Article(id=1241321696184037873, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.02.011, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1730390400000, receivedDateStr=2024-11-01, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773883755011, onlineDateStr=2026-03-19, pubDate=1743436800000, pubDateStr=2025-04-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773883755011, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773883755011, creator=13701087609, updateTime=1773883755011, updator=13701087609, issue=Issue{id=1241321691524158287, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='2', pageStart='1', pageEnd='204', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773883753901, creator=13701087609, updateTime=1773884632018, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241325374676726363, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241325374676726364, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=64, endPage=68, ext={EN=ArticleExt(id=1241321696540553731, articleId=1241321696184037873, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Effect of Different Oxidants on Flotation Performance of Gold-Bearing Pyrite, columnId=1236276106932842717, journalTitle=Mining and Metallurgical Engineering, columnName=MINERAL PROCESSING, runingTitle=null, highlight=null, articleAbstract=

As for a gold-bearing pyrite from Hebei Province, the influence of four oxidants, including H2SO4, H2O2, HNO3 and KMnO4, on its floatability was investigated, and the adsorption of collectors on pyrite was also explored by infrared (IR) analysis and electrochemistry measurement. The flotation test shows that with H2SO4, H2O2 and HNO3 as oxidants, moderate oxidation can promote the floatability of pyrite, while the oxidation of KMnO4 can obviously depress the floatability of pyrite. The IR analysis shows that the effects of these four oxidants on pyrite-collector interaction are in the following descending order: HNO3>KMnO4>H2O2>H2SO4. The oxidation of KMnO4 may passivate pyrite and reduce its floatability. Electrochemical analysis shows that H2SO4 and HNO3 have obvious oxidation effects on pyrite. By increasing oxidant concentration, the double xanthate formed on pyrite due to its reaction with xanthate will be oxidized by H2O2 solution, and the hydrophobic layer on pyrite will be destroyed, leading to the decline of pyrite's floatability.

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以河北某含金黄铁矿单矿物为研究对象,考察了氧化剂H2SO4、H2O2、HNO3、KMnO4对矿物可浮性的影响,并利用红外光谱检测和电化学测试探究了捕收剂在黄铁矿表面的吸附情况。结果表明:H2SO4、H2O2、HNO3为氧化剂时,适度氧化可促进黄铁矿上浮,KMnO4氧化对黄铁矿可浮性有明显的抑制作用;4种氧化剂氧化对黄铁矿与捕收剂间作用的影响程度从大到小排序为:HNO3>KMnO4>H2O2>H2SO4;KMnO4氧化可能使黄铁矿表面钝化,降低其可浮性;氧化剂H2SO4、HNO3对黄铁矿表面氧化效果较为显著;增大氧化剂浓度,黄铁矿与黄药作用后表面生成的双黄药会被H2O2溶液氧化,黄铁矿表面疏水层被破坏,进而导致其可浮性下降。

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代淑娟(1967—),女,辽宁新民人,博士,教授,研究方向为难处理金选冶及菱镁矿选矿研究。E-mail:
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刘子源(2000—),男,辽宁锦州人,硕士,研究方向为难处理金选冶。E-mail:

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刘子源(2000—),男,辽宁锦州人,硕士,研究方向为难处理金选冶。E-mail:

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Main element analysis results of pyrite

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FeAgAu
28.50%74.4 g/t0.99 g/t
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黄铁矿主要元素分析结果

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FeAgAu
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不同氧化剂对某含金黄铁矿浮选性能的影响
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刘子源 1, 2 , 代淑娟 1, 2 , 苑林松 2 , 李鹏程 2 , 陈瑜 2
矿冶工程杂志 | 选矿 2025,45(2): 64-68
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矿冶工程杂志 | 选矿 2025, 45(2): 64-68
不同氧化剂对某含金黄铁矿浮选性能的影响
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刘子源1, 2 , 代淑娟1, 2 , 苑林松2, 李鹏程2, 陈瑜2
作者信息
  • 1.辽宁科技大学 化学工程学院,辽宁 鞍山 114051
  • 2.辽宁科技大学 矿业工程学院,辽宁 鞍山 114051
  • 刘子源(2000—),男,辽宁锦州人,硕士,研究方向为难处理金选冶。E-mail:

通讯作者:

