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Article(id=1322904495042212646, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322844250153275555, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1734451200000, receivedDateStr=2024-12-18, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793334609994, onlineDateStr=2026-10-30, pubDate=1748102400000, pubDateStr=2025-05-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793334609994, onlineIssueDateStr=2026-10-30, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793334609994, creator=13701087609, updateTime=1793334609994, updator=13701087609, issue=Issue{id=1322844250153275555, tenantId=1146029695717560320, journalId=1225396423026438145, year='2025', volume='45', issue='5', pageStart='1', pageEnd='288', issueExtLink='null', onlineDate='null', pubDate='1748102400000', pubDateStr='2025-05-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793320246494, creator='13701087609', updateTime=1793320246494, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=49, endPage=56, ext={EN=ArticleExt(id=1322904496833180455, articleId=1322904495042212646, tenantId=1146029695717560320, journalId=1225396423026438145, language=EN, title=Carbide Slag and Silica Fume Synergistically Improving the Performance of β-Hemihydrate Phosphogypsum Backfill Cementing Material, columnId=null, journalTitle=Mining Research and Development, columnName=null, runingTitle=null, highlight=null, articleAbstract=

To address the issues of short setting time, poor water resistance and inadequate strength when β-hemihydrate phosphogypsum (β-HPG) is used as backfill cementing materials, two industrial solid wastes, carbide slag and silica fume were introduced. The effects of these wastes on the workability, water resistance, and strength of β-HPG were analyzed. The microstructure and pore structure of the modified β-HPG were investigated by SEM. Additionally, the environmental behavior, cost, and carbon emissions of the modified β-HPG were evaluated. The results indicate that the combined use of carbide slag and silica fume significantly extends the setting time of β-HPG slurry and enhances its fluidity. After modification, the compressive strength of β-HPG backfill is substantially increased, reaching a 28-day strength value of 36.6 MPa, with a reduced water absorption rate of 2.7% and an elevated softening coefficient of 0.885. The incorporation of silica fume and carbide slag can improve the micromorphology and pore structure of β-HPG backfill. The generated calcium silicate hydrate, a hydraulic hydration product, enhances the compactness of backfill. Carbide slag and silica fume effectively neutralize residual acids in the β-HPG and immobilize phosphorus and heavy metal elements within the hardened body. When the content of carbide slag is 10% and the content of silica fume is 15%−20%, the β-HPG cementing material exhibits favorable economic and environmental benefits.

, authors=Lijun WANG1, Yuxia GUO2, 3, authorsList=Lijun WANG, Yuxia GUO, authorCompany=null, correspAuthors=Yuxia GUO, 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, fund=null), CN=ArticleExt(id=1322904499169407802, articleId=1322904495042212646, tenantId=1146029695717560320, journalId=1225396423026438145, language=CN, title=电石渣和硅灰协同提升β半水磷石膏充填胶凝材料性能研究, columnId=1226462294490657775, journalTitle=矿业研究与开发, columnName=采矿与矿山充填, runingTitle=null, highlight=null, articleAbstract=

为解决β半水磷石膏作为充填胶凝材料时的凝结时间短、耐水性差及强度不足等问题，引入了两种工业固废电石渣和硅灰，分析了其对β半水磷石膏工作性能、耐水性能及强度的影响，使用扫描电镜探究了改性后β半水磷石膏充填体的微观形貌及孔隙结构，并对改性后β半水磷石膏的环境行为、成本和碳排放进行了评估。结果表明：电石渣与硅灰共同作用能够显著延长β半水磷石膏料浆的凝结时间并提升其流动性；经过改性处理，β半水磷石膏充填体的抗压强度得到了大幅增强，28 d的强度值可达36.6 MPa，吸水率降低至2.7%，同时软化系数提高到0.885；掺硅灰和电石渣改善了β半水磷石膏充填体的微观形貌和孔隙结构，生成的水硬性水化产物水化硅酸钙提高了充填体的致密性；电石渣和硅灰有效中和了半水磷石膏中的残余酸并固化充填体内部的磷及重金属元素；当电石渣掺量为10%、硅灰掺量为15%~20%时，β半水磷石膏胶凝材料具有较好的经济效益和环境效益。

, authors=王利军1, 郭育霞2, 3, authorsList=王利军, 郭育霞, authorCompany=null, correspAuthors=郭育霞, authorNote=

