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Article(id=1148106727137997499, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1148106708670477182, articleNumber=1003-3033(2025)03-0159-10, orderNo=null, doi=10.16265/j.cnki.issn1003-3033.2025.03.0731, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1729612800000, receivedDateStr=2024-10-23, revisedDate=1735056000000, revisedDateStr=2024-12-25, acceptedDate=null, acceptedDateStr=null, onlineDate=1751659574541, onlineDateStr=2025-07-05, pubDate=1743091200000, pubDateStr=2025-03-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1751659574541, onlineIssueDateStr=2025-07-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1751659574541, creator=13701087609, updateTime=1751659574541, updator=13701087609, issue=Issue{id=1148106708670477182, tenantId=1146029695717560320, journalId=1146031787341344770, year='2025', volume='35', issue='3', pageStart='1', pageEnd='268', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1751659570138, creator=13701087609, updateTime=1757401518130, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1172190184155238915, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1148106708670477182, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1172190184155238916, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1148106708670477182, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=159, endPage=168, ext={EN=ArticleExt(id=1149767350146220386, articleId=1148106727137997499, tenantId=1146029695717560320, journalId=1146031787341344770, language=EN, title=Study on synergistic effect of mixed surfactants on wetting bituminous coal, columnId=1149733269173878863, journalTitle=China Safety Science Journal, columnName=Safety engineering technology, runingTitle=null, highlight=null, articleAbstract=

In order to solve the problem that the traditional spray technology in coal mine dust pollution control is not ideal and the spray dust reduction performance is low，Sodium dodecyl sulfate (SDS)，Coconut Diethanol Amide (CDEA) and Cocoamidopropyl Betaine(CAB-35) were selected in this paper. The wettability of the three surfactants was first analyzed macroscopically by contact angle test. Then，combined with molecular dynamics simulation and quantum chemical analysis，the action mechanism of single/compound surfactants on bituminous coal was studied from a microscopic perspective. The results show that among the single surfactants，SDS has the smallest contact angle and the largest molecular orbital energy difference，and is more likely to form high-strength hydrogen bonds with water molecules； the mixed surfactants all show better wettability of bituminous coal than single surfactants，and the contact angle is smaller when non-ionic surfactants are mixed with anionic or zwitterionic surfactants，and the contact angle reduction rate is also much greater than that of single solutions，and the synergistic effect is more prominent; In the CDEA+CAB-35 (4∶2) system，water and surfactants form more and higher strength hydrogen bonds，and the surfactant molecules pull each other to form a tight adsorption layer，which attracts water molecules to infiltrate the surface of coal dust and improves the wettability of coal dust to the best extent.

, correspAuthors=Linquan TONG, 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=Miao LEI, Deji JING, Linquan TONG, Jingguang FAN, Xin JIA, Jianhua LIU), CN=ArticleExt(id=1148106734721298744, articleId=1148106727137997499, tenantId=1146029695717560320, journalId=1146031787341344770, language=CN, title=复配表面活性剂润湿烟煤的协同作用研究, columnId=1149733269727526997, journalTitle=中国安全科学学报, columnName=安全工程技术, runingTitle=null, highlight=null, articleAbstract=

为解决煤矿粉尘污染治理中传统的喷雾技术治理效果不太理想、喷雾降尘性能较低的问题，选取十二烷基硫酸钠(SDS)、椰子油脂肪酸二乙醇酰胺(CDEA)和椰油酰胺丙基甜菜碱(CAB-35)3种表面活性剂，首先通过接触角试验宏观分析表面活性剂的润湿性，再结合分子动力学模拟以及量子化学分析，从微观角度研究单一/复配后表面活性剂对烟煤的影响作用机制。结果表明：单一表面活性剂中SDS接触角最小，分子轨道能量差最大，更易与水分子形成较高强度的氢键;复配表面活性剂均表现出优于单一表面活性剂的烟煤润湿性，非离子与阴离子或两性离子活性剂复配时接触角更小，接触角降低速率也远大于单溶液，协同增效作用更突出;CDEA+CAB-35(4∶2)体系中水与表面活性剂形成更多较高强度的氢键，活性剂分子相互牵引形成紧密的吸附层，吸引水分子浸润煤尘表面，煤尘润湿性能力最佳。

