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Article(id=1148106701632434562, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1148106698197295351, articleNumber=1003-3033(2025)02-0040-09, orderNo=null, doi=10.16265/j.cnki.issn1003-3033.2025.02.1081, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1725984000000, receivedDateStr=2024-09-11, revisedDate=1732032000000, revisedDateStr=2024-11-20, acceptedDate=null, acceptedDateStr=null, onlineDate=1751659568460, onlineDateStr=2025-07-05, pubDate=1740672000000, pubDateStr=2025-02-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1751659568460, onlineIssueDateStr=2025-07-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1751659568460, creator=13701087609, updateTime=1751659568460, updator=13701087609, issue=Issue{id=1148106698197295351, tenantId=1146029695717560320, journalId=1146031787341344770, year='2025', volume='35', issue='2', pageStart='1', pageEnd='252', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1751659567641, creator=13701087609, updateTime=1757401525528, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1172190215188894212, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1148106698197295351, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1172190215188894213, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1148106698197295351, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=40, endPage=48, ext={EN=ArticleExt(id=1149767844285563735, articleId=1148106701632434562, tenantId=1146029695717560320, journalId=1146031787341344770, language=EN, title=Study on the impact of abnormal gases in filling work faces on sensor cross-interference, columnId=1149733269173878863, journalTitle=China Safety Science Journal, columnName=Safety engineering technology, runingTitle=null, highlight=null, articleAbstract=

In order to elucidate the specific causes of abnormal alarms from CH4 and CO sensors in the return corner of the backfill working face，a systematic investigation was conducted. Initially，a programmed heating-gas chromatography (GC) experiment was carried out on filling materials，complemented by on-site GC measurements，to evaluate whether the alarms were attributable to CH4 and CO concentrations exceeding threshold limits. Subsequently，a portable gas detector was employed to monitor various filling materials，identifying the primary materials responsible for triggering the sensor alarms. Finally，GC-mass spectrometry (MS) analysis was performed to characterize the volatile components of adhesives and their interference effects on CH4 and CO sensors. The results indicate that the alarms triggered by CH4 and CO sensors were caused by the volatile gases from adhesives，rather than by an excessive concentration of CH4 or CO. The primary constituents of the adhesive VOCs were alkanes，while secondary components included alcohols and esters. Key interfering substances for CH4 sensor were alkanes such as C5H12，C6H12，and C6H14，with minor contributions from alcohols and esters such as CH4O，C2H4O2，and C3H8O2. All ten tested combustible gases exhibited cross-interference effects on CH4 sensor. Interfering substances for CO sensor included CH4O，C2H4O2，and C3H8O2. While the sensors demonstrated short-term resilience to interference under abnormal gas atmospheres，their stability and anti-interference performance significantly deteriorated with prolonged exposure.

, correspAuthors=Hui ZHUO, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Wei LU, Rui LUO, Qingsong ZHANG, Hui ZHUO, Jinliang LI, Sichao ZHU), CN=ArticleExt(id=1148106710314643473, articleId=1148106701632434562, tenantId=1146029695717560320, journalId=1146031787341344770, language=CN, title=充填工作面异常气体对传感器交叉干扰的影响研究, columnId=1149733269727526997, journalTitle=中国安全科学学报, columnName=安全工程技术, runingTitle=null, highlight=null, articleAbstract=

为明确充填工作面回风隅角CH4、CO传感器异常报警的具体原因，开展传感器异常报警诱因的系统性分析。首先，通过充填材料程序升温-气相色谱(GC)试验，并结合现场GC分析结果，判断CH4、CO传感器报警是否由CH4、CO气体体积分数超限所致；然后，利用便携式气体检测仪监测各类充填原材料，确定导致传感器报警的主要充填原材料;最后，进行GC-质谱(MS)试验，分析胶黏剂挥发性成分及其对CH4、CO传感器的干扰效应。结果表明：CH4、CO传感器报警由胶黏剂挥发气体引起，并非CH4、CO气体体积分数超限；胶黏剂挥发气体的主要成分为烷烃类，次要成分为醇酯类等其他气体；对CH4传感器的主要干扰气体为C5H12、C6H12、C6H14等烷烃类气体，次要干扰气体为CH4O、C2H4O2、C3H8O2等，试验所测10种可燃气体均对CH4传感器产生交叉干扰；对CO传感器的干扰气体为CH4O、C2H4O2、C3H8O2，传感器在短期内处于异常气体气氛下，具备一定抗干扰能力，但长期暴露下其稳定性和抗干扰能力下降。

, correspAuthors=卓辉, authorNote=null, correspAuthorsNote=
**卓辉(1992—)，男，安徽萧县人，博士，讲师，主要从事热动力灾害防治、采空区监测预警等方向研究。E-mail：。
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陆伟 (1977—)，男，四川广安人，博士，教授，主要从事矿井热动力灾害防治、防灭火材料研发等方面研究。E-mail：。

张青松 教授

李金亮 副教授

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陆伟 (1977—)，男，四川广安人，博士，教授，主要从事矿井热动力灾害防治、防灭火材料研发等方面研究。E-mail：。

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陆伟 (1977—)，男，四川广安人，博士，教授，主要从事矿井热动力灾害防治、防灭火材料研发等方面研究。E-mail：。