王利军（1980—），男，山西忻州人，高级工程师，主要从事煤矿绿色开采研究。E-mail:

, correspAuthorsNote=
郭育霞（1977—），女，山西阳城人，博士，教授，主要从事充填开采与固废资源化利用研究。E-mail:
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王利军（1980—），男，山西忻州人，高级工程师，主要从事煤矿绿色开采研究。E-mail:

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王利军（1980—），男，山西忻州人，高级工程师，主要从事煤矿绿色开采研究。E-mail:

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Mix proportions of the tests

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试验编号半水磷石膏/%电石渣/%硅灰/%减水剂/%水胶比
对照组10000
D5G5905510.38
D5G1085510
D5G1580515
D5G2075520
D10G585105
D10G10801010
D10G15751015
D10G20701020
D15G580155
D15G10751510
D15G15701515
D15G20651520
), ArticleFig(id=1322904514805773163, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, language=CN, label=表1, caption=

试验配合比

, figureFileSmall=null, figureFileBig=null, tableContent=
试验编号半水磷石膏/%电石渣/%硅灰/%减水剂/%水胶比
对照组10000
D5G5905510.38
D5G1085510
D5G1580515
D5G2075520
D10G585105
D10G10801010
D10G15751015
D10G20701020
D15G580155
D15G10751510
D15G15701515
D15G20651520
), ArticleFig(id=1322904514881270636, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, language=EN, label=Table 2, caption=

Leaching concentration of phosphorus and heavy metal elements

, figureFileSmall=null, figureFileBig=null, tableContent=
样品浸出浓度/(mg/L)
PPbCdAsCrNi
对照组1.483 70.091 30.020 10.071 10.115 20.135 9
D5G50.826 60.074 60.015 90.062 50.107 90.116 2
D5G200.531 50.069 20.011 40.051 70.093 10.093 5
D15G200.488 30.063 00.010 20.048 40.081 60.091 1
GB/T 30760—2024规定值—≤0.3≤0.03≤0.10.2≤0.2
), ArticleFig(id=1322904515002905453, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, language=CN, label=表2, caption=

磷和重金属元素浸出浓度

, figureFileSmall=null, figureFileBig=null, tableContent=
样品浸出浓度/(mg/L)
PPbCdAsCrNi
对照组1.483 70.091 30.020 10.071 10.115 20.135 9
D5G50.826 60.074 60.015 90.062 50.107 90.116 2
D5G200.531 50.069 20.011 40.051 70.093 10.093 5
D15G200.488 30.063 00.010 20.048 40.081 60.091 1
GB/T 30760—2024规定值—≤0.3≤0.03≤0.10.2≤0.2
), ArticleFig(id=1322904515099374446, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, language=EN, label=Table 3, caption=

Comparison of prices and carbon emissions of filling cementitious materials

, figureFileSmall=null, figureFileBig=null, tableContent=
材料价格/(元/t)碳排放/(kg/t)
P·O 42.5水泥403930.0
β半水磷石膏15096.0
电石渣12067.0
硅灰60014.8
), ArticleFig(id=1322904515170677615, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, language=CN, label=表3, caption=

充填胶凝材料价格及碳排放对比

, figureFileSmall=null, figureFileBig=null, tableContent=
材料价格/(元/t)碳排放/(kg/t)
P·O 42.5水泥403930.0
β半水磷石膏15096.0
电石渣12067.0
硅灰60014.8
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电石渣和硅灰协同提升β半水磷石膏充填胶凝材料性能研究
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王利军 1 , 郭育霞 2, 3
矿业研究与开发 | 采矿与矿山充填 2025,45(5): 49-56
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矿业研究与开发 |采矿与矿山充填 2025 , 45 (5) : 49 -56
电石渣和硅灰协同提升β半水磷石膏充填胶凝材料性能研究
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[Author(id=1322904501417554757, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=wangljcg@163.com, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1322904501639852871, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, authorId=1322904501417554757, language=EN, stringName=Lijun WANG, firstName=Lijun, middleName=null, lastName=WANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1.Jinneng Holding Group Xinzhou Company, Xinzhou, Shanxi 034000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1322904501723738952, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322904495042212646, authorId=1322904501417554757, language=CN, stringName=王利军, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1.晋能控股集团忻州公司，山西　忻州市　034000, bio={"content":"

