Article(id=1322907632092197240, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322907425740825534, 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=1724515200000, receivedDateStr=2024-08-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793335357926, onlineDateStr=2026-10-30, pubDate=1750780800000, pubDateStr=2025-06-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793335357926, onlineIssueDateStr=2026-10-30, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793335357926, creator=13701087609, updateTime=1793335357926, updator=13701087609, issue=Issue{id=1322907425740825534, tenantId=1146029695717560320, journalId=1225396423026438145, year='2025', volume='45', issue='6', pageStart='1', pageEnd='300', issueExtLink='null', onlineDate='null', pubDate='1750780800000', pubDateStr='2025-06-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793335308726, creator='13701087609', updateTime=1793335308726, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=247, endPage=254, ext={EN=ArticleExt(id=1322907633874776442, articleId=1322907632092197240, tenantId=1146029695717560320, journalId=1225396423026438145, language=EN, title=Selective Inhibition Mechanism of a New Inhibitor in Copper Sulfur Flotation Separation, columnId=null, journalTitle=Mining Research and Development, columnName=null, runingTitle=null, highlight=null, articleAbstract=

A new inhibitor PN has been developed for copper sulfur flotation separation to address issues such as pipeline blockage and environmental pollution caused by the use of lime inhibitors. The selective inhibition performance and adsorption mechanism of PN inhibitor in flotation process were studied through systematic tests. The results indicate that PN inhibitor has a good selective inhibitory effect on pyrite, but has almost no effect on chalcopyrite. The results of the artificial mixed ore separation test show that under low alkali conditions (pH=8), the optimal separation effect of pyrite and chalcopyrite can be achieved when the dosage of PN inhibitor is 5 mg/L, and a copper concentrate with a copper grade of 31.3% and a copper recovery rate of 92.9% can be obtained. The contact angle measurement results indicate that PN inhibitor can selectively enhance the hydrophilic properties of pyrite surface. The analysis of the microstructure characteristics and elemental content changes of pyrite before and after PN treatment further confirms that PN inhibitor undergo physical adsorption on the surface of pyrite, which can achieve selective inhibition of pyrite. The research results prove that PN inhibitors has the potential to replace lime in copper sulfur separation.

, authors=Lulin LU1, Xiaokun FU1, Yuzhen CHEN1, Xingrong ZHANG1, Jianhua CHEN2, authorsList=Lulin LU, Xiaokun FU, Yuzhen CHEN, Xingrong ZHANG, Jianhua CHEN, authorCompany=null, correspAuthors=Xingrong ZHANG, 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=1322907639620972948, articleId=1322907632092197240, tenantId=1146029695717560320, journalId=1225396423026438145, language=CN, title=一种新型抑制剂在铜硫浮选分离中的选择性抑制机理研究, columnId=1226462297560892399, journalTitle=矿业研究与开发, columnName=选矿与资源综合利用, runingTitle=null, highlight=null, articleAbstract=

针对铜硫浮选分离过程中采用石灰抑制剂存在的管道堵塞和环境污染等问题,开发了一种新型抑制剂PN用于铜硫分离。通过系统试验对PN抑制剂在浮选过程中的选择性抑制性能和吸附机理进行了研究。结果表明:PN抑制剂对黄铁矿具有良好的选择性抑制作用,而对黄铜矿几乎无影响;人工混合矿分离试验结果表明,在低碱条件下(pH=8), PN抑制剂用量为5 mg/L时实现了最佳的黄铁矿和黄铜矿分离效果,可获得铜品位为31.3%,铜回收率为92.9%的铜精矿;接触角测量结果表明,PN抑制剂可选择性增强黄铁矿表面的亲水性能;PN处理前后黄铁矿的微观形貌特征与元素含量变化分析进一步证实,PN抑制剂在黄铁矿表面发生了物理吸附,可实现对黄铁矿的选择性抑制。研究结果表明,PN抑制剂具有在铜硫分离中替代石灰的应用潜力。

, authors=鲁路林1, 付晓坤1, 陈玉贞1, 张行荣1, 陈建华2, authorsList=鲁路林, 付晓坤, 陈玉贞, 张行荣, 陈建华, authorCompany=null, correspAuthors=张行荣, authorNote=