, correspAuthors=佟林全, authorNote=null, correspAuthorsNote=
** 佟林全(1988—)，男，辽宁辽阳人，硕士，高级工程师，主要从事职业卫生工程及职业健康管理方面的研究。E-mail：。
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雷 淼 (2000—)，女，陕西渭南人，硕士研究生，研究方向为职业安全健康。E-mail：。

荆德吉，教授；

樊晶光，教授

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2 Key Laboratory of Mine Thermo-motive Disaster and Prevention Ministry of Education，Liaoning Technical University，Huludao Liaoning 125105，China
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2 辽宁工程技术大学 矿山热动力灾害与防治教育部重点实验室，辽宁 葫芦岛 125105
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雷 淼 (2000—)，女，陕西渭南人，硕士研究生，研究方向为职业安全健康。E-mail：。

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雷 淼 (2000—)，女，陕西渭南人，硕士研究生，研究方向为职业安全健康。E-mail：。

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2 辽宁工程技术大学 矿山热动力灾害与防治教育部重点实验室，辽宁 葫芦岛 125105
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荆德吉，教授；

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荆德吉，教授；

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樊晶光，教授

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樊晶光，教授

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tableContent=null), ArticleFig(id=1165678481800175859, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106727137997499, language=CN, label=图12, caption=表面活性剂分子的表面静电势分布, figureFileSmall=FHvt1a3Xxqbtro2wHJlYNQ==, figureFileBig=AaF7dV0gPPlNZ6Tsb1D78A==, tableContent=null), ArticleFig(id=1165678481867284724, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106727137997499, language=EN, label=Table 1, caption=

Industrial element analysis of BZ bituminous coal%

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工业分析 元素分析
水分 灰分 挥发分 固定碳 C H N S O
0.84 7.21 24.26 67.69 83.3 4.0 7.89 1.12 3.69
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BZ烟煤工业元素分析

, figureFileSmall=null, figureFileBig=null, tableContent=
工业分析 元素分析
水分 灰分 挥发分 固定碳 C H N S O
0.84 7.21 24.26 67.69 83.3 4.0 7.89 1.12 3.69
), ArticleFig(id=1165678481993113846, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106727137997499, language=EN, label=Table 2, caption=

Surfactant complex solution number

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复配比例 1∶5 2∶4 3∶3 4∶2 5∶1
CDEA∶CAB-35 A1 A2 A3 A4 A5
SDS∶CAB-35 B1 B2 B3 B4 B5
CDEA∶SDS C1 C2 C3 C4 C5
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复配溶液编号

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复配比例 1∶5 2∶4 3∶3 4∶2 5∶1
CDEA∶CAB-35 A1 A2 A3 A4 A5
SDS∶CAB-35 B1 B2 B3 B4 B5
CDEA∶SDS C1 C2 C3 C4 C5
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复配表面活性剂润湿烟煤的协同作用研究
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雷淼 1, 2, 3 , 荆德吉 1, 2, 3 , 佟林全 4, 5, ** , 樊晶光 4, 5 , 贾鑫 4, 5 , 刘建华 4, 5
中国安全科学学报 | 安全工程技术 2025,35(3): 159-168
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中国安全科学学报 | 安全工程技术 2025, 35(3): 159-168
复配表面活性剂润湿烟煤的协同作用研究
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雷淼1, 2, 3 , 荆德吉1, 2, 3, 佟林全4, 5, ** , 樊晶光4, 5, 贾鑫4, 5, 刘建华4, 5
作者信息
  • 1 辽宁工程技术大学 安全科学与工程学院，辽宁 阜新 123000
  • 2 辽宁工程技术大学 矿山热动力灾害与防治教育部重点实验室，辽宁 葫芦岛 125105
  • 3 辽宁工程技术大学 鄂尔多斯研究院，内蒙古 鄂尔多斯 017010
  • 4 中华人民共和国国家卫生健康委 职业安全卫生研究中心，北京 102308
  • 5 中国人民共和国国家卫生健康委 粉尘危害工程防护重点实验室，北京 102308