王利军（1980—），男，山西忻州人，高级工程师，主要从事煤矿绿色开采研究。E-mail:

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王利军（1980—），男，山西忻州人，高级工程师，主要从事煤矿绿色开采研究。E-mail:

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王利军1 , 郭育霞2, 3
作者信息
  • 1.晋能控股集团忻州公司，山西　忻州市　034000
  • 2.太原理工大学 矿业工程学院，山西　太原　030024
  • 3.山西浙大新材料与化工研究院，山西　太原　030024
通讯作者:
郭育霞（1977—），女，山西阳城人，博士，教授，主要从事充填开采与固废资源化利用研究。E-mail:
作者简介:

王利军（1980—），男，山西忻州人，高级工程师，主要从事煤矿绿色开采研究。E-mail:

Carbide Slag and Silica Fume Synergistically Improving the Performance of β-Hemihydrate Phosphogypsum Backfill Cementing Material
Lijun WANG1 , Yuxia GUO2, 3
Affiliations
  • 1.Jinneng Holding Group Xinzhou Company, Xinzhou, Shanxi 034000, China
  • 2.College of Mining Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024, China
  • 3.Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan, Shanxi 030024, China
出版时间: 2025-05-25
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摘要
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为解决β半水磷石膏作为充填胶凝材料时的凝结时间短、耐水性差及强度不足等问题，引入了两种工业固废电石渣和硅灰，分析了其对β半水磷石膏工作性能、耐水性能及强度的影响，使用扫描电镜探究了改性后β半水磷石膏充填体的微观形貌及孔隙结构，并对改性后β半水磷石膏的环境行为、成本和碳排放进行了评估。结果表明：电石渣与硅灰共同作用能够显著延长β半水磷石膏料浆的凝结时间并提升其流动性；经过改性处理，β半水磷石膏充填体的抗压强度得到了大幅增强，28 d的强度值可达36.6 MPa，吸水率降低至2.7%，同时软化系数提高到0.885；掺硅灰和电石渣改善了β半水磷石膏充填体的微观形貌和孔隙结构，生成的水硬性水化产物水化硅酸钙提高了充填体的致密性；电石渣和硅灰有效中和了半水磷石膏中的残余酸并固化充填体内部的磷及重金属元素；当电石渣掺量为10%、硅灰掺量为15%~20%时，β半水磷石膏胶凝材料具有较好的经济效益和环境效益。

β半水磷石膏  /  充填胶凝材料  /  电石渣掺量  /  硅灰掺量

To address the issues of short setting time, poor water resistance and inadequate strength when β-hemihydrate phosphogypsum (β-HPG) is used as backfill cementing materials, two industrial solid wastes, carbide slag and silica fume were introduced. The effects of these wastes on the workability, water resistance, and strength of β-HPG were analyzed. The microstructure and pore structure of the modified β-HPG were investigated by SEM. Additionally, the environmental behavior, cost, and carbon emissions of the modified β-HPG were evaluated. The results indicate that the combined use of carbide slag and silica fume significantly extends the setting time of β-HPG slurry and enhances its fluidity. After modification, the compressive strength of β-HPG backfill is substantially increased, reaching a 28-day strength value of 36.6 MPa, with a reduced water absorption rate of 2.7% and an elevated softening coefficient of 0.885. The incorporation of silica fume and carbide slag can improve the micromorphology and pore structure of β-HPG backfill. The generated calcium silicate hydrate, a hydraulic hydration product, enhances the compactness of backfill. Carbide slag and silica fume effectively neutralize residual acids in the β-HPG and immobilize phosphorus and heavy metal elements within the hardened body. When the content of carbide slag is 10% and the content of silica fume is 15%−20%, the β-HPG cementing material exhibits favorable economic and environmental benefits.