鲁路林(1998—),女,安徽宿州人,硕士研究生,研究方向为浮选药剂研发。E-mail:

, correspAuthorsNote=
张行荣(1984—),男,山东济南人,博士,教授,主要从事浮选药剂开发、矿产资源加工利用、亲疏水材料等研究。E-mail:
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鲁路林(1998—),女,安徽宿州人,硕士研究生,研究方向为浮选药剂研发。E-mail:

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tableContent=null), ArticleFig(id=1322907644847075787, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=EN, label=Fig.7, caption=Variation of the adsorption capacity of PN inhibitor on pyrite surface with its dosage, figureFileSmall=C7lqv7uiZW0HcBEM7ny82w==, figureFileBig=Ix5tnaqAU7oplnlootI/uQ==, tableContent=null), ArticleFig(id=1322907644947739084, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=CN, label=图7, caption=PN抑制剂在黄铁矿表面吸附量随用量的变化, figureFileSmall=C7lqv7uiZW0HcBEM7ny82w==, figureFileBig=Ix5tnaqAU7oplnlootI/uQ==, tableContent=null), ArticleFig(id=1322907645014847949, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=EN, label=Fig.8, caption=Infrared spectrogram, figureFileSmall=ZN+4GW1hpsF9D4IMABMrlA==, figureFileBig=ULS3jVK+QUtDY1BAeKe1Zw==, tableContent=null), ArticleFig(id=1322907645077762510, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=CN, label=图8, caption=红外光谱图, figureFileSmall=ZN+4GW1hpsF9D4IMABMrlA==, figureFileBig=ULS3jVK+QUtDY1BAeKe1Zw==, tableContent=null), ArticleFig(id=1322907645203591631, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=EN, label=Fig.9, caption=XPS spectragrams of pyrite before and after PN treatment, figureFileSmall=sFmNATSH2O8hUssSs8hFvQ==, figureFileBig=TDUUD+wUxmeP0VSf72o+xw==, tableContent=null), ArticleFig(id=1322907645274894800, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=CN, label=图9, caption=PN处理前后黄铁矿XPS谱图, figureFileSmall=sFmNATSH2O8hUssSs8hFvQ==, figureFileBig=TDUUD+wUxmeP0VSf72o+xw==, tableContent=null), ArticleFig(id=1322907645350392273, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=EN, label=Fig.10, caption=SEM-EDS analysis of the pyrite before and after PN treatment, figureFileSmall=VFM65G6eSqiSIXcpEjBJKQ==, figureFileBig=3xZhrcbKxTFksgzzYNzkGw==, tableContent=null), ArticleFig(id=1322907645417501138, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=CN, label=图10, caption=PN处理前后黄铁矿SME-EDS分析, figureFileSmall=VFM65G6eSqiSIXcpEjBJKQ==, figureFileBig=3xZhrcbKxTFksgzzYNzkGw==, tableContent=null), ArticleFig(id=1322907645480415699, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=EN, label=Table 1, caption=

XPS analysis results of pyrite before and after PN treatment

, figureFileSmall=null, figureFileBig=null, tableContent=
样品Fe 2pS 2pC 1sN 1sO 1s
PN处理前黄铁矿13.3831.6524.434.4726.08
PN处理后黄铁矿13.0428.9424.544.9228.57
), ArticleFig(id=1322907647170720212, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=CN, label=表1, caption=

PN处理前后黄铁矿的XPS分析结果

, figureFileSmall=null, figureFileBig=null, tableContent=
样品Fe 2pS 2pC 1sN 1sO 1s
PN处理前黄铁矿13.3831.6524.434.4726.08
PN处理后黄铁矿13.0428.9424.544.9228.57
), ArticleFig(id=1322907647250411989, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=EN, label=Table 2, caption=

Element content of the pyrite surface before and after PN treatment

, figureFileSmall=null, figureFileBig=null, tableContent=
样品FeSCNO
PN处理前黄铁矿34.5434.916.610.382.87
PN处理后黄铁矿33.6632.539.061.093.84
), ArticleFig(id=1322907647317520854, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322907632092197240, language=CN, label=表2, caption=