代淑娟(1967—),女,辽宁新民人,博士,教授,研究方向为难处理金选冶及菱镁矿选矿研究。E-mail:
Effect of Different Oxidants on Flotation Performance of Gold-Bearing Pyrite
Ziyuan LIU1, 2 , Shujuan DAI1, 2 , Linsong YUAN2, Pengcheng LI2, Yu CHEN2
Affiliations
  • 1.School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China
  • 2.School of Mining Engineering, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China
出版时间: 2025-04-01 doi: 10.3969/j.issn.0253-6099.2025.02.011
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以河北某含金黄铁矿单矿物为研究对象,考察了氧化剂H2SO4、H2O2、HNO3、KMnO4对矿物可浮性的影响,并利用红外光谱检测和电化学测试探究了捕收剂在黄铁矿表面的吸附情况。结果表明:H2SO4、H2O2、HNO3为氧化剂时,适度氧化可促进黄铁矿上浮,KMnO4氧化对黄铁矿可浮性有明显的抑制作用;4种氧化剂氧化对黄铁矿与捕收剂间作用的影响程度从大到小排序为:HNO3>KMnO4>H2O2>H2SO4;KMnO4氧化可能使黄铁矿表面钝化,降低其可浮性;氧化剂H2SO4、HNO3对黄铁矿表面氧化效果较为显著;增大氧化剂浓度,黄铁矿与黄药作用后表面生成的双黄药会被H2O2溶液氧化,黄铁矿表面疏水层被破坏,进而导致其可浮性下降。

黄铁矿  /  浮选  /  氧化剂  /  氧化  /  电化学  /  金  /  丁基黄药  /  捕收剂

As for a gold-bearing pyrite from Hebei Province, the influence of four oxidants, including H2SO4, H2O2, HNO3 and KMnO4, on its floatability was investigated, and the adsorption of collectors on pyrite was also explored by infrared (IR) analysis and electrochemistry measurement. The flotation test shows that with H2SO4, H2O2 and HNO3 as oxidants, moderate oxidation can promote the floatability of pyrite, while the oxidation of KMnO4 can obviously depress the floatability of pyrite. The IR analysis shows that the effects of these four oxidants on pyrite-collector interaction are in the following descending order: HNO3>KMnO4>H2O2>H2SO4. The oxidation of KMnO4 may passivate pyrite and reduce its floatability. Electrochemical analysis shows that H2SO4 and HNO3 have obvious oxidation effects on pyrite. By increasing oxidant concentration, the double xanthate formed on pyrite due to its reaction with xanthate will be oxidized by H2O2 solution, and the hydrophobic layer on pyrite will be destroyed, leading to the decline of pyrite's floatability.