β-hemihydrate phosphogypsum  /  Backfill cementing material  /  Content of carbide slag  /  Content of silica fume
王利军, 郭育霞. 电石渣和硅灰协同提升β半水磷石膏充填胶凝材料性能研究. 矿业研究与开发, 2025 , 45 (5) : 49 -56 .
Lijun WANG, Yuxia GUO. Carbide Slag and Silica Fume Synergistically Improving the Performance of β-Hemihydrate Phosphogypsum Backfill Cementing Material[J]. Mining Research and Development, 2025 , 45 (5) : 49 -56 .
正文
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0　引言
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随着全球经济的快速发展，对矿产资源的需求也在持续增加。传统地表及浅部矿产资源已经无法满足日益增长的需求，因此，深部矿产资源开采成为必然趋势[1]。充填采矿技术作为一种高效、安全的采矿方法，能够适应深部开采的特殊条件，被广泛应用于深部矿产资源的开采中[2]。随着开采深度增加，对充填体性能提出了更高要求，包括良好的工作性能及足够的抗压强度等。
当前，充填采矿主要依赖水泥作为黏结剂，其成本达到了充填总成本的70%以上，碳排放超过全球总排放的8%[3-4]。在高昂成本及环保的压力下，充填采矿的可持续发展受到限制。磷石膏作为磷酸生产的固体副产物，全球堆存量超过70　亿t，但利用率不足14%[5-6]。因此，将磷石膏进行处理改性制备胶凝材料已经成为当下研究的热点。毕颖等[7]将磷石膏与水泥等混合制备复合充填材料，分析了料浆的流动性能、力学性能及渗透性能。赵静等[8]采用生石灰、矿渣协同磷石膏制备膏体充填材料，探究了充填胶凝材料工作性能及强度等的变化规律，并通过毒性浸出试验评估其环境相容性。
然而，磷石膏作为磷酸生产过程中的副产物，不可避免地含有硫酸、磷酸等杂质，这些杂质在溶解后会显著影响磷石膏作为胶凝材料的性能。将磷石膏在150~200 ℃的低温范围内煅烧为β半水磷石膏[9]，可以有效去除磷石膏中的杂质，并具备较好的胶凝特性，已被学者们开发为充填胶凝材料[10-11]。然而，由于矿井环境的复杂性，尤其是矿井水的存在，对β半水磷石膏胶凝材料的凝结时间、强度和耐水性构成了挑战[12]，以往关于这些方面尤其是耐水性的研究较为薄弱。因此，需要对β半水磷石膏进行改性以满足充填采矿的需求。
硅灰作为硅铁合金冶炼的副产品，具备火山灰活性，能够有效提升材料的强度、抗渗透性以及耐水性能[13]。然而，硅灰通常需要碱性激发剂的辅助才能充分发挥其水化反应潜力[14]。电石渣作为乙炔气体制造过程中产生的副产品，富含氢氧化钙，可以作为一种碱性激发剂，为硅灰的水化过程提供碱性环境[15]。
基于此，本文将工业固废电石渣和硅灰掺入β半水磷石膏充填胶凝材料中，系统研究了其对β半水磷石膏充填胶凝材料工作性能、强度及耐水性的改善效果。探究了电石渣和硅灰的最佳掺入比例，并采用扫描电镜对改性后β半水磷石膏充填体的微观结构进行了分析。此外，通过pH和电感耦合等离子体发射光谱仪评估了改性后β半水磷石膏充填胶凝材料的环境行为，并在此基础上分析了改性后β半水磷石膏充填胶凝材料的成本和碳排放，研究结果可以为β半水磷石膏在充填采矿中的应用提供参考。
1　材料与方法
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1.1　原材料及配合比
试验所采用的原材料有β半水磷石膏、电石渣和硅灰，对应的pH分别为5.24, 12.65和8.17。原材料的微观形貌、粒径分布及化学组成如图1所示。由图1可以看出，β半水磷石膏以四方板状为主，电石渣呈现出不规则块状分布，硅灰表现出显著的团聚特征，众多微小的球形颗粒紧密堆叠。从原材料粒径分布可以看出，β半水磷石膏拥有三者之中最大的粒径尺寸，而硅灰的粒径尺寸最小。