PN处理前后黄铁矿表面元素含量

, figureFileSmall=null, figureFileBig=null, tableContent=
样品FeSCNO
PN处理前黄铁矿34.5434.916.610.382.87
PN处理后黄铁矿33.6632.539.061.093.84
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一种新型抑制剂在铜硫浮选分离中的选择性抑制机理研究
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鲁路林 1 , 付晓坤 1 , 陈玉贞 1 , 张行荣 1 , 陈建华 2
矿业研究与开发 | 选矿与资源综合利用 2025,45(6): 247-254
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矿业研究与开发 |选矿与资源综合利用 2025 , 45 (6) : 247 -254
一种新型抑制剂在铜硫浮选分离中的选择性抑制机理研究
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鲁路林1 , 付晓坤1, 陈玉贞1, 张行荣1 , 陈建华2
作者信息
  • 1.青岛科技大学 化工学院,山东 青岛市 266042
  • 2.广西大学 化学化工学院,广西 南宁 530004
通讯作者:
张行荣(1984—),男,山东济南人,博士,教授,主要从事浮选药剂开发、矿产资源加工利用、亲疏水材料等研究。E-mail:
作者简介:

鲁路林(1998—),女,安徽宿州人,硕士研究生,研究方向为浮选药剂研发。E-mail:

Selective Inhibition Mechanism of a New Inhibitor in Copper Sulfur Flotation Separation
Lulin LU1 , Xiaokun FU1, Yuzhen CHEN1, Xingrong ZHANG1 , Jianhua CHEN2
Affiliations
  • 1.College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao, Shandong 266042, China
  • 2.School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004, China
出版时间: 2025-06-25
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针对铜硫浮选分离过程中采用石灰抑制剂存在的管道堵塞和环境污染等问题,开发了一种新型抑制剂PN用于铜硫分离。通过系统试验对PN抑制剂在浮选过程中的选择性抑制性能和吸附机理进行了研究。结果表明:PN抑制剂对黄铁矿具有良好的选择性抑制作用,而对黄铜矿几乎无影响;人工混合矿分离试验结果表明,在低碱条件下(pH=8), PN抑制剂用量为5 mg/L时实现了最佳的黄铁矿和黄铜矿分离效果,可获得铜品位为31.3%,铜回收率为92.9%的铜精矿;接触角测量结果表明,PN抑制剂可选择性增强黄铁矿表面的亲水性能;PN处理前后黄铁矿的微观形貌特征与元素含量变化分析进一步证实,PN抑制剂在黄铁矿表面发生了物理吸附,可实现对黄铁矿的选择性抑制。研究结果表明,PN抑制剂具有在铜硫分离中替代石灰的应用潜力。

新型抑制剂  /  黄铁矿  /  黄铜矿  /  铜硫浮选分离  /  作用机理

A new inhibitor PN has been developed for copper sulfur flotation separation to address issues such as pipeline blockage and environmental pollution caused by the use of lime inhibitors. The selective inhibition performance and adsorption mechanism of PN inhibitor in flotation process were studied through systematic tests. The results indicate that PN inhibitor has a good selective inhibitory effect on pyrite, but has almost no effect on chalcopyrite. The results of the artificial mixed ore separation test show that under low alkali conditions (pH=8), the optimal separation effect of pyrite and chalcopyrite can be achieved when the dosage of PN inhibitor is 5 mg/L, and a copper concentrate with a copper grade of 31.3% and a copper recovery rate of 92.9% can be obtained. The contact angle measurement results indicate that PN inhibitor can selectively enhance the hydrophilic properties of pyrite surface. The analysis of the microstructure characteristics and elemental content changes of pyrite before and after PN treatment further confirms that PN inhibitor undergo physical adsorption on the surface of pyrite, which can achieve selective inhibition of pyrite. The research results prove that PN inhibitors has the potential to replace lime in copper sulfur separation.