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张青松 教授

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张青松 教授

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李金亮 副教授

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李金亮 副教授

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Journal of Chongqing Normal University:Natural Science Edition, 2023, 40(4): 136-142., articleTitle=Determination of the bioactivity of water pepper extract and GC-MS analysis of its volatile components, refAbstract=null), Reference(id=1165681989593084400, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=1, pageEnd=9, url=null, language=null, rfNumber=[14], rfOrder=24, authorNames=杨永婧, 任静怡, 李政达, journalName=食品与发酵工业, refType=null, unstructuredReference=杨永婧, 任静怡, 李政达, 等. 基于定量描述性分析法和GC-MS对低温发酵面包特征香味物质的分析[J/OL]. 食品与发酵工业: 1-9[2024-10-17]. https://doi.org/10.13995/j.cnki.11-1802/ts.039329., articleTitle=基于定量描述性分析法和GC-MS对低温发酵面包特征香味物质的分析, refAbstract=null), Reference(id=1165681989874102770, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=1, pageEnd=9, url=null, language=null, rfNumber=[14], rfOrder=25, authorNames=YANG Yongjing, REN Jingyi, LI Zhengda, journalName=Food and Fermentation Industries, refType=null, unstructuredReference=YANG Yongjing, REN Jingyi, LI Zhengda, et al. 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Food and Fermentation Industries: 1-9[2024-10-17]. https://doi.org/10.13995/j.cnki.11-1802/ts.039329., articleTitle=Analysis of characteristic aroma substances in low temperature fermented bread by quantitative descriptive analysis and gas chromatography-mass spectrometry, refAbstract=null), Reference(id=1165681990159315444, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, doi=null, pmid=null, pmcid=null, year=2024, volume=45, issue=17, pageStart=191, pageEnd=198, url=null, language=null, rfNumber=[15], rfOrder=26, authorNames=陈宝蓉, 曹洪宇, 张雨萌, journalName=食品科学, refType=null, unstructuredReference=陈宝蓉, 曹洪宇, 张雨萌, 等. 不同热处理对马乳中蛋白及风味物质的影响[J]. 食品科学, 2024, 45(17):191-198., articleTitle=不同热处理对马乳中蛋白及风味物质的影响, refAbstract=null), Reference(id=1165681990444528117, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, doi=null, pmid=null, pmcid=null, year=2024, volume=45, issue=17, pageStart=191, pageEnd=198, url=null, language=null, rfNumber=[15], rfOrder=27, authorNames=CHEN Baorong, CAO Hongyu, ZHANG Yumeng, journalName=Food Science, refType=null, unstructuredReference=CHEN Baorong, CAO Hongyu, ZHANG Yumeng, et al. Effect of different heat treatments on protein and volatile compounds in mare milk[J]. Food Science, 2024, 45(17):191-198., articleTitle=Effect of different heat treatments on protein and volatile compounds in mare milk, refAbstract=null)], funds=[Fund(id=1165681981405802925, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, awardId=2023YFC3009102, language=CN, fundingSource=国家重点研发计划(2023YFC3009102), fundOrder=null, country=null), Fund(id=1165681981644878255, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, awardId=52204192, language=CN, fundingSource=国家自然科学基金资助(52204192), fundOrder=null, country=null), Fund(id=1165681982001394097, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, awardId=2022m07020006, language=CN, fundingSource=安徽省重点研究与开发计划项目(2022m07020006), fundOrder=null, country=null), Fund(id=1165681982093668786, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, awardId=2021yjrc42, language=CN, 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figureFileSmall=I2WGt+hQ35UszzC4H21W2g==, figureFileBig=Q6RQhqFjkvt5aVm7VMhokQ==, tableContent=null), ArticleFig(id=1165681973688283533, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=图1, caption=工作面回风隅角CH4体积分数变化情况, figureFileSmall=I2WGt+hQ35UszzC4H21W2g==, figureFileBig=Q6RQhqFjkvt5aVm7VMhokQ==, tableContent=null), ArticleFig(id=1165681973960913294, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=EN, label=Fig.2, caption=Temperature variation during solidification process of filling materials, figureFileSmall=hJJovt6gdAl7T8j/NcmjdQ==, figureFileBig=Hruo9dj7hc8KLrGvj+MGow==, tableContent=null), ArticleFig(id=1165681974267097487, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=图2, caption=充填材料固化过程温度变化, figureFileSmall=hJJovt6gdAl7T8j/NcmjdQ==, figureFileBig=Hruo9dj7hc8KLrGvj+MGow==, tableContent=null), 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label=Fig.6, caption=Total ion chromatogram of volatile compounds in adhesive at 30 ℃, figureFileSmall=xhTI3XOknyFc/tlscPSC6w==, figureFileBig=2JQtXDakwz+jnOO5ljngmw==, tableContent=null), ArticleFig(id=1165681976523633047, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=图6, caption=30 ℃条件下胶黏剂挥发性物质的部分离子流色谱, figureFileSmall=xhTI3XOknyFc/tlscPSC6w==, figureFileBig=2JQtXDakwz+jnOO5ljngmw==, tableContent=null), ArticleFig(id=1165681976783679896, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=EN, label=Fig.7, caption=Cross-interference effect of reagent volatile gases on CH4 sensor, figureFileSmall=rtIpVyZeOpGKnSAAZMqt5A==, figureFileBig=4zjm4Yu4G9jtNZ34IOou6A==, tableContent=null), ArticleFig(id=1165681977047921049, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=图7, caption=试剂挥发气体对CH4传感器交叉干扰影响, 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figureFileSmall=7yp+2uyZf/jtOLvK78lunA==, figureFileBig=wZUSDpOSDkg3tS+I3Yxfpg==, tableContent=null), ArticleFig(id=1165681978398486941, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=图9, caption=试剂挥发气体对CO传感器交叉干扰影响, figureFileSmall=7yp+2uyZf/jtOLvK78lunA==, figureFileBig=wZUSDpOSDkg3tS+I3Yxfpg==, tableContent=null), ArticleFig(id=1165681978729836958, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=EN, label=Table 1, caption=