根据表1中的配合比，依次将β半水磷石膏、电石渣和硅灰倒入水泥胶砂搅拌机中搅拌30 s，然后按0.38的水胶比向搅拌机中加入含有1%聚羧酸减水剂的纯净水，继续搅拌180 s。部分混合均匀的料浆用于测试凝结时间和流动性，其余料浆则倒入40 mm×40 mm×40 mm的标准三联模具中，1 d后拆模置于标准室中养护。
1.2　试验方法
1.2.1　流动性及凝结时间
依据《混凝土外加剂匀质性试验方法》（GB/T 8077—2012），进行了料浆流动性测试，测试板尺寸为400 mm×400mm，采用截锥圆模（高度60 mm，上口直径36 mm，下口直径60 mm），测定料浆在测试板上停止流动时的最大直径。根据《水泥标准稠度用水量、凝结时间、安定性检验方法》（GB/T 1346—2011），采用维卡仪来测定料浆的初凝和终凝时间。每个配合比的料浆均进行3次重复测试，并取其平均值作为最终的测试结果。
1.2.2　强度及耐水性测试
根据《水泥胶砂强度检验方法(ISO法)》（GB/T 17671—2021)，对试件进行抗压强度及耐水性测试。抗压强度测试加载速率为0.5 kN/s，每组配比取3个试件，对测试结果取平均值。在耐水性试验中，将养护28d的样品经过干燥处理后，在20 ℃的水中浸泡24 h，以测定吸水后试件的质量变化并计算吸水率。同时，比较吸水后试件和在空气中养护相同天数试件的抗压强度，前者与后者的比值为软化系数。
1.2.3　微观结构及pH测试
采用JCM-7000型扫描电镜分析β半水磷石膏充填胶凝材料硬化体的微观结构，放大倍数为10~100　000倍，加速电压为5~15kV，分辨率为5 nm。pH测试时，将不同龄期的试样研磨成粉末，烘干后根据固液比为1:5倒入去离子水，使用磁力搅拌器搅拌60 min，然后静置30 min过滤出浸出液，测定浸出液的pH。
1.2.4　浸出元素测试
依据《固体废物　浸出毒性浸出方法　水平振荡法》(HJ　557—2010)，将养护至28d的样品进行破碎处理，使其粒径降至3 mm以下。随后，将破碎的样品与去离子水混合后置于水平振荡器内进行振荡处理。8 h后对混合液进行过滤，利用Agilent720 ES型电感耦合等离子体发射光谱仪对浸出液中的磷元素及重金属元素含量进行定量分析。
2　试验结果与分析
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2.1　凝结时间及流动性
凝结时间是充填作业高效、安全和稳定进行的重要因素。凝结时间过短导致充填困难，而凝结时间过长则会延长充填周期。电石渣与硅灰掺量对β半水磷石膏料浆凝结时间的影响如图2所示。在对照组中，单一β半水磷石膏料浆的初凝和终凝时间分别为6 min和8min，这对充填采矿作业极为不利。然而，随着电石渣和硅灰的加入，这种情况得到了显著改善，凝结时间随着这两种材料的掺量增加而明显延长，当电石渣掺量为15%和硅灰掺量为20%时，β半水磷石膏料浆的初凝时间和终凝时间分别达到了96 min及105 min，凝结时间延长了10倍以上。一方面，硅灰因其粒径细小，能够有效填充β半水磷石膏颗粒之间的空隙，增大颗粒间距，从而降低了水化反应的速度。另一方面，在电石渣提供的碱性环境中，硅灰逐渐水化，产生的水化产物紧密包裹在β半水磷石膏晶体周围，形成了一层阻碍水化反应的屏障，进一步增加了凝结时间。
充填料浆的流动性对充填采矿有重要影响，如果充填材料流动性不足，会降低充填开采的连续性及采矿效率。图3展示了电石渣和硅灰掺量对β半水磷石膏料浆流动性的影响。数据显示，随着电石渣掺量的增加，β半水磷石膏料浆的流动性显著降低，以硅灰掺量5%为例，当电石渣掺量从5%增加至15%时，半水磷石膏料浆的流动度从237 mm降至208 mm。这主要是电石渣较强的吸水能力导致浆体中自由水的减少。另一方面，硅灰掺量的增加使得料浆的流动性先提升后下降，在15%的掺量时达到流动度峰值。硅灰的微小球形颗粒和光滑表面在初期掺入时起到了润滑作用，从而提高了料浆的流动性。但随着硅灰掺量的持续增加，其火山灰活性开始发挥作用，吸引了更多的水分子附着在颗粒表面，减少了浆体内的自由水，导致流动性下降。值得注意的是，对照组中单一β半水磷石膏的流动度仅为170 mm，表明硅灰和电石渣的加入显著改善了β半水磷石膏料浆的流动性。