    • 雷 淼 (2000—)，女，陕西渭南人，硕士研究生，研究方向为职业安全健康。E-mail：。

    荆德吉，教授；

    樊晶光，教授

通讯作者:

** 佟林全(1988—)，男，辽宁辽阳人，硕士，高级工程师，主要从事职业卫生工程及职业健康管理方面的研究。E-mail：。
Study on synergistic effect of mixed surfactants on wetting bituminous coal
Miao LEI1, 2, 3 , Deji JING1, 2, 3, Linquan TONG4, 5, ** , Jingguang FAN4, 5, Xin JIA4, 5, Jianhua LIU4, 5
Affiliations
  • 1 College of Safety Science and Engineering，Liaoning Technical University，Fuxin Liaoning 123000，China
  • 2 Key Laboratory of Mine Thermo-motive Disaster and Prevention Ministry of Education，Liaoning Technical University，Huludao Liaoning 125105，China
  • 3 Ordos Research Institute，Liaoning Technical University，Ordos Inner Mongolia 017010，China
  • 4 National Center for Occupational Safety and Health，National Health Commission of the People's Republlic of China，Beijing 102308，China
  • 5 Key Laboratory for Engineering Control of Dust Hazard，National Health Commission of the People's Republlic of China，Beijing 102308，China
出版时间: 2025-03-28 doi: 10.16265/j.cnki.issn1003-3033.2025.03.0731
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摘要
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为解决煤矿粉尘污染治理中传统的喷雾技术治理效果不太理想、喷雾降尘性能较低的问题，选取十二烷基硫酸钠(SDS)、椰子油脂肪酸二乙醇酰胺(CDEA)和椰油酰胺丙基甜菜碱(CAB-35)3种表面活性剂，首先通过接触角试验宏观分析表面活性剂的润湿性，再结合分子动力学模拟以及量子化学分析，从微观角度研究单一/复配后表面活性剂对烟煤的影响作用机制。结果表明：单一表面活性剂中SDS接触角最小，分子轨道能量差最大，更易与水分子形成较高强度的氢键;复配表面活性剂均表现出优于单一表面活性剂的烟煤润湿性，非离子与阴离子或两性离子活性剂复配时接触角更小，接触角降低速率也远大于单溶液，协同增效作用更突出;CDEA+CAB-35(4∶2)体系中水与表面活性剂形成更多较高强度的氢键，活性剂分子相互牵引形成紧密的吸附层，吸引水分子浸润煤尘表面，煤尘润湿性能力最佳。

表面活性剂  /  润湿  /  烟煤  /  协同作用  /  分子动力学

In order to solve the problem that the traditional spray technology in coal mine dust pollution control is not ideal and the spray dust reduction performance is low，Sodium dodecyl sulfate (SDS)，Coconut Diethanol Amide (CDEA) and Cocoamidopropyl Betaine(CAB-35) were selected in this paper. The wettability of the three surfactants was first analyzed macroscopically by contact angle test. Then，combined with molecular dynamics simulation and quantum chemical analysis，the action mechanism of single/compound surfactants on bituminous coal was studied from a microscopic perspective. The results show that among the single surfactants，SDS has the smallest contact angle and the largest molecular orbital energy difference，and is more likely to form high-strength hydrogen bonds with water molecules； the mixed surfactants all show better wettability of bituminous coal than single surfactants，and the contact angle is smaller when non-ionic surfactants are mixed with anionic or zwitterionic surfactants，and the contact angle reduction rate is also much greater than that of single solutions，and the synergistic effect is more prominent; In the CDEA+CAB-35 (4∶2) system，water and surfactants form more and higher strength hydrogen bonds，and the surfactant molecules pull each other to form a tight adsorption layer，which attracts water molecules to infiltrate the surface of coal dust and improves the wettability of coal dust to the best extent.