Gas inspection record sheet

, figureFileSmall=null, figureFileBig=null, tableContent=
工艺 检查地点 检查时间 CH4/% CO/10-6
充填 回风隅角 1：50 0.33 112
3：00 0.32 116
移架 47号架后顶板 1：10 0.39 460
30号架后顶板 10:00 0.44 750
), ArticleFig(id=1165681978926969247, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=表1, caption=

气体检查记录

, figureFileSmall=null, figureFileBig=null, tableContent=
工艺 检查地点 检查时间 CH4/% CO/10-6
充填 回风隅角 1：50 0.33 112
3：00 0.32 116
移架 47号架后顶板 1：10 0.39 460
30号架后顶板 10:00 0.44 750
), ArticleFig(id=1165681979224764832, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=EN, label=Table 2, caption=

Volatile gases from adhesive at 30 ℃

, figureFileSmall=null, figureFileBig=null, tableContent=
饱和烃 不饱和烃 其他
C5H12 C6H10 CH4O
C6H14 C6H12 C2H4O2
C7H16 C7H14 C3H6O2
C8H18 C8H10 C3H8O2
C9H20 C8H16 CH2Cl2
C10H22 C10H20 —
C11H24 — —
C12H26 — —
C13H28 — —
), ArticleFig(id=1165681979484811681, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=表2, caption=

30 ℃条件下胶黏剂挥发性气体

, figureFileSmall=null, figureFileBig=null, tableContent=
饱和烃 不饱和烃 其他
C5H12 C6H10 CH4O
C6H14 C6H12 C2H4O2
C7H16 C7H14 C3H6O2
C8H18 C8H10 C3H8O2
C9H20 C8H16 CH2Cl2
C10H22 C10H20 —
C11H24 — —
C12H26 — —
C13H28 — —
), ArticleFig(id=1165681979757441442, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=EN, label=Table 3, caption=

Qualitative analysis of volatile gases from selected adhesives at 30 ℃

, figureFileSmall=null, figureFileBig=null, tableContent=
分子式 中文名称 保留时间/s 匹配度/%
CH4O 甲醇 1.196 95
C2H4O2 甲酸甲酯 1.323 92
C3H8O2 二甲氧基甲烷 1.384 92
C5H12 正戊烷 1.494 96
CH2Cl2 二氯甲烷 1.537 93
C6H14 正己烷 1.784 96
C6H12 甲基环戊烷 1.977 95
C8H16 1-辛烯 2.449 94
C8H18 异辛烷 2.866 97
C10H20 1-癸烯 5.563 92
), ArticleFig(id=1165681980084597155, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=表3, caption=

30 ℃条件下部分胶黏剂挥发气体定性表

, figureFileSmall=null, figureFileBig=null, tableContent=
分子式 中文名称 保留时间/s 匹配度/%
CH4O 甲醇 1.196 95
C2H4O2 甲酸甲酯 1.323 92
C3H8O2 二甲氧基甲烷 1.384 92
C5H12 正戊烷 1.494 96
CH2Cl2 二氯甲烷 1.537 93
C6H14 正己烷 1.784 96
C6H12 甲基环戊烷 1.977 95
C8H16 1-辛烯 2.449 94
C8H18 异辛烷 2.866 97
C10H20 1-癸烯 5.563 92
), ArticleFig(id=1165681980466278820, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=EN, label=Table 4, caption=

Heat of combustion for selected substances

, figureFileSmall=null, figureFileBig=null, tableContent=
物质名 燃烧热/(kJ·mol-1) 沸点/℃
甲烷 -891 -161.5
正戊烷 -3 535.73 36
甲基环戊烷 -3 969.86 71.8
正己烷 -4 159.1 69
1-辛烯 -5 353.18 125.6
异辛烷 -5 496.48 107
1-癸烯 -6 223.9 170.6
甲醇 -764.9 64.7
甲酸甲酯 -1 003.20 32
二甲氧基甲烷 -1 975.68 40.5
), ArticleFig(id=1165681980675994022, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106701632434562, language=CN, label=表4, caption=

部分物质燃烧热

, figureFileSmall=null, figureFileBig=null, tableContent=
物质名 燃烧热/(kJ·mol-1) 沸点/℃
甲烷 -891 -161.5
正戊烷 -3 535.73 36
甲基环戊烷 -3 969.86 71.8
正己烷 -4 159.1 69
1-辛烯 -5 353.18 125.6
异辛烷 -5 496.48 107
1-癸烯 -6 223.9 170.6
甲醇 -764.9 64.7
甲酸甲酯 -1 003.20 32
二甲氧基甲烷 -1 975.68 40.5
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Different volume fractions of VOC