2.2　抗压强度及耐水性
β半水磷石膏不同龄期充填体的抗压强度随电石渣与硅灰掺量变化如图4所示。对照组单一β半水磷石膏充填体的3 d强度达到9.7MPa,28 d强度仅提升至10.3 MPa。从图4可以看出，电石渣对β半水磷石膏的早期强度有着显著影响。随着电石渣掺量的增加，β半水磷石膏充填体的抗压强度也随之增加，且这一增强效果在硅灰掺量增加时更为显著。当15%电石渣和20%硅灰掺入时，β半水磷石膏充填体3 d的抗压强度高达21.5 MPa，并在28 d时进一步提升至36.6 MPa，这表明电石渣和硅灰的加入能显著提高β半水磷石膏充填体的强度。然而，值得注意的是，在28 d养护期时，过量电石渣的掺入对抗压强度产生了负面影响。电石渣能够激发硅灰的水化反应，生成水化硅酸钙，从而促进充填体强度的增长。然而，当硅灰掺量较低时，充填体中水化硅酸钙的生成量并不会随着电石渣掺量的增加而持续增加，过量电石渣反而会以氢氧化钙的形式存在于充填体中，导致抗压强度有所下降。
由于矿山井下常含有矿井水，若胶凝材料的耐水性不足，充填体强度会逐渐降低，从而对矿井安全构成威胁。β半水磷石膏存在耐水性较差的固有属性，本次试验测得其吸水率高达14.7%，软化系数仅为0.59。然而，如图5所示，电石渣和硅灰的加入显著改善了β半水磷石膏的耐水性能。随着这两种材料掺量的增加，β半水磷石膏的吸水率逐渐降低，当掺入15%电石渣和20%硅灰时，吸水率降至2.7%，软化系数则提升至0.885。《墙体材料应用统一技术规范》（GB 50574—2010)指出，对于长期处于水中或潮湿环境的重要建筑物或构筑物时，选取的建筑材料软化系数不应小于0.85。从结果来看，当硅灰掺量为15%时，除了5%电石渣的组别外，其他组别的材料均达到了规范要求，当硅灰掺量为20%时，所有组别的材料均达到规范要求，显示出优异的耐水增强效果。
2.3　微观形貌及孔隙结构
图6为单一β半水磷石膏及D10G20组充填体28 d龄期时的微观形貌。由图6可以看出，单一β半水磷石膏充填体已经基本水化为短柱状的二水石膏晶体，晶体间通过堆叠和错位咬合形成了具有一定强度的微观结构。然而，晶体之间存在较多孔隙，导致其强度和耐水性不佳。在加入电石渣和硅灰后，充填体内部形成了大量水硬性凝胶状的水化硅酸钙，这些凝胶填充了石膏晶体间的孔隙，使得充填体更加致密，从而提高了其强度和耐水性。此外，充填体中还存在着部分未反应的球状硅灰颗粒，这些细小的硅灰颗粒同样能够填充到充填体中，进一步增强其密实度和强度。
孔隙结构是评估充填体密实度的重要参数，对充填体的宏观性能具有显著影响。对充填体SEM图像进行分析，得到充填体孔隙结构如图7所示。由图7可以看出，单一β半水磷石膏充填体养护28 d孔隙率高达23.7%，且孔径尺寸较大。在掺入电石渣和硅灰之后，孔隙率和孔隙数量均有所下降，单个孔隙面积也减少至4 μm2以下。表明孔隙结构得到了有效改善，充填体的密实性得到增强。
2.4　环境和经济效益
2.4.1　pH变化
由于β半水磷石膏是由磷石膏低温煅烧而来，残留的硫酸及磷酸等杂质会对环境产生一定影响。不同配合比的β半水磷石膏充填胶凝材料pH随龄期的变化如图8所示。从图8可以观察到，单一β半水磷石膏料浆在初期显示出弱酸性，其pH在前3 d内快速上升，表明水化反应较为迅速。当掺入电石渣和硅灰后，料浆的pH迅速升至12以上，这是因为电石渣中的Ca(OH)2有效中和了β半水磷石膏中的H+，随着电石渣掺量的增加，料浆的pH也随之升高。在相同电石渣掺量的情况下，随着硅灰掺量的增加，料浆pH在后期呈现下降趋势，这表明硅灰在后期仍然发生水化作用，表现出显著的“火山灰反应”特征。
2.4.2　磷和重金属元素浸出风险
在充填采矿中应用充填胶凝材料时，必须考虑浸出元素对周边环境的影响。表2为不同电石渣和硅灰掺量的β半水磷石膏充填体28 d龄期时磷元素和重金属元素的浸出浓度。由表2可以看出，经过低温煅烧的单一β半水磷石膏对照组具有较低的磷和重金属元素浸出浓度。加入电石渣和硅灰后，形成的水化硅酸钙能够有效地包裹β半水磷石膏，显著降低了磷元素的浸出，并对重金属元素实现了有效的固化，这一现象在硅灰掺量较高时更为显著。此外，所有试样的浸出液中重金属元素浓度均未超过《水泥窑协同处置固体废物技术规范》（GB/T 30760—2024)规定的毒性限值，具有较好的环境友好性。