pyrite  /  flotation  /  oxidant  /  oxidation  /  electrochemistry  /  gold  /  butyl xanthate  /  collector
刘子源, 代淑娟, 苑林松, 李鹏程, 陈瑜. 不同氧化剂对某含金黄铁矿浮选性能的影响. 矿冶工程杂志, 2025 , 45 (2) : 64 -68 . DOI: 10.3969/j.issn.0253-6099.2025.02.011
Ziyuan LIU, Shujuan DAI, Linsong YUAN, Pengcheng LI, Yu CHEN. Effect of Different Oxidants on Flotation Performance of Gold-Bearing Pyrite[J]. Mining and Metallurgical Engineering, 2025 , 45 (2) : 64 -68 . DOI: 10.3969/j.issn.0253-6099.2025.02.011
黄铁矿是全球分布极广、资源储量极大的一种硫化矿[1-2]。目前浮选是选别硫化矿的主要方法[3-4]。硫化矿具有氧化特性;氧化会改变矿物表面的可浮性,同时影响捕收剂与矿物表面的相互作用,对浮选分离有较大影响[5-6]。在硫化矿氧化浮选过程中,常用的氧化剂有过氧化氢、次氯酸钠、高锰酸钾、重铬酸钾等。通过调整氧化还原剂用量,创造对浮选有利的氧化还原环境,可获得较好的浮选效果[7-9]
硫化矿物的氧化以及氧化对矿物可浮性的影响已引起广泛关注,但以往研究多为定性研究,较少对硫化矿物氧化规律、氧化对矿物可浮性影响规律进行定量描述。本文以河北某含金黄铁矿单矿物为研究对象,探究氧化对矿物浮选产生的影响,通过红外光谱检测和电化学测试相结合的方法进行机理分析,为硫化矿物的有效分离提供参考,对金矿石浮选回收也具有重要意义。
黄铁矿单矿物取自河北金厂峪,样品中主要矿物为黄铁矿,主要脉石矿物为石英。黄铁矿主要元素分析结果见表1。由表1可知,黄铁矿中铁含量(质量分数)较高,且含有微量的金银元素,黄铁矿纯度较高,符合单矿物试验标准。
氧化试验:取-0.074 mm粒级黄铁矿矿样4 g,在矿浆质量分数20%、搅拌转速350 r/min条件下加入氧化剂进行磁力搅拌,对其进行氧化试验;氧化后静置,烧杯底部矿样用于浮选试验。4种氧化剂分别为硫酸(H2SO4,质量分数10%)、硝酸(HNO3,质量分数10%)、过氧化氢(H2O2,质量分数1%)、高锰酸钾(KMnO4,质量分数1%)。
浮选试验:采用条件试验法,在室温(21 ℃)条件下考察氧化剂用量和氧化时间两个因素对矿物氧化后可浮性的影响;取原矿或不同氧化条件氧化后的矿物4 g于XFGC型充气挂槽式浮选机中进行浮选,浮选矿浆质量分数11.76%,在自然pH值(pH值约6)、捕收剂丁基黄药用量250 g/t(搅拌3 min)、起泡剂2#油用量60 mg/L(搅拌1 min)条件下进行浮选,浮选时间3 min。
检测:采用NICOLET 380 FT-IR红外光谱仪对药剂作用前后的原矿或不同氧化条件氧化后的矿物进行红外光谱检测;采用Vertex One EIS电化学工作站,在三电极工作体系、不同浓度氧化剂溶液中分别进行无捕收剂和有捕收剂条件下的矿物循环伏安扫描测试。
对未被氧化的黄铁矿样品进行浮选试验,试验结果显示,其回收率为77.65%。
氧化剂用量350 mg/L,氧化剂种类对黄铁矿回收率的影响如图1所示。由图1可知:以H2SO4为氧化剂时,随着氧化时间增加,黄铁矿回收率整体呈下降趋势,但均高于未氧化黄铁矿回收率,氧化时间15 min时黄铁矿回收率达到峰值87.88%;以HNO3为氧化剂时,随着氧化时间增加,黄铁矿回收率呈现先上升后下降的趋势,氧化时间45 min时黄铁矿回收率达到峰值83.35%,氧化时间15~45 min的黄铁矿回收率均高于未氧化黄铁矿回收率;以H2O2为氧化剂时,随着氧化时间增加,黄铁矿回收率呈下降再上升的趋势,氧化时间15 min时黄铁矿回收率达到峰值82.53%,之后黄铁矿回收率随着氧化时间增加开始下降,氧化时间45 min时黄铁矿回收率为77.18%,与未氧化黄铁矿回收率接近,氧化时间超过45 min后黄铁矿回收率又缓慢回升;以KMnO4为氧化剂时,随着氧化时间增加,黄铁矿回收率整体呈下降趋势,各氧化时间条件下的黄铁矿回收率均低于未氧化黄铁矿回收率,氧化时间15~30 min的黄铁矿回收率下降明显。