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液体体积/mL 0.5 1 1.5 2 2.5 3 3.5 4
正戊烷/% 1.05 2.10 3.15 4.20 5.25 6.30 7.35 8.40
甲基环戊烷/% 1.10 2.20 3.30 4.40 5.50 6.60 7.70 8.80
正己烷/% 0.93 1.86 2.79 3.72 4.65 5.58 6.51 7.44
1-辛烯/% 0.78 1.56 2.34 3.12 3.90 4.68 5.46 6.24
异辛烷/% 0.74 1.48 2.22 2.96 3.70 4.44 5.18 5.92
1-癸烯/% 0.64 1.29 1.94 2.59 3.24 3.88 4.53 5.18
甲醇/% 3.03 6.06 9.09 12.12 15.15 18.18 21.21 24.24
甲酸甲酯/% 1.95 3.89 5.84 7.78 9.73 11.68 13.63 15.58
二甲氧基甲烷/% 1.39 2.78 4.17 5.56 6.95 8.34 9.73 11.12
二氯甲烷/% 1.91 3.82 5.73 7.64 9.55 11.46 13.37 15.28
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不同体积分数的VOC

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液体体积/mL 0.5 1 1.5 2 2.5 3 3.5 4
正戊烷/% 1.05 2.10 3.15 4.20 5.25 6.30 7.35 8.40
甲基环戊烷/% 1.10 2.20 3.30 4.40 5.50 6.60 7.70 8.80
正己烷/% 0.93 1.86 2.79 3.72 4.65 5.58 6.51 7.44
1-辛烯/% 0.78 1.56 2.34 3.12 3.90 4.68 5.46 6.24
异辛烷/% 0.74 1.48 2.22 2.96 3.70 4.44 5.18 5.92
1-癸烯/% 0.64 1.29 1.94 2.59 3.24 3.88 4.53 5.18
甲醇/% 3.03 6.06 9.09 12.12 15.15 18.18 21.21 24.24
甲酸甲酯/% 1.95 3.89 5.84 7.78 9.73 11.68 13.63 15.58
二甲氧基甲烷/% 1.39 2.78 4.17 5.56 6.95 8.34 9.73 11.12
二氯甲烷/% 1.91 3.82 5.73 7.64 9.55 11.46 13.37 15.28
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充填工作面异常气体对传感器交叉干扰的影响研究
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陆伟 1, 2 , 罗瑞 1 , 张青松 1, 2 , 卓辉 1, 2, ** , 李金亮 1, 2 , 朱思超 3
中国安全科学学报 | 安全工程技术 2025,35(2): 40-48
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中国安全科学学报 | 安全工程技术 2025, 35(2): 40-48
充填工作面异常气体对传感器交叉干扰的影响研究
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陆伟1, 2 , 罗瑞1, 张青松1, 2, 卓辉1, 2, ** , 李金亮1, 2, 朱思超3
作者信息
  • 1 安徽理工大学 安全科学与工程学院，安徽 淮南 232001
  • 2 安徽理工大学 矿山安全高效开采安徽省高校工程技术研究中心，安徽 淮南 232001
  • 3 枣庄矿业(集团) 岱庄煤业有限公司，山东 枣庄 277000

    • 陆伟 (1977—)，男，四川广安人，博士，教授，主要从事矿井热动力灾害防治、防灭火材料研发等方面研究。E-mail：。

    张青松 教授

    李金亮 副教授

通讯作者:

**卓辉(1992—)，男，安徽萧县人，博士，讲师，主要从事热动力灾害防治、采空区监测预警等方向研究。E-mail：。
Study on the impact of abnormal gases in filling work faces on sensor cross-interference
Wei LU1, 2 , Rui LUO1, Qingsong ZHANG1, 2, Hui ZHUO1, 2, ** , Jinliang LI1, 2, Sichao ZHU3
Affiliations
  • 1 School of Safety and Engineering，Anhui University of Science and Technology，Huainan Anhui 232001，China
  • 2 Anhui Province University Engineering Technology Research Center for Safe and Efficient Mining，Anhui University of Science and Technology，Huainan Anhui 232001，China
  • 3 Daizhuang Coal Mining Company，Zaozhuang Mining (Group) Co.，Ltd.，Zaozhuang Shandong 277000，China
出版时间: 2025-02-28 doi: 10.16265/j.cnki.issn1003-3033.2025.02.1081
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摘要
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为明确充填工作面回风隅角CH4、CO传感器异常报警的具体原因，开展传感器异常报警诱因的系统性分析。首先，通过充填材料程序升温-气相色谱(GC)试验，并结合现场GC分析结果，判断CH4、CO传感器报警是否由CH4、CO气体体积分数超限所致；然后，利用便携式气体检测仪监测各类充填原材料，确定导致传感器报警的主要充填原材料;最后，进行GC-质谱(MS)试验，分析胶黏剂挥发性成分及其对CH4、CO传感器的干扰效应。结果表明：CH4、CO传感器报警由胶黏剂挥发气体引起，并非CH4、CO气体体积分数超限；胶黏剂挥发气体的主要成分为烷烃类，次要成分为醇酯类等其他气体；对CH4传感器的主要干扰气体为C5H12、C6H12、C6H14等烷烃类气体，次要干扰气体为CH4O、C2H4O2、C3H8O2等，试验所测10种可燃气体均对CH4传感器产生交叉干扰；对CO传感器的干扰气体为CH4O、C2H4O2、C3H8O2，传感器在短期内处于异常气体气氛下，具备一定抗干扰能力，但长期暴露下其稳定性和抗干扰能力下降。

