尾渣  /  钒  /  浸出  /  萤石  /  双氧水

In order to realize the high value utilization of solid and liquid wastes, extraction of vanadium from vanadium tailings with titanium dioxide waste acid was studied. The effects of leaching temperature, leaching time, solid mass to liquid volume ratio, waste acid concentration and other technological parameters on vanadium leaching rate were investigated by orthogonal experiments, and the optimal leaching conditions were determined. In order to further improve the vanadium leaching rate, the appropriate amount of leaching aid (fluorite) and oxidant (hydrogen peroxide) was discussed. The results show that the order of influence of the process parameters on vanadium leaching rate is leaching temperature> leaching time> solid mass to liquid volume ratio> titanium dioxide waste acid concentration. Under the optimum conditions of temperature of 80 ℃, leaching time of 2 h, solid mass to liquid volume ratio of 1∶5 and waste acid concentration of 5%, the vanadium leaching rate is about 53%. After adding 7% fluorite and 5% hydrogen peroxide, the vanadium leaching rate can be increased to 71.09%.

titanium dioxide waste acid  /  vanadium tailings  /  vanadium  /  leaching  /  fluorite  /  hydrogen peroxide
李军, 吴恩辉, 徐众, 侯静, 彭文静, 李宏. 用钛白废酸从提钒尾渣中提钒试验研究. 湿法冶金, 2024 , 43 (1) : 29 -33 . DOI: 10.13355/j.cnki.sfyj.2024.01.005
Jun LI, Enhui WU, Zhong XU, Jing HOU, Wenjing PENG, Hong LI. Extraction of Vanadium from Vanadium Tailing Slag with Titanium Dioxide Waste Acid[J]. Hydrometallurgy of China, 2024 , 43 (1) : 29 -33 . DOI: 10.13355/j.cnki.sfyj.2024.01.005
提钒尾渣是钒渣提钒后副产物。攀钢、承钢等企业年产提钒尾渣约50万t[1],大量提钒尾渣被堆存,长期占用场地,所含可溶性Cr6+、V5+等若得不到妥善处理,将会对周边环境造成严重污染,同时也可能给人体健康带来危害。目前,综合回收提钒尾渣的方法主要分为火法、湿法和直接利用法。火法可实现铁、钒、铬、镓等有价元素的综合回收,但能耗高,污染大[2-4];湿法工艺包括直接酸浸法[5]、氧压酸浸法[6]、多种酸组合浸出法[7]等,与火法相比,湿法工艺较简单,能耗更低,但耗酸量较大,成本较高,钒回收率也不十分理想;直接利用法是将提钒尾渣直接制成钒钛黑瓷等特定功能材料[8-13],但元素综合回收效果欠佳,易造成资源浪费。因此,探寻一种从提钒尾渣中高效提取有价金属元素的方法,对于综合回收利用此类资源具有重要意义。