New inhibitor  /  Pyrite  /  Chalcopyrite  /  Copper sulfur flotation separation  /  Action mechanism
鲁路林, 付晓坤, 陈玉贞, 张行荣, 陈建华. 一种新型抑制剂在铜硫浮选分离中的选择性抑制机理研究. 矿业研究与开发, 2025 , 45 (6) : 247 -254 .
Lulin LU, Xiaokun FU, Yuzhen CHEN, Xingrong ZHANG, Jianhua CHEN. Selective Inhibition Mechanism of a New Inhibitor in Copper Sulfur Flotation Separation[J]. Mining Research and Development, 2025 , 45 (6) : 247 -254 .
铜是一种重要的有色金属,广泛应用于交通运输、建筑和国防等领域[1]。然而,我国铜资源相对贫乏,《中国矿产资源报告》(2023)显示,截至2022年底,我国铜矿储量为4 077.18 万 t,但仅占全球铜资源总量的3%[2]。而且,我国铜资源以低品位矿为主,富铜矿占比不足20%,总体上呈现出规模小、贫矿多、伴生资源占比大等特点[3]。近年来,新能源产业发展为铜资源带来新的增量需求,预计2035年前我国铜资源消耗将保持增长态势,2035—2050年需求将维持高位。但由于国内铜资源基础薄弱,供应能力受限,铜资源供应仍将主要依靠国外进口[4]。
我国的铜矿资源以硫化铜矿为主,铜硫共生是硫化铜矿石中常见的矿石类型[5]。矿石目标矿物中,硫化铁与硫化铜两者具有相近的天然可浮性[6],加之矿石中矿物嵌布关系复杂,导致铜硫选择性浮选分离困难。抑硫浮铜的优先浮选工艺[7]是选别致密块状铜硫矿石的主要方法。传统工艺中,黄铁矿和黄铜矿的分离主要是向矿浆中加入大量石灰,调节矿浆至高碱性环境从而对黄铁矿进行抑制。但过量石灰易导致管道堵塞、废水污染环境等问题[8-10]。为解决上述问题的同时实现铜硫高效分离,很多学者对黄铁矿抑制剂进行了大量研究,其中低碱条件下有效抑制黄铁矿是研究的重要方向[11]。已有研究表明,部分有机抑制剂可以在低碱条件下实现铜硫分离,包括纤维素类[12]、多糖类[13]、有机酸类[14]、木质素磺酸盐类聚合物[15]等。但是这些抑制剂选择性较差,用量大时可能导致矿物整体被抑制,实际应用受限[16]。因此,本文开发了一种新型黄铁矿抑制剂PN,通过浮选试验、接触角测量、紫外吸附量测量、扫描电镜-能谱(SEM-EDS)分析、红外光谱(FTIR)分析和X射线光电子能谱(XPS)分析探究了PN抑制剂对黄铁矿浮选行为及其作用机理,通过优化浮选药剂制度,取得了较好的选别指标,实现了低碱条件下铜硫高效分离。
抑制剂PN为实验室自制的一种新型硫抑制剂,属于有机大分子化合物,含多个羧基、羟基以及氨基;试验所用的捕收剂为市售丁基黄原酸钠(简称丁黄),纯度不低于85.0%;起泡剂则采用分析纯甲基异丁基甲醇(MIBC);pH调整剂选用工业级石灰。
PN抑制剂制备过程中所用到的仪器包括恒温加热磁力搅拌器、电热恒温水浴锅以及电动搅拌器;浮选试验使用的主要仪器为充气挂槽浮选机(型号XFGC Ⅱ),矿浆pH采用酸度计测定;此外,采用超声波清洗器(型号KS5200E)清洗矿物表面,采用紫外分光光度计(型号UV1800PC)测试药剂在矿物表面的吸附量。
浮选试验固定转速为1 758 r/min,浮选槽体积为30 mL。试验前,将2 g黄铁矿或黄铜矿(粒径为38~74 μm)在超声浴中预处理5 min,然后将样品送入浮选槽,用石灰水溶液调节矿浆pH。搅拌3 min后,加入PN抑制剂。搅拌3 min后,再加入一定量的捕收剂和起泡剂,再搅拌3 min,然后刮泡浮选5 min,收集精矿(泡沫产物)和尾矿进行干燥称重并计算回收率。根据元素分析试验结果,计算人工混合矿浮选回收率。浮选试验流程如图1所示。回收率计算公式如下。