surfactants  /  wetting  /  bituminous coal  /  synergistic effect  /  molecular dynamics
雷淼, 荆德吉, 佟林全, 樊晶光, 贾鑫, 刘建华. 复配表面活性剂润湿烟煤的协同作用研究. 中国安全科学学报, 2025 , 35 (3) : 159 -168 . DOI: 10.16265/j.cnki.issn1003-3033.2025.03.0731
Miao LEI, Deji JING, Linquan TONG, Jingguang FAN, Xin JIA, Jianhua LIU. Study on synergistic effect of mixed surfactants on wetting bituminous coal[J]. China Safety Science Journal, 2025 , 35 (3) : 159 -168 . DOI: 10.16265/j.cnki.issn1003-3033.2025.03.0731
正文
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0 引言
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煤尘治理是矿井安全生产中的难题，其危害主要体现在煤尘自身所具有的自燃性、爆炸性以及煤尘导致的工人尘肺病等方面[1]，此外矿井扬尘还会造成空气污染，严重影响生态环境，因此，高效煤尘防治技术及降尘材料的研发已成为绿色矿山建设的重要部分。
为降低煤尘质量浓度，煤矿多采用煤层注水、喷雾等湿式降尘方法[2-3]。煤的润湿性是煤吸附液体的一种能力，降尘过程中煤的润湿性直接影响着煤尘被液滴浸润的效果，加入表面活性剂可以有效改善煤的润湿性能。学者们借助分子模拟技术，揭示了更深理论层次下表面活性剂与煤尘粒子间的相互作用机制，例如：WANG Yihan等[4]采用纳米粒径电位测量等方法，研究表面活性剂的电位变化以及煤的微观结构变化对其润湿性的影响，得出表面活性剂可通过增强水煤界面作用能，有效润湿煤尘。周群等[5]采用红外光谱、接触角等试验手段，研究磁化与活性剂的协同机制，结果表明：磁化作用可以通过改变活性剂在溶液表面的吸附方式来提高溶液湿润性能。李树刚等[6]采用分子模拟手段，研究表面活性剂对煤体润湿性能的影响机制，认为表面活性剂分子疏水烷基链的空间分布差异是影响煤润湿性能的主要原因之一。聂文等[7]利用量子化学计算表面活性剂、水和煤分子的前线轨道能量差与表面静电势，结合表面张力等试验结果，讨论了不同表面活性剂的煤尘润湿性，得出表面活性剂的煤尘润湿能力与其分子轨道能量差的大小有直接关系。
分子模拟技术虽然弥补了试验微观机制揭示上的不足，但较少有学者同时将试验、分子动力学和量子化学相结合，探究多组分表面活性剂复配以及复配体系与烟煤的接触特征和润湿机制。鉴于此，笔者将以烟煤为研究对象，考察3种表面活性剂及复配溶液的润湿性能，以期揭示表面活性剂复配的协同增效机制，进而优选出效果最佳的烟煤抑尘剂配方。
1 材料制备及试验方法
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1.1 试验煤样
文中选用煤样为山西省临汾市豹子沟煤业公司10105工作面9号煤层的烟煤(BZ烟煤)，现场取样后封存。分析煤样工业元素，测定其元素相对含量，见表1。
将烟煤煤样破碎研磨，研磨后将粒径小于150μm的煤粉进行后续试验。使用压片机在30 MPa压力下持续加压5 min制得直径为20 mm、厚度为4 mm的圆柱状煤片。
1.2 表面活性剂制备
阳离子表面活性剂的极性基团易吸附到煤表面，亲油基与水接触使煤尘的润湿性变差[8-9]。因此选择无毒无害阴离子、非离子和两性离子表面活性剂各1种：十二烷基硫酸钠(Sodium Dodecyl Sulfate，SDS)、椰子油脂肪酸二乙醇酰胺(Coconut Diethanol Amide，CDEA)和椰油酰胺丙基甜菜碱(Cocoamidopropyl Betaine，CAB-35)。3种表面活性剂以1：5、2：4、3：3、4：2、5：1的比例两两混合复配并进行编号，见表2。