目前,钛白粉的生产工艺主要以硫酸法为主,每生产1 t钛白粉会产生6 t左右浓度20%的钛白废酸。为高值化利用钛白废酸和提钒尾渣,降低生产成本,提高经济效益,试验研究了用钛白废酸浸出提钒尾渣中的钒,考察了各工艺参数对钒浸出率的影响规律。
提钒尾渣:攀枝花某企业采用钠化焙烧—水浸提钒后的残渣,主要化学成分见表1,粒度分布见表2。由表1看出:提钒尾渣中铁氧化物、TiO2、SiO2质量分数较高;V2O5、Cr2O3质量分数分别为2.08%和2.24%,二者相当,与其他工业含钒尾渣相比,钒、铬含量较高;此外还含少量MnO、Na2O、CaO和MgO等氧化物。由表2看出:粒度稍大,200目以上占38.8%。
提钒尾渣的X射线衍射图谱如图1所示,可以看出,其主要物相为三氧化二铁、硅酸盐相。
提钒尾渣物相组成在空间上的分布直接影响其物理化学性质,因此,有必要对提钒尾渣的空间结构和元素分布进行研究,图23为提钒尾渣的SEM分析结果、元素面扫及分布。可以看出:提钒尾渣呈聚合状和条状,聚合状颗粒较大,直径为30~60 μm,条状颗粒尺寸较小,为10 μm;白色尖晶石被灰色硅酸盐相包裹,部分尖晶石呈分散状,另一部分尖晶石连结在一起,尖晶石颗粒大小一般为2~10 μm;白色区域的尖晶石相主要含有Ti、V、Cr和Fe等元素;灰色区域的硅酸盐相主要含有Ca、Si、Al和Fe等元素;O元素分布于所有区域。
钛白废酸:取自攀枝花海峰鑫有限公司,采用硫酸法钛白工艺产生的废酸,主要成分见表3。其他试剂有氟化钙、5%双氧水、3%高锰酸钾,均为分析纯。
SZCL-3B型磁力搅拌电热套,巩义市瑞力仪器设备有限公司;SHZ-D(Ⅲ)型循环水真空抽滤机,郑州市亚荣仪器有限公司。
提钒尾渣中的钒主要以+3价和+4价存在,部分以+5价存在,其中+3价钒不与硫酸反应,在浸出过程中需将不溶性+3价钒尽量多地转化为可溶性的+4价或+5价钒,以提高钒回收率[13]。提钒尾渣中各氧化物可与废酸中H2SO4发生反应,见式(1)~(4)。提钒尾渣中Ca与H2SO4反应生成CaSO4沉淀,Fe、V与H2SO4反应后生成可溶于酸的FeSO4、(VO2)2SO4、VOSO4
CaO+H2SO4═══════CaSO4↓+H2O;
FeO+H2SO4═══════FeSO4+H2O;
V2O5+H2SO4═══════(VO2)2SO4+H2O;
V2O4+2H2SO4═══════2VOSO4+2H2O。
提钒尾渣中钒分布在尖晶石结构中,尖晶石被硅酸盐包裹。为了破坏硅酸盐结构,促进钒浸出,加入助浸剂萤石(CaF2)。CaF2与废酸中H2SO4生成HF,可破坏提钒尾渣中的硅酸盐相,使硅酸盐包裹的含钒尖晶石相得以释放。发生的化学反应见式(5)~(6)。
CaF2+H2SO4═══════2HF+CaSO4↓;
CaSi2O5+10HF═══════CaF2+2SiF4+5H2O。
硅酸盐相被破坏后,释放出的三价钒不与酸反应,通过加入高锰酸钾[14]或双氧水[15-16]等氧化剂,可将低价钒氧化成高价钒,高价钒可与酸反应被浸出。发生的化学反应见式(7)~(10)。
5V2O3+11H2SO4+4KMnO4═══════5(VO2)2SO4+2K2SO4+4MnSO4+11H2O;
5V2O4+8H2SO4+2KMnO4═══════5(VO2)2SO4+K2SO4+2MnSO4+8H2O;
V2O3+H2SO4+2H2O2═══════(VO2)2SO4+3H2O;
V2O4+H2SO4+H2O2═══════(VO2)2SO4+2H2O。
称取一定质量提钒尾渣放入烧杯中,按照一定固液质量体积比加入钛白废酸,再加入一定量助浸剂萤石(CaF2)和3%高锰酸钾或5%双氧水氧化剂,烧杯在磁力搅拌器加热套中搅拌加热,浸出反应一定时间后停止搅拌和加热,真空抽滤,滤渣称重,测定其中的钒含量,计算钒浸出率。
$\eta =\left(1-\frac{{m}_{1}{w}_{1}}{{m}_{0}{w}_{0}}\right)\times 100\%。$
式中:η—钒浸出率,%;m0—提钒尾渣质量,g;w0—提钒尾渣中钒质量分数,%;m1—滤渣质量,g;w1—滤渣中钒质量分数,%。
影响提钒尾渣中钒浸出的主要因素有浸出温度、废酸浓度、浸出时间、固液质量体积比、粒度等。通过条件试验,提钒尾渣中的钒进入酸浸液中,可为后续沉淀钒提供原料。固定试验条件:提钒尾渣每次称取50 g;搅拌速度200 r/min,粒度-200目占40%左右。选择浸出温度、钛白废酸浓度、浸出时间、固液质量体积比4个因素,设计4因素3水平(L9(34))正交试验。正交试验因素、水平及结果见表4