式中:εpm为黄铁矿或黄铜矿纯矿物的回收率,%;mf、mt分别为精矿和尾矿质量,g;εp/c为人工混合矿物分离时精矿中黄铜矿的回收率,%;β1、β2分别为精矿和尾矿中黄铜矿的品位,%。
根据上式进行计算,所得回收率为3次独立浮选试验结果的平均值[17]。
矿物的浮选性能与表面的润湿性密切相关,因此,本研究对不同PN抑制剂剂量处理下的黄铁矿和黄铜矿的疏水性进行测量。试验前,对黄铜矿和黄铁矿样品进行浮选药剂吸附处理:首先将2 g矿物与30 mL去离子水置于50 mL烧杯中,超声预处理5 min,使用磁力搅拌器进行搅拌,转速为1 200 r/min;然后加入PN抑制剂,继续搅拌10 min后过滤,用去离子水洗涤3次,并于50 ℃以下烘干。将干燥后的样品压制成光滑薄片,用于接触角测量。每次测量重复3次,测试结果取平均值[18-19]。
采用紫外可见分光光度计测定了PN抑制剂在黄铁矿表面的吸附量。试验过程如下:将1.0 g矿物样品与20 mL去离子水混合在50 mL烧杯中,超声预处理5 min,使用磁力搅拌器进行搅拌,转速为1 200 r/min;调节浮选矿浆至预期pH并稳定2 min,然后向浮选矿浆中加入不同用量的PN,搅拌5 min;吸附完成后,取上清液在2 000 r/min条件下离心1 h;将离心后的样品静置2 h,取3 mL上清液进行吸附量测试[20-21]。
对PN以及PN处理前后的黄铁矿进行红外光谱分析。样品制备过程为:将2 g矿物样品(黄铁矿)和30 mL去离子水置于50 mL烧杯中,药剂的添加方法与浮选试验流程一致;试剂与矿物相互作用后,将样品过滤干燥,取1%(质量分数)的矿物样品与光谱级KBr混合压片。采用NicoletIS10傅里叶变换红外光谱仪在4 000~400 cm−1波数范围内进行测试,所有测试均在室温(25±1 ℃)条件下进行[22-23]。
采用XPS分析PN抑制剂处理前后黄铁矿样品的表面化学状态。待测样品制备过程:将2 g黄铁矿和30 mL的去离子水加入50 mL烧杯中,超声预处理5 min;加入5 mg/L的PN抑制剂作用15 min,过滤干燥后制样。能谱扫描范围为0~1 400 eV,标定能量为100 eV,步长为1.0 eV。采用Avantage软件处理数据,以C 1s峰(284.8 eV)作为基准进行结合能校正[24-25]。
采用扫描电镜(SEM)结合能谱分析(EDS)研究PN处理前后黄铁矿表面微观形貌及元素组成变化。将2.0 g矿物与30 mL去离子水置于50 mL烧杯中,超声预处理5 min,加入PN抑制剂后用磁力搅拌器搅拌15 min使其充分反应,过滤后真空干燥24 h。将矿物粉末均匀粘附在导电黏合剂上制成样品,并在SEM测试之前进行喷金处理。
由于黄铜矿和黄铁矿具有极相似的天然可浮性,在自然状态下二者很难分离,通常在低碱条件下选择性抑制黄铁矿来浮选黄铜矿。以PN为抑制剂,丁黄(用量为30 mg/L)为捕收剂、MIBC(用量为10 mg/L)为起泡剂,研究了抑制剂用量对黄铁矿、黄铜矿浮选回收率的影响,试验结果见图2。
由图2可以看出,当PN抑制剂用量较低时(1 mg/L),抑制作用并不明显。随着抑制剂用量的增加,黄铁矿的回收率逐渐降低,但黄铜矿的回收率几乎无变化,这说明PN抑制剂可以对黄铁矿进行选择性抑制。当PN抑制剂用量达5 mg/L时,黄铁矿的回收率下降到20%以下,而黄铜矿的回收率在90%以上。由此可见,在一定的用量下,PN抑制剂对黄铁矿的抑制有明显的选择性,能够用于黄铁矿和黄铜矿的分离。
在浮选过程中,矿浆pH是一个重要参数。本文研究了PN抑制剂用量为5 mg/L条件下,矿浆pH对黄铁矿和黄铜矿可浮性的影响。选用氧化钙调节矿浆pH,试验结果如图3所示。由图3可以看出,在整个测试范围内,PN抑制剂对黄铜矿的抑制效果不明显,对黄铁矿的抑制效果较好,黄铁矿的回收率维持在20%左右。pH为8时,黄铁矿和黄铜矿回收率差值较大,因此选择pH为8作为混合矿分离的最佳pH。