1.3 接触角试验
制备质量分数为0.05%的单一表面活性剂溶液及复配溶液。采用接触角测量仪测量纯水与各溶液在BZ烟煤表面的接触角。测量过程中，将煤片放置在测量平台上方，确定基准点后，将溶液缓慢滴到煤片表面测量出接触角，输出溶液接触煤片后6 s的接触角数据。每组试验测量3次，并求出均值以降低试验误差。
2 分子模拟方法
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2.1 分子动力学模型及参数设置
基于前期对BZ烟煤的试验参数测定，选用孟祥曦[10]构建的豹子沟烟煤分子模型作为煤样的基本模型，分子动力学模拟体系如图1所示。
使用Materials Studio软件中Forcite模块对烟煤和表面活性剂分子进行几何优化，使用Amorphous Cell模块为20个烟煤分子、6个表面活性剂分子和2 000个水分子分别构建底面为4 nm×4 nm的盒子，利用Build Layer模块构建水/煤、水/表面活性剂/煤吸附体系，并在水分子上方添加100 Å的真空层以消除周期性结构的影响，并对其进行几何优化以达到能量稳定构型。
2.2 量子化学
使用Gaussian几何优化各分子，并开展表面静电势计算分析，同时利用Multiwfn结合分子可视化程序获得不同分子结构中的静电势分布、极值点位置。
3 表面活性剂润湿烟煤的协同作用
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3.1 抑尘剂润湿性试验分析
液体在固态物质表面的接触角是衡量液体对该物质表面润湿性的重要参数之一，各体系与煤样的接触角如图2所示。由图2可知：纯水接触角为80.9°，该样品煤样为较亲水性矿物。添加表面活性剂后水煤接触角显著减小，SDS、CDEA和CAB-35的接触角分别为16.1、19.6和44.2°。
复配表面活性剂中非离子-阴离子和非离子-两性离子表面活性剂复配展现了较好的协同增效作用，其中，A4体系协同增效作用最明显，接触角为13.7°。SDS与CAB-35协同增效作用不佳，因为两性离子表面活性剂亲水基团所带的正电与阴离子表面活性剂的负电基团产生静电吸引，减少了表面活性剂亲水基附近的水分子。
溶液体系接触到煤样后6 s内接触角变化曲线如图3所示，得到曲线斜率k，|k|越大表示接触角变化速率越快。接触角随溶液与煤样接触时间的增加呈减小趋势，单一表面活性剂的|k|值排序为：CDEA>SDS>CAB-35；复配表面活性剂|k|排序为：A4>C1>C2>A5>B3>B4>A2>C3>C5>B5>C4>A3>B2>A1>B1，接触角越小的溶液体系，其接触角减小速率也更快。
3.2 分子动力学分析
3.2.1 水的均方位移(MSD)
不同表面活性剂的加入会对水-表面活性剂-煤体系中水的迁移行为产生不同的影响，基于水的均方位移(Mean Squared Displacement，MSD)曲线和自扩散系数D，分析水在煤表面的迁移[11-12]。MSD可表示：
M S D = N - 1 ∑ i r i ( t ) - r i ( 0 ) 2
式中：N为原子个数； r i ( 0 )为初始位置矢量；ri(t)为时间t后的位置矢量；i为第i个原子。
自扩散系数可表示为：
D = l i m t → ∞ ( M S D / ( 6 t ) ) = 1 6 K   M S D
式中KMSD为MSD曲线的斜率。
各体系水分子MSD曲线与D如图4所示，由图4可知：水的自扩散系数越大，水分子运动越剧烈。纯水、SDS、CDEA、CAB-35水分子的D值分别为2.70×10-5、7.94×10-5、4.45×10-5、3.70×10-5 cm2/ps，表面活性剂体系中水在煤表面的流动性均增强，SDS体系中水的D值最高，意味着水分子更容易扩散和浸润煤表面;而CAB-35中水的D值较小，提高水浸润进煤表面的能力较弱。