表4看出:在选定的试验条件范围内,各因素对钒浸出率的影响顺序为浸出温度>浸出时间>固液质量体积比>钛白废酸浓度;确定优化试验条件为温度80 ℃,浸出时间2 h,固液质量体积比1∶5,钛白废酸浓度5%。
为了验证提钒尾渣酸浸试验稳定性,在上述优化试验条件进行3组验证试验,结果见表5。可以看出:在优化条件下,3组试验结果相近,相差不大,钒平均浸出率为53%左右,说明浸出结果较稳定。
在优化浸出条件下钒浸出率也仅为53%左右,为进一步提高钒浸出率,考察助浸剂萤石对提钒尾渣酸浸过程中钒浸出率的影响规律。提钒尾渣50 g,浸出时间2 h,钛白废酸浓度5%,固液质量体积比1∶5,温度80 ℃,萤石加入量对钒浸出率的影响试验结果如图4所示。
图4看出:随萤石加入量增加,钒浸出率不断升高;萤石加入量增至7%时,钒浸出率达62.58%;进一步增加萤石加入量,钒浸出率变化不大。这是因为萤石中的F-离子能破坏包裹在尖晶石外面的硅酸盐结构中的Si—O键,疏通含钒矿物的孔洞,促进酸与钒尖晶石矿物发生反应,提高钒浸出率。
在提钒尾渣50 g、温度80 ℃、浸出时间2 h、钛白废酸浓度5%、固液质量体积比1∶5、萤石加入量7%条件下,考察不同氧化剂对钒浸出率的影响,试验结果如图5所示。可以看出:以5%双氧水作为氧化剂从提钒尾渣中浸出钒,钒浸出率高于3%高锰酸钾,说明双氧水的氧化效果更佳。
以处理1 t含钒尾渣为计算基准,估算经济效益。人工费按原料成本8%计算,折旧费按水电成本10%计算,原料及产品价格为目前市场平均价格,该工艺经济效益估算结果见表6。按上述提钒尾渣浸出率70%、水解率90%、综合回收率为63%进行计算,1 t提钒尾渣可以生产富钒料24.25 kg,富钒料中V2O5质量分数为54%,可得到13.1 kg五氧化二钒产品。根据目前富钒料售价4万元/t计算,合计844元/t,扣除成本385.28元/t,每处理1 t含钒废渣产生经济效益458.72元,按照年处理含钒废渣2万t计算,每年可产生经济效益917万元,经济效益显著。
以钛白废酸为浸出剂、萤石为助浸剂、双氧水为氧化剂能提高钒尾渣中钒浸出率。针对提钒尾渣50 g,在温度80 ℃、浸出时间2 h、钛白废酸浓度5%、固液质量体积比1∶5、萤石加入量7%最佳试验条件下,钒浸出率为62.58%,再加入5%双氧水进行氧化,钒浸出率可提升至71.09%。
钛白废酸与提钒尾渣为原料生产富钒料,可降低钛白废酸酸度,使含钒废渣中的钒资源得到回收,实现主要固体和液体废弃物的高值化利用。该工艺生产成本低,具有一定的经济效益。
  • 四川省高等学校重点实验室项目(FQWLY-2021-Z-08)
  • 四川省高校重点实验室项目(2023JXY01)
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2024年第43卷第1期
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doi: 10.13355/j.cnki.sfyj.2024.01.005
  • 接收时间:2023-08-08
  • 首发时间:2025-09-10
  • 出版时间:2024-02-20
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  • 收稿日期:2023-08-08
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四川省高等学校重点实验室项目(FQWLY-2021-Z-08)
四川省高校重点实验室项目(2023JXY01)
作者信息
    1 攀枝花学院 钒钛学院, 四川 攀枝花 617000
    2 钒钛资源综合利用四川省重点实验室, 四川 攀枝花 617000
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https://castjournals.cast.org.cn/joweb/sfyj/CN/10.13355/j.cnki.sfyj.2024.01.005
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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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