综上,在不同抑制剂用量和矿浆pH条件下,研究了PN抑制剂对两种矿物可浮性的影响。结果表明:黄铁矿可浮性随着PN抑制剂用量的增大而降低,而黄铜矿的浮选回收率基本保持不变。在抑制剂用量为5 mg/L的条件下,黄铁矿抑制剂效果即可达到最佳;在低碱条件下(pH=8),该抑制剂对黄铁矿具有较好的选择性抑制作用。
将1 g黄铜矿和1 g黄铁矿进行混合得到人工混合矿物,在不同抑制剂用量下对黄铜矿产率、Cu回收率和Cu品位进行分析。固定矿浆pH为8,捕收剂用量为30 mg/L,起泡剂用量为10 mg/L,试验结果如图4和图5所示。
从图4可以看出,随着抑制剂用量的增加,黄铜矿产率呈现出先下降后趋于平稳的趋势。当抑制剂用量为5 mg/L时,产率约为50%。由图5可知,随着抑制剂用量的增大,Cu品位总体呈现出增大的趋势,在抑制剂用量为5 mg/L时,Cu品位达到31.3%,Cu回收率为92.9%,分离效果最佳。
不同PN抑制剂用量下黄铁矿和黄铜矿的接触角如图6所示。
由图6(a)可知,不加抑制剂的黄铁矿表面的接触角为63.4°,这说明黄铁矿具有一定的天然亲水性。随着PN用量增加,黄铁矿的接触角逐渐减小,当PN浓度为5 mg/L时,黄铁矿接触角降低至16.7°。在此条件下,黄铁矿具有较强的亲水性,使其很难从矿浆中浮出,浮选性能受到抑制,这与单矿物浮选试验结果一致。由图6(b)可知,黄铜矿的接触角同样随PN抑制剂用量的增加而减小,但与黄铁矿相比,黄铜矿的接触角变化并不明显。这说明经PN抑制剂处理后,两种矿物的亲水性均发生变化,且黄铁矿的接触角明显小于黄铜矿,进而说明PN抑制剂更易吸附于黄铁矿表面,从而为黄铁矿和黄铜矿的选择性浮选分离创造了有利条件。
PN抑制剂在黄铁矿表面的吸附量随其用量的变化如图7所示。试验结果表明,随着PN抑制剂用量的增加,其在黄铁矿表面的吸附量逐渐增大,当抑制剂用量达到5 mg/L时,PN抑制剂在黄铁矿表面的吸附量基本达到平衡,此时,PN抑制剂在黄铁矿表面的吸附量为0.046 mg/g。继续增加抑制剂用量,其在黄铁矿表面的吸附量基本不再变化,说明此时吸附量已经达到饱和。
为了进一步研究PN抑制剂在黄铁矿表面的作用机理,当抑制剂用量为5 mg/L的条件下,对PN抑制剂、PN处理前后的黄铁矿红外光谱图进行了对比分析,如图8所示。
根据红外光谱手册可知[26-27],1 648.1 cm−1为羰基(C═O)伸缩振动,2 921.6 cm−1为—CH2伸缩振动,3 436.1 cm−1出现了N—H伸缩振动锋。PN处理前黄铁矿的红外光谱特征峰分别出现在3 440.2 cm−1、1 382.0 cm−1处,与文献[19]结果一致。PN处理后的黄铁矿红外光谱图显示出与PN抑制剂类似的特征吸收带,其中1 648.1 cm−1处出现了抑制剂PN的羰基(C═O)特征吸收峰,证实了抑制剂的成功吸附。此外,谱图中未出现新的特征峰,表明PN抑制剂主要通过物理吸附作用的形式附着于黄铁矿表面。
表1为PN处理前后黄铁矿的XPS分析结果,由表1可知,PN抑制剂处理前后黄铁矿表面的原子浓度变化不大。与处理前相比,PN处理后的黄铁矿S2p的相对原子浓度下降了2.71个百分点,这表明黄铁矿表面被抑制剂所覆盖;同时,N 1s的相对原子浓度增加了0.45个百分点,这是由PN抑制剂中的N元素所引起的,表明PN抑制剂已经吸附于黄铁矿表面。
图9(a)为PN抑制剂处理前后黄铁矿的XPS谱图,从图中可以看出,与处理前相比,PN抑制剂处理后的黄铁矿表面没有出现新的元素峰,峰强度变化不大,主要元素的结合能也没有发生变化。进一步分析表明,PN处理前后的黄铁矿的Fe 2p、S 2p、O 1s谱图基本一致,结合能未发生明显偏移。上述结果表明,PN抑制剂主要以物理吸附的形式作用于黄铁矿表面,这与红外光谱分析结果一致。