复配体系中，A组中随着CDEA比例增大D值先变大后变小，A3体系的D值最大为8.52×10-5 cm2/ps，说明此时水分子运动最剧烈。B组D值整体偏小，SDS含量越大其水分子的D值越大，体系水分子扩散能力增强。C组中C4体系中水的D值最高，达到8.97×10-5 cm2/ps，阴离子表面活性剂之间的缝隙被非离子表面活性剂填充，彼此之间相互吸附，以更紧密的排列方式分布在煤层表面，水向煤尘颗粒内部渗透的趋势增强，从而使水可以更迅速的浸润煤尘。
3.2.2 相对数密度分布
复配体系各分子相对数密度分布曲线如图5所示。由图5可知：表面活性剂分子主要分布在水煤相交的范围内，说明表面活性剂主要作用于水煤界面。根据每个体系对水分子的迁移能力和煤与水之间的重叠面积评估其润湿性能[13]，对重叠面积中水分子曲线进行积分，积分结果表示水的浸润深度，各体系水分子浸润深度和水合层厚度如图6所示。
水合层厚度的大小取决于固体表面性质和环境条件[14]。一般来说，当固体表面具有良好的润湿性时，水分子更容易吸附在固体表面上，形成较厚的水合层。相反，当固体表面具有较差的润湿性时，水分子难以吸附在固体表面上，进而形成较薄的水合层。
较厚的水合层表示水分子更易吸附在固体表面，可以增加液体与固体表面之间的接触面积，提高润湿性能，因此，水合层厚度较大的固体表面往往更容易被液体湿润。3种表面活性剂中SDS体系水的浸润深度和水合层厚度均达到最大值，水分子与煤表面之间的相互作用增强。在复配体系中水合层厚度由大到小依次为A4>C5>C4>A5>B3>A3>其他，水分子浸润深度由大到小依次为A4>C5>C4>C3>C1>B2>其他，活性剂分子通过吸附的方法改变煤体表面组成，非极性的碳链亲油基与煤表面结合，另一端极性亲水基伸入水中，形成水化膜，降低了水的表面张力，固液界面张力显著减小，使得煤更容易被润湿。
3.2.3 径向分布函数
径向分布函数是指给定某个粒子的坐标，其他粒子在空间的分布概率，可以用来研究物质的有序性，当空间内存在粒子近程有序，径向分布函数曲线中就会出现峰，峰高且尖说明有序性强，其原子之间的联系也就越紧密[13]。径向分布函数表达式如下：
g ( r ) = d N / 4 π ρ r 2 d r
式中：dN为某原子与中心原子的距离为r到r+dr之间的原子总数目；ρ为该原子的平均数目密度。
为更好的分析表面活性剂与水分子之间的相互作用，计算表面活性剂头基与水分子之间的径向分布函数，如图7所示。
由图7a可知：SDS、CDEA与CAB-35的第1波峰分别位于2.425 Å、2.725 Å与2.725 Å，均小于3 Å，因此，第1水合层受静电作用形成；第2波峰位置均大于3 Å，第2水合层受范德华力作用形成。SDS的极性基头的吸附层距离头基的距离近且峰值高，其与水分子易形成高强度氢键，吸附结构稳定，具有更稳定的保水效果。图7b可知：A4体系的RDF曲线峰值最高，体系前2个峰的位置均小于3 Å，第1、第2水合层都是由于受到氢键的作用形成的，说明复配表面活性剂相较于单一表面活性剂保水能力更强。由图7c、图7d可知：B、C体系中阴离子表面活性剂SDS对水合层的形成和峰的强度起到主导作用。
CDEA+CAB-35(4：2)体系中水与表面活性剂分子之间距离更短，RDF曲线峰值最高，水和表面活性剂分子近距离接触的概率大幅提升，有益于形成更多氢键。
各体系氢键分析结果如图8所示，由图8可知：复配表面活性剂与水形成的氢键数目明显多于单一表面活性剂，A4体系的氢键个数最多，比生成氢键最多的单一活性剂溶液增加了55.3%，且键长最短、键角大，氢键作用力强，与上述径向分布函数分析相一致。
3.2.4 复配表面活性剂协同作用机制