充填工作面  /  异常气体  /  传感器  /  交叉干扰  /  回风隅角  /  异常报警  /  胶黏剂

In order to elucidate the specific causes of abnormal alarms from CH4 and CO sensors in the return corner of the backfill working face，a systematic investigation was conducted. Initially，a programmed heating-gas chromatography (GC) experiment was carried out on filling materials，complemented by on-site GC measurements，to evaluate whether the alarms were attributable to CH4 and CO concentrations exceeding threshold limits. Subsequently，a portable gas detector was employed to monitor various filling materials，identifying the primary materials responsible for triggering the sensor alarms. Finally，GC-mass spectrometry (MS) analysis was performed to characterize the volatile components of adhesives and their interference effects on CH4 and CO sensors. The results indicate that the alarms triggered by CH4 and CO sensors were caused by the volatile gases from adhesives，rather than by an excessive concentration of CH4 or CO. The primary constituents of the adhesive VOCs were alkanes，while secondary components included alcohols and esters. Key interfering substances for CH4 sensor were alkanes such as C5H12，C6H12，and C6H14，with minor contributions from alcohols and esters such as CH4O，C2H4O2，and C3H8O2. All ten tested combustible gases exhibited cross-interference effects on CH4 sensor. Interfering substances for CO sensor included CH4O，C2H4O2，and C3H8O2. While the sensors demonstrated short-term resilience to interference under abnormal gas atmospheres，their stability and anti-interference performance significantly deteriorated with prolonged exposure.