2.4.3　成本和碳排放
除性能外，成本和碳排放是评估β半水磷石膏作为充填胶凝材料能够广泛应用的两个重要因素。表3为本研究所使用的原材料与普通硅酸盐水泥的价格与碳排放分析[16-20]。由表3可以看出，β半水磷石膏和电石渣的价格和碳排放远低于水泥，尽管硅灰的价格略高于水泥，但在减少碳排放方面具有明显优势。
为了深入探究成本、碳排放量与制备的胶凝材料强度之间的关系，建立了单位抗压强度下胶凝材料的价格与碳排放模型，如图9所示。
由图9可以看出，单一β半水磷石膏胶凝材料单位强度的价格达到14.6 元/t，高于水泥的9.48 元/t。掺加电石渣和硅灰后，胶凝材料单位强度的价格显著降低，最低达到6.43 元/t，相比于水泥降低了32.2%。在碳排放方面，由于水泥生产过程中需要经历高温煅烧，导致碳排放量较高，单位强度的碳排放量达到21.9 kg/t，而β半水磷石膏制备的胶凝材料单位强度碳排放量较低，尤其是硅灰掺量较多时，单位强度碳排放量最低可降至2.06 kg/t，约为水泥的1/10，展现了优异的经济效益和环境效益。综合考虑工作性能、力学性能和耐水性能，当电石渣掺量为10%、硅灰掺量为15%~20%时，β半水磷石膏胶凝材料表现出较好的性能和效益。
3　结论
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本文研究了工业固废电石渣和硅灰对β半水磷石膏充填胶凝材料的工作性能、强度、耐水性能的影响，探究了改性后β半水磷石膏充填体的微观形貌及孔隙结构，评估了改性后β半水磷石膏的环境行为、碳排放和成本，确定了电石渣和硅灰的最佳掺入比例，得出以下主要结论。
（1）β半水磷石膏料浆的初凝时间和终凝时间分别为6 min及8min，同时掺入电石渣和硅灰后可分别延长至96 min及105 min，且β半水磷石膏料浆的流动度可以提升至200 mm以上，流动性得到显著增强。
（2）电石渣和硅灰显著提升了β半水磷石膏充填体的抗压强度，28 d时可达到36.6 MPa，是单一β半水磷石膏的3.55倍。β半水磷石膏吸水率高达14.7%，软化系数仅为0.59，在掺入电石渣和硅灰后，吸水率可降至2.7%，软化系数达到0.885。
（3）单一β半水磷石膏水化后主要由短柱状二水石膏晶体组成，晶体间具有较多的孔隙，致密性较差。当掺入电石渣和硅灰后，充填体内部生成大量凝胶状水化硅酸钙，填充了石膏晶体间的孔隙，孔隙率、孔隙数量及孔径尺寸均显著降低。
（4）电石渣和硅灰可以有效中和β半水磷石膏中的残留酸并固化内部的磷元素，对重金属元素的浸出也起到了抑制作用。当电石渣掺量为10%、硅灰掺量为15%~20%时，β半水磷石膏胶凝材料展现出优异的性能，并具有较好的经济效益和环境效益。
基金
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  • 国家自然科学基金联合基金重点项目(U23A20131)
文献
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2025年第45卷第5期
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  • 接收时间：2024-12-18
  • 首发时间：2026-10-30
  • 出版时间：2025-05-25
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  • 收稿日期：2024-12-18
基金
国家自然科学基金联合基金重点项目(U23A20131)
作者信息
    1.晋能控股集团忻州公司，山西　忻州市　034000
    2.太原理工大学 矿业工程学院，山西　太原　030024
    3.山西浙大新材料与化工研究院，山西　太原　030024

通讯作者:

郭育霞（1977—），女，山西阳城人，博士，教授，主要从事充填开采与固废资源化利用研究。E-mail:
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
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