两性离子表面活性剂CAB-35同时含有正负电荷基团，非离子表面活性剂CDEA不含电荷，2种表面活性剂之间电荷相互作用可以改变溶液的物理化学性质，提高复配体系中水油界面和溶液表面的活性。A4体系中表面活性剂分子之间的协同作用如图9所示，在A4复配体系中反应中期CDEA分子与CAB-35分子均以平躺的方式覆盖在煤分子层表面;反应平衡后，2种表面活性剂分子的亲油基与煤分子的疏水点位相互吸引，使分子从平躺状态转变为亲油基吸附于煤尘表面，亲水基朝向水分子的定向分布状态。在复配体系中，CAB-35的离子基团与CDEA分子的极性基团产生相互作用力，相互牵引形成混合胶束，CDEA分子的加入减小了CAB-35分子之间的静电斥力，使这种混合胶束具有强于2种单体表面活性剂的亲水性。由于2种表面活性剂的亲油基团均为具有相似结构性质的碳链，更容易相互结合，形成比较稳定的结构，向着煤分子层表面移动，最终亲油基聚集在一起，吸附到煤分子的疏水点位上，增加了煤表面的亲水面积，大大提高了煤尘的亲水性。同时，活性剂分子的亲水基伸向溶液内部，非离子表面活性剂CDEA可与水产生较强氢键作用，两性离子表面活性剂CAB-35的加入进一步增强了这种氢键作用，使得更多的水分子被吸引，迁移到煤尘表面，进而达到促进煤尘润湿的目的。
4 表面活性剂影响烟煤润湿性的协同作用
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4.1 分子前线轨道
水分子以及表面活性剂分子同煤分子接触并相互作用，其结果受各分子表面静电势所主导，故分析各相关分子的表面静电势，有助于理解表面活性剂影响煤润湿性的协同作用机制。
分子中有按能级排列的分子或位元，最高占据分子轨道(Highest Occupied Molecular Orbital，HOMO)为最高能级的分子已占据的分子轨道，最低占有分子轨道(Lowest Unoccupied Molecular Orbital，LUMO)为最低能量的未被电子占据的分子轨道。二者的能量差ΔE=LUMO-HOMO可以反映电子从已占据轨道跃迁到空轨道的能力，ΔE越大，分子的反应活性越低，分子越稳定，ΔE越小则相反[15-16]。
利用Dmol3模块分析表面活性剂分子轨迹能量，所得结果如图10所示。SDS的轨道能量差最大，CAB-35的最小，表明在BZ烟煤表面SDS具有较高的分子活性，对煤样的润湿效果更优。表面活性剂分子的HOMO、LUMO均位于其亲水基团处，这就意味着表面活性剂的高活性、易发生反应的区域主要集中在极性基头上。基于轨道能量HOMO与LUMO的分布可进一步分析分子表面静电势。
4.2 表面静电势分布
分子表面静电势通过影响固液界面相互作用力来促进或阻碍润湿现象。利用Gaussian计算分子表面静电势，结合分子可视化程序得到分子表面静电势分布图，预测其吸附位点，水与烟煤的表面静电势分布如图11所示。
由图11a可知：水分子的最高负电势为-155.71 kJ/mol，最高正电势为192.72 kJ/mol，水分子的表面正负静电势*促使溶液中水分子相互吸引，正负电位之间形成氢键，使其紧密连接。比较物质与水分子的表面静电势极值，可判断物质与水是否为易吸附的，若物质表面静电势大于水的表面静电势，则说明物质可以被水吸附。由图11b可知：BZ烟煤分子表面负电势最大为-200.75 kJ/mol，正电势最大为215.07 kJ/mol。BZ烟煤表面正负电势极值均大于水分子表面正负电势极值，其负静电势的主要分布区域为氧原子和含氧官能团附近，故水分子比较容易被烟煤分子吸引，进而产生润湿现象。
表面活性剂分子的表面静电势分布如图12所示，由图12可知：SDS、CAB-35和CDEA的静电势极值区域与HOMO、LUMO分布相一致。SDS的正负电势极值分别为571.12和-195.23 kJ/mol，正电势极值点在Na+处，负电势极值点位于头基的O原子附近；CAB-35最高正电势点位于头基的第1个H原子附近，其值为196.90 kJ/mol，表面最高负电势极值点处于分子中部O原子附近，为-183.30 kJ/mol，头基的O原子附近也存在2个负电势极值分别为-87.74和-142.70 kJ/mol；CDEA的最高正电势极值点为228.71 kJ/mol，位于头基中羟基的H原子处，负电势极值点位于头基的2个O原子附近，分别为-185.22和-184.01 kJ/mol。