backfill working face  /  abnormal gases  /  sensors  /  cross-interference  /  return corner  /  abnormal alarms  /  adhesives
陆伟, 罗瑞, 张青松, 卓辉, 李金亮, 朱思超. 充填工作面异常气体对传感器交叉干扰的影响研究. 中国安全科学学报, 2025 , 35 (2) : 40 -48 . DOI: 10.16265/j.cnki.issn1003-3033.2025.02.1081
Wei LU, Rui LUO, Qingsong ZHANG, Hui ZHUO, Jinliang LI, Sichao ZHU. Study on the impact of abnormal gases in filling work faces on sensor cross-interference[J]. China Safety Science Journal, 2025 , 35 (2) : 40 -48 . DOI: 10.16265/j.cnki.issn1003-3033.2025.02.1081
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0 引言
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煤炭开采过程中，煤自燃及瓦斯事故严重威胁矿井安全生产及工人生命健康[1-2]。气体传感器对矿井火灾及瓦斯灾害早期监测预警至关重要，一旦出现误报警或漏报警现象，将严重影响工作面的安全生产。气体传感器监测的准确性是矿井安全生产及灾害早期预警的前提[3-4]。因此，研究不同原理气体传感器受异常气体交叉干扰影响及精确测量井下常见混合气体体积分数，对保证煤矿井下安全生产具有重要意义。
目前，国内外学者针对气体传感器在特定环境下的交叉干扰特性和多气体混合物体积分数检测方法开展了大量研究。例如：陈勇冉[5]针对井下实际的气体类型，采用理论分析和试验验证相结合的方法，探究了不同工作原理条件下的气体传感器的交叉干扰特性。景元杰[6]研究了基于信息融合技术的多元混合气体浓度检测方法，指出该方法可精确检测混合气体的浓度。MAJDER等[7]研究了波兰救援单位使用的电化学CO传感器，发现Cl2、H2S、NH3等气体不会对传感器造成交叉干扰影响，H2则对其产生了显著的交叉干扰效应，且传感器的使用时间及方式会影响其对H2的反应。GONG Shuli[8]基于模式识别法，利用多气体传感器形成传感器阵列，实现了CO、H2S、SO2和 H2气体混合物的精确监测。梁运涛等[9]分析了煤矿中用于CH4检测的5种技术(催化燃烧法、热导法、光干涉法、非分散红外光谱法和可调谐半导体激光光谱法)，得出不同方法在不同矿井条件下的适用性，为煤矿CH4监测提供指导。现有研究主要集中于验证煤矿井下常见气体对气体传感器的交叉干扰影响以及研究如何实现对多组分混合气体浓度的精确测量。然而，针对充填工作面存在复杂挥发性有机化合物(Volatile Organic Compounds，VOCs)对气体传感器交叉干扰的影响仍缺乏相关研究。
鉴于此，笔者拟选取枣庄矿业(集团)岱庄煤业33上38充填工作面回风隅角CH4、CO传感器异常报警为研究对象，采用气相色谱(Gas Chromatography，GC)分析方法探究工作面现场及充填原材料固化过程中CH4、CO释放体积分数，揭示传感器异常报警原因；利用GC-质谱(Mass Spectrometry，MS)联用仪进一步分析异常气体成分及其对CH4、CO传感器的交叉干扰影响，以期为矿井环境中异常气体对传感器产生干扰的研究提供参考。
1 工作面及传感器异常报警概况
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综采工作面采用走向长壁后退式采煤法开采，利用膏体充填法处理采空区顶板。工作面走向长379 m，倾向长52~165 m(平均108 m)，工作面内煤层赋存稳定，厚度2.5~3.5 m，平均厚度为3.1 m。瓦斯绝对涌出量为1.35 m3/min，相对涌出量为1.09 m3/t。正常生产期间，CH4体积分数在0.01%~0.03%之间。工作面煤自燃倾向性为Ⅱ类，回采过程中采用粉煤灰、矸石和水泥作为主要充填材料直接充实采空区;辅助充填原材料为隔离布、稻草秸秆和胶黏剂。2023年3月19日，33上38工作面移架过程中，回风隅角CH4传感器发生异常报警现象，CH4体积分数变化如图1所示，CH4体积分数最高达到2.15%，报警时长持续46 s。充填工作面回风隅角使用CH4传感器、CO传感器原理分别为催化燃烧式和电化学式。
利用催化燃烧式CH4传感器和电化学式CO便携式传感器监测现场充填及移架工艺流程中的气体，CH4、CO气体传感器皆出现不同程度的异常现象，其中，CH4体积分数在移架过程最高达到0.44%，与工作面正常生产期间CH4体积分数相差较大，CO传感器示数在移架过程中最高达到750×10-6，远超井下CO安全标准24×10-6。具体数据见表1。
2 充填材料及工作面CH4、CO分析
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2.1 充填材料固化过程放热分析
为研究工作面充填原材料在固化过程中的内部温度变化，采用热电偶测量预定配比的充填原材料(水泥∶粉煤灰∶煤矸石∶水的配比为1∶1.4∶3.6∶2.2，水泥用量为50 g)固化过程中的温度。试验条件下，水温20.8 ℃，环境温度25 ℃。充填材料固化过程中温度随时间的变化如图2所示。
由图2可知：充填材料在填充后接近20 min时达到最高温度22.6 ℃，且温度呈现快速上升趋势，随后温度逐渐下降。根据相似模拟试验，大体积充填过程中充填体的最高温度升幅不超过5 ℃。因此，推测工作面充填结束后，混合充填材料在固化过程中其内部温度与工作面温度的差异较小。上述试验结果能够为后续充填原材料程序升温试验设置最高温度提供参考。
2.2 单一充填原材料
岱庄煤矿属于低瓦斯矿井；煤层采用充填方式开采，井下采空区均被粉煤灰、水泥等充实，煤自燃现象不会发生。若井下CH4和CO传感器超限报警，气体来源可能是充填过程中各类原材料因氧化升温产生。因此，利用煤自燃特性测试仪，在20~100 ℃范围内开展粉煤灰、水泥、胶黏剂和稻草秸秆程序升温—GC试验。试验条件如下：分别将20 g各类充填原材料样品置于煤样罐中，升温速率设为0.5 ℃/min，气体流量为50 mL/min，每隔10 ℃抽取气体进行1次色谱分析[10⇓-12]。各单一充填原材料在20~100 ℃条件下CH4和CO气体体积分数变化趋势如图3所示。