图10为PN处理前后黄铁矿SEM-EDS分析结果,表2为PN处理前后黄铁矿表面元素含量的变化。由SEM分析可知,PN处理前的黄铁矿表面附着少量矿物颗粒,表面相对光滑;PN处理后的黄铁矿表面出现大量颗粒附着物,显著增加了矿物表面粗糙度。由EDS分析可知,PN处理前后的黄铁矿表面元素含量出现了明显的变化。与处理前相比,PN处理后的黄铁矿C含量由6.61%提高到9.06%,O含量由2.87%提高到3.84%,N含量由0.38%提高到1.09%,S含量由34.91%降低至32.53%。这些形貌特征和元素含量的变化证实了PN抑制剂在黄铁矿表面的成功吸附,可实现对黄铁矿的选择性抑制。
本文研究了PN抑制剂对黄铁矿的浮选抑制性能和吸附机理,根据试验结果和分析可以得出以下结论。
(1)单一纯矿物浮选试验结果表明,PN抑制剂对黄铁矿的抑制作用较强,对黄铜矿抑制作用不明显。当PN用量为5.0 mg/L时,黄铁矿回收率低于20%,黄铜矿回收率在90%以上,可以实现黄铁矿和黄铜矿的有效分离。人工混合矿物浮选分离试验结果表明,在pH=8、丁黄用量为30 mg/L、MIBC用量为10 mg/L、PN抑制剂用量为5 mg/L的条件下,人工混合矿物浮选分离得到铜品位为31.3%,铜回收率为92.9%的铜精矿,分离效果良好。
(2)接触角测量结果表明,PN抑制剂可以增强黄铁矿表面的亲水性,而对黄铜矿的亲水性影响较小,从而实现选择性抑制黄铁矿。吸附量测试结果进一步证实了PN抑制剂能够选择性吸附于黄铁矿表面,其饱和吸附量可达0.046 mg/g。
(3)红外光谱和XPS分析结果表明,PN抑制剂主要以物理吸附形式吸附于黄铁矿表面。SEM-EDS分析显示,PN处理后的黄铁矿表面附着物大量增加,且C、N、O元素含量明显上升。以上分析测试结果均证明PN抑制剂已经成功吸附于黄铁矿表面,PN可以作为黄铁矿选择性抑制剂,实现铜硫高效分离。
  • 山东省泰山学者青年专家项目(tsqn202312202)
  • 国家自然科学基金面上项目(51974030)
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2025年第45卷第6期
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  • 接收时间:2024-08-25
  • 首发时间:2026-10-30
  • 出版时间:2025-06-25
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  • 收稿日期:2024-08-25
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山东省泰山学者青年专家项目(tsqn202312202)
国家自然科学基金面上项目(51974030)
作者信息
    1.青岛科技大学 化工学院,山东 青岛市 266042
    2.广西大学 化学化工学院,广西 南宁 530004

通讯作者:

张行荣(1984—),男,山东济南人,博士,教授,主要从事浮选药剂开发、矿产资源加工利用、亲疏水材料等研究。E-mail:
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2种不同金属材料的力学参数
科
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属数
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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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