3种表面活性剂亲水基的负电势极值与水分子正电势极值的电势差要大于水分子之间的正负电势极值电势差，才能使水分子能够脱离开彼此的静电吸引，然后吸附在表面活性剂的亲水基团上。SDS与水分子的电势差大于CAB-35和CDEA，说明结构内活性位点更多，活性位点之间的表面电子互相影响使其分子内部结构更分散，与水发生静电作用形成氢键的概率更大，提升烟煤润湿的能力更强。
5 结论
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1) 阴离子表面活性剂SDS接触角最低为16.1°，比纯水降低了80.1%。而CDEA+CAB-35(4∶2)体系接触角为13.7°，与SDS相比降低了14.9%，并且接触角的降低速率最大，说明复配溶液的协同效果良好。
2) CDEA+CAB-35(4∶2)体系的水分子浸润深度深，水煤界面水合层厚度大，表面活性剂分子与水分子接触概率增大，形成的氢键数量多，相比单一表面活性剂体系中生成氢键最多的SDS，氢键数量增加了55.3%。
3) 在吸附构型中，CDEA+CAB-35(4∶2)体系协同作用明显，2种活性剂分子的亲水基和亲油基均可产生相互作用力，缔结形成亲水性较强的稳定混合胶束，吸附在水煤界面上成为连接水煤分子的桥梁，吸引水分子迁移到煤尘表面，进而达到促进煤尘润湿的目的。
4) BZ烟煤的正负电势极值比水大，说明该烟煤可被水润湿。SDS、CDEA、CAB-35头基的最大静电势均比水分子大，可与水形成氢键，增强煤尘界面对水分子的相互作用能力，提高水对烟煤表面的润湿性。阴离子表面活性剂的分子轨道能量差与表面静电势差最大，说明其分子极性强，对烟煤表面润湿性的提升作用最佳。
基金
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  • 辽宁省教育厅科学研究经费重点项目(LJKZ0323)
  • 内蒙古自治区自然科学基金资助(2022QN05009)
文献
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2025年第35卷第3期
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doi: 10.16265/j.cnki.issn1003-3033.2025.03.0731
  • 接收时间：2024-10-23
  • 首发时间：2025-07-05
  • 出版时间：2025-03-28
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  • 收稿日期：2024-10-23
  • 修回日期：2024-12-25
基金
辽宁省教育厅科学研究经费重点项目(LJKZ0323)
内蒙古自治区自然科学基金资助(2022QN05009)
作者信息
    1 辽宁工程技术大学 安全科学与工程学院，辽宁 阜新 123000
    2 辽宁工程技术大学 矿山热动力灾害与防治教育部重点实验室，辽宁 葫芦岛 125105
    3 辽宁工程技术大学 鄂尔多斯研究院，内蒙古 鄂尔多斯 017010
    4 中华人民共和国国家卫生健康委 职业安全卫生研究中心，北京 102308
    5 中国人民共和国国家卫生健康委 粉尘危害工程防护重点实验室，北京 102308

通讯作者:

** 佟林全(1988—)，男，辽宁辽阳人，硕士，高级工程师，主要从事职业卫生工程及职业健康管理方面的研究。E-mail：。
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https://castjournals.cast.org.cn/joweb/zgaqkxxb/CN/10.16265/j.cnki.issn1003-3033.2025.03.0731
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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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