由图3可知：在20~100 ℃条件下，粉煤灰和水泥产生的CH4气体体积分数始终维持在约2×10-6，胶黏剂的CH4气体体积分数约为1×10-6，而稻草秸秆几乎不产生CH4气体，各类充填原材料在100 ℃时仅产生微量CH4气体。粉煤灰和胶黏剂在40 ℃前不产生CO气体；随着温度上升，CO气体体积分数缓慢增加，在温度达到100 ℃时，CO体积分数约为5×10-6；水泥在100 ℃之前基本不产生CO气体；稻草秸秆在30 ℃前不产生CO气体，但随着温度上升，CO气体体积分数缓慢增加，温度达到100 ℃时，稻草秸秆产生CO体积分数接近12×10-6。
2.3 充填材料固化过程
为模拟混合充填材料在固化过程中是否释放大量CH4和CO气体，在20~100 ℃升温范围内，对配置预定配比的混合充填材料进行程序升温试验，以确定混合充填料固化过程中CH4和CO气体体积分数的变化特征。试验条件与单一充填原材料的试验条件相同，混合充填材料固化过程中CH4和CO气体体积分数的变化情况如图4所示。
由图4可知：混合材料的CH4释放量最高约为7 ×10-6，在60 ℃之前未检测到CO气体的产生，但随着试验环境温度上升，CO体积分数逐渐增加，温度达到100 ℃时CO体积分数接近5×10-6。
通过分析单一充填原材料和预定比例混合充填材料固化过程的程序升温试验中的CH4和CO气体体积分数变化特征，并结合岱庄矿采空区内CH4和CO的实际情况，初步确定井下工作面仅存在微量的CH4和CO气体。
2.4 现场气样GC分析
为进一步验证工作面回风隅角CH4、CO气体体积分数的真实情况，分别在工作面中部、回风隅角和工作面回风巷现场采集气样，利用GC进行分析，各地点CH4体积分数10天变化曲线如图5所示。
由图5可知：工作面中部、回风隅角和工作面回风巷的CH4体积分数相对较为稳定，最高体积分数未超过0.03%。其中，回风隅角的CH4体积分数相对较高，主要是因为回风隅角处于通风系统的末端，空气流动速度较慢，且空气流动路径复杂，易形成死角，导致CH4在此处积聚。工作面中部和工作面回风巷的通风效果较好，CH4体积分数较低。对于CO气体，经GC分析，CO气体体积分数为0。通过分析现场气样及各充填原材料在程序升温过程中产生气体的GC，确定井下仅存微量的CH4和CO气体，未达到CH4和CO传感器的报警条件。
3 异常气体对传感器交叉干扰的影响
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3.1 异常气体确定
通过对充填原材料进行程序升温试验，现场采集气样进行色谱分析，工作面回风隅角CH4和CO传感器报警不是由于CH4和CO气体体积分数超限造成的。通过使用气体检测仪监测各种充填原材料储存仓库中的气体，发现充填过程使用的胶黏剂产生挥发性气体会导致CH4和CO气体传感器异常报警，由此确定传感器异常报警的原因是胶黏剂挥发性气体对其造成了交叉干扰。
3.1.1 试验材料与方法
试验所用的胶黏剂为鲁班胶黏剂，主要用于充填工作面井下隔离作业。胶黏剂的制作成分主要包括6号油、松香、石油树脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物胶片和CH4等有机材料。由于充填材料固化过程温度与工作面温度相差不大，因此，选用GC-MS联用仪分析胶黏剂在30 ℃条件下挥发气体成分，试验条件如下：顶空条件为，炉内温度30 ℃；定量管温度50 ℃；顶空瓶压力50 kPa；顶空萃取时间30 min。GC-MS条件设置如下：进样温度220 ℃；流量1.5 mL/min；气体为高纯氦气；检测器为电子捕获检测器(Electron Capture Detector，ECD)；色谱柱为SH-Rxi-5Sil MS(30 m ×0.25 mm × 0.25 μm)；柱温程序为60 ℃(3 min)，后以10 ℃/min升温至160 ℃，160 ℃(2 min)[13⇓-15]。
3.1.2 结果与分析
通过GC-MS技术获得胶黏剂在30℃条件下挥发气体的总离子流色谱图，截取出峰物质离子流色谱图如图6所示。通过将色谱图中的各个波峰与MS谱库进行比对分析，确定了胶黏剂气体的挥发性成分(匹配度>80)，结果见表2。
根据图6和表2可知：挥发性成分的主要出峰时间集中在7.5 min前，烃类物质是胶黏剂挥发性气体的主要组成部分，其中C5H12和C6H14等物质存在多种同分异构体，胶黏剂挥发气体主要为VOCs。为保证分析数据的准确性，将匹配度大于92%的组分认为是胶黏剂材料确实存在的挥发性气体，整理30 ℃条件下胶黏剂挥发的部分饱和烃、不饱和烃及醇酯类挥发性气体定性结果，具体分析结果见表3。同时，选择表3中物质对应分析纯试剂(500 mL)获得相应气体，测试各气体组分对CH4、CO传感器的交叉干扰影响。
3.2 异常气体对传感器交叉干扰影响
3.2.1 异常气体对CH4传感器交叉干扰影响
根据催化燃烧式CH4传感器的CH4气体检测原理，几乎所有碳氢化合物都会对传感器产生交叉干扰。干扰程度主要取决于传感器对各气体的选择性、灵敏度及气体自身燃烧热值、体积分数大小。部分物质的燃烧热和沸点见表4，大部分VOC气体的燃烧热值高于CH4，燃烧时释放大量热量，若VOC气体在充填工作面附近积聚，容易导致催化燃烧式CH4传感器发生误报警。
为探究各分析纯试剂挥发气体对催化燃烧式CH4传感器的交叉干扰影响，使用流速为500 mL/min的抽气泵将试剂挥发气体抽入装有CH4气体传感器的气袋中(2 L)。每次抽气泵运转15 s(试剂瓶内气体挥发形成饱和蒸气压需要一定时间)，约抽取125 mL挥发性气体，等待30 s(传感器响应时间为30 s)，观察传感器示数变化，后续重复试验，各试剂挥发气体对CH4传感器的交叉干扰影响变化程度如图7所示。
由图7可知：各试剂挥发气体中，对CH4传感器存在交叉干扰的气体主要包括C5H12、C6H12、C6H14、CH4O、C2H4O2、C3H8O2和CH2Cl2。随着抽取时间和气体量的增加，各挥发气体对CH4传感器的干扰呈线性增长趋势。其中，C5H12在自然挥发条件下对传感器的干扰最大，其次为C2H4O2，而C6H14和C3H8O2的干扰相当;C6H12和CH2Cl2也相当，CH4O干扰影响最小。
为进一步精确定量分析各组分气体对CH4传感器的交叉干扰影响程度，并确定C8H16(1-辛烯)、C8H18(异辛烷)、C10H20(1-癸烯)气体是否对CH4传感器产生交叉干扰，配置不同体积分数的VOC气体，测试其对CH4传感器的交叉干扰，试验方法如下：购买10 L透明特氟龙气袋，分别抽取定量分析纯试剂(0.5、1、1.5、2mL等)至密封气袋中，密封气袋内充满空气，待试剂完全挥发后，测试密封气袋内气体对CH4传感器的交叉干扰影响。密封气袋内各成分气体的体积分数计算方法如下：
m = ρ × V 1
n = m M
V = n R T P
C = V V 2
式中：m为抽取定量分析纯试剂的质量，g；ρ为试剂密度，g/mL;V1为试剂体积，mL；M为物质摩尔质量，g/mol;n为物质的量，mol;V为试剂完全挥发后气体体积，L；R为理想气体常数，取8.314 J/(mol·K)；T为计算温度，取298.15 K；P为标准大气压，取101.325 kPa；C为计算所得气体体积分数，%；V2为所用气袋体积，取10 L。各体积试剂完全挥发后于密封气袋内体积分数见表5，各组分气体对CH4传感器的交叉干扰影响定量曲线如图8所示。
由图8可知：当各类气体体积分数为2 %时，烷烃类气体对CH4传感器的交叉干扰影响显示体积分数在1%以上，醇酯类等其他气体对传感器交叉干扰影响低于1%，各气体组分随体积分数上升对CH4传感器的交叉干扰影响呈线性上升趋势。因此，烷烃类气体对CH4传感器造成交叉干扰影响较大，醇酯类气体影响次之，CH2Cl2体积分数为7.64%时，CH4传感器的读数为0.09%，相比烷烃和CH4O等气体对CH4传感器的影响可以忽略不计。通过上述试验，确定了胶黏剂10种典型挥发性气体不同体积分数对CH4传感器交叉干扰影响程度，胶黏剂挥发的混合挥发性有机物是导致岱庄煤矿井下催化燃烧式CH4传感器误报警的主要原因。
3.2.2 异常气体对CO传感器交叉干扰影响
由文献[5]可知：电化学气体传感器由于制作传感元件和工艺等因素的不同，即使是同一厂家生产的不同型号传感器，对其造成交叉干扰影响的气体也具有不确定性[5]。因此，需要对购买的分析纯试剂气体逐一进行试验。试验条件如下：从分析纯试剂瓶内抽取15 s气体至气袋内(2 L)，气袋内装有A、B传感器(试验所用A、B传感器为同一型号，于试验前已进行过重复试验，相比于B传感器，A传感器在异常气体环境中的暴露时间较短)，等待5 min(传感器大约在5 min后开始有示数变化，随后传感器示数一直呈缓慢上升状态)，记录当前传感器示数。此时继续抽取15 s的气体，等待5 min，记录CO传感器示数，后续重复试验。A、B传感器于同一气氛条件下，各试剂挥发气体对其交叉干扰影响如图9所示。
由图9可知：各试剂挥发气体中仅有CH4O、C2H4O2和C3H8O2对CO传感器有交叉干扰影响。其中，C2H4O2对CO传感器的交叉干扰影响最大，C3H8O2和CH4O的影响相当。多组重复试验发现，CO传感器在短时间内处于异常气体气氛条件下，对异常气体具有一定的抗干扰能力(基本不造成交叉干扰影响)。然而，随着长时间暴露于异常气体气氛，传感器的稳定性及抗干扰能力降低，其对异常气体的响应值会上升。试验中，CO气体传感器对这3种气体的响应都出现了滞后现象，即传感器在接近5 min时开始出现示数变化，且一直缓慢上升。造成这种现象的主要原因是物质分子在电极表面吸附、解离或发生反应时，某些阶段较为耗时，从而延长了整体反应时间，较慢的电化学反应速度会导致传感器响应延迟和示数逐渐上升。另一方面，各气体在传感器表面和内部的扩散速度较慢，导致传感器对气体体积分数的响应时间延长。
4 结论
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1) 工作面充填、移架过程仅产生微量CH4、CO气体，传感器报警并非CH4、CO指标气体超限，而是胶黏剂挥发异常气体所致。
2) 胶黏剂挥发气体中所有可燃气体均会对催化燃烧CH4传感器造成交叉干扰，其中烷烃类气体对CH4传感器造成的交叉干扰影响较大，醇酯类气体的影响次之，影响程度由大到小依次为C6H14、C5H12、C8H18、C6H12、C10H20、C3H8O2、C8H16、C2H4O2、CH4O、CH2Cl2。
3) 胶黏剂挥发气体中对CO传感器造成交叉干扰影响的气体较少，主要有CH4O、C2H4O2、C3H8O2；CO传感器短期内对异常气体具有较好的抗干扰能力，但长期暴露于异常气体中传感器的稳定性及抗干扰能力显著降低，对异常气体的响应值上升。
基金
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  • 国家重点研发计划(2023YFC3009102)
  • 国家自然科学基金资助(52204192)
  • 安徽省重点研究与开发计划项目(2022m07020006)
  • 安徽理工大学高层次引进人才科研启动基金资助(2021yjrc42)
文献
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doi: 10.16265/j.cnki.issn1003-3033.2025.02.1081
  • 接收时间：2024-09-11
  • 首发时间：2025-07-05
  • 出版时间：2025-02-28
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  • 收稿日期：2024-09-11
  • 修回日期：2024-11-20
基金
国家重点研发计划(2023YFC3009102)
国家自然科学基金资助(52204192)
安徽省重点研究与开发计划项目(2022m07020006)
安徽理工大学高层次引进人才科研启动基金资助(2021yjrc42)
作者信息
    1 安徽理工大学 安全科学与工程学院，安徽 淮南 232001
    2 安徽理工大学 矿山安全高效开采安徽省高校工程技术研究中心，安徽 淮南 232001
    3 枣庄矿业(集团) 岱庄煤业有限公司，山东 枣庄 277000

通讯作者:

**卓辉(1992—)，男，安徽萧县人，博士，讲师，主要从事热动力灾害防治、采空区监测预警等方向研究。E-mail：。
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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