氧化时间30 min,氧化剂用量对黄铁矿可浮性的影响如图2所示。由图2可知:以H2SO4为氧化剂时,随着氧化剂用量增加,黄铁矿回收率总体呈先下降后上升的态势,但均高于未氧化黄铁矿回收率,H2SO4用量350 mg/L时黄铁矿回收率达到最小值81.35%,继续加大氧化剂用量,回收率出现明显上升的趋势,氧化剂用量650 mg/L时黄铁矿回收率达到峰值91.70%;以HNO3为氧化剂时,随着氧化剂用量增加,黄铁矿回收率整体呈现先上升后下降的趋势,氧化剂用量500 mg/L时黄铁矿回收率达到峰值83.70%,之后继续增加氧化剂用量,黄铁矿回收率轻微下降,推测增大氧化剂用量至500 mg/L以上后,可能会使黄铁矿表面产物产量增加,从而降低矿物表面活性,不利于捕收剂吸附;以H2O2为氧化剂时,随着氧化剂用量增加,黄铁矿回收率呈上升趋势,但上升幅度不大,氧化剂用量650 mg/L时黄铁矿回收率达到峰值79.65%;以KMnO4为氧化剂时,随着氧化剂用量增加,黄铁矿回收率总体呈两段式变化,氧化剂用量200~350 mg/L和500~650 mg/L时,黄铁矿回收率呈下降趋势,且前者下降幅度较大,氧化剂用量350 mg/L时,黄铁矿回收率达到最低值57.88%。
以H2SO4为氧化剂时,氧化对黄铁矿的上浮有一定促进作用,氧化时间30 min时,控制H2SO4用量在500~650 mg/L范围内可使黄铁矿回收率达到较高水平。以HNO3为氧化剂时,随着氧化时间及氧化剂用量增大,HNO3对黄铁矿上浮先促进、后促进效果减弱;控制氧化剂用量350 mg/L、氧化时间30~45 min范围内或氧化时间30 min、氧化剂用量350~500 mg/L范围内,可使黄铁矿回收率达到较高水平。H2O2氧化对黄铁矿的上浮有微弱的促进作用。KMnO4氧化对黄铁矿的上浮有较强的抑制作用。
黄铁矿与各药剂作用前后的红外光谱如图3所示。从图3可以看出,黄铁矿与丁基黄药作用后,分别在2 924.82、2 856.25 cm-1处有新的吸收峰产生,结合文献[10]分析得知这些吸收峰为双黄药的特征吸收峰,说明黄铁矿与丁基黄药作用后,矿物表面生成了疏水性双黄药。黄铁矿被H2SO4氧化再与丁基黄药作用后,双黄药的特征吸收峰水平变化不明显,说明H2SO4氧化对黄铁矿表面与捕收剂丁基黄药间的作用影响较小。黄铁矿被HNO3氧化再与丁基黄药作用后,双黄药的特征吸收峰消失,说明HNO3氧化可抑制黄铁矿矿物表面与捕收剂丁基黄药作用,进而对黄铁矿的上浮产生抑制作用。黄铁矿被H2O2氧化再与丁基黄药作用后,双黄药的特征吸收峰明显弱于氧化前的水平,没有新的特征吸收峰生成,说明H2O2氧化对黄铁矿矿物表面与捕收剂丁基黄药间产生了抑制作用。黄铁矿被KMnO4氧化再与丁基黄药作用后,双黄药的特征吸收峰变弱,且3 115.04、986.87 cm-1处有新的吸收峰产生,结合文献[11]分析,可能是黄铁矿在KMnO4氧化后发生了钝化,KMnO4与黄铁矿表面活化膜反应生成了亲水性金属羟基化合物,从而对黄铁矿可浮性产生抑制作用。
综上所述,HNO3氧化对黄铁矿与捕收剂间的作用影响较大,H2O2次之,H2SO4、KMnO4氧化对黄铁矿与捕收剂间的作用影响较小。结合浮选试验现象分析可得,以H2SO4、HNO3及H2O2为氧化剂时,氧化浮选中的促进上浮现象可能是黄铁矿氧化后自身表面生成疏水物质,当疏水物质继续被氧化后,促进效果减弱;KMnO4氧化可能使黄铁矿表面发生钝化,生成亲水性金属羟基化合物,抑制其上浮。
无捕收剂作用时,黄铁矿电极在不同浓度氧化剂溶液中的循环伏安曲线如图4所示。从图4可以看出,黄铁矿在氧化剂溶液中氧化所产生的循环伏安曲线出现了明显的阳极电流。氧化剂浓度在5×10-4 mol/L以上时,随着氧化剂浓度增大,H2SO4、HNO3溶液对应的循环伏安曲线阳极电流值逐渐提高,而H2O2、KMnO4对应的循环伏安曲线阳极电流值变化不太明显。由上述分析可知,H2SO4、HNO3作为氧化剂对黄铁矿表面氧化效果较为显著。
丁基黄药用量1 mmol/L时,黄铁矿电极在不同浓度氧化剂溶液中的循环伏安曲线如图5所示。从图5可以看出,在有捕收剂参与的条件下,黄铁矿在氧化剂溶液中所产生的循环伏安曲线出现了明显的阳极电流,发生了电化学作用。氧化剂浓度在5×10-4 mol/L以上时,随着氧化剂浓度增大,H2SO4、HNO3、KMnO4对应的循环伏安曲线阳极电流值逐渐提高,而H2O2对应的循环伏安曲线阳极电流值没有明显变化。反向扫描时,4种氧化剂对应的循环伏安曲线都出现较弱的还原峰。由上述分析可知,H2O2为氧化剂可氧化黄铁矿与丁基黄药作用后生成的双黄药,随着疏水性产物吸附量减少,黄铁矿表面疏水性减弱,可浮性降低。
1)浮选试验结果表明:以H2SO4、HNO3、H2O2为氧化剂时,适度的氧化对黄铁矿的上浮有一定促进作用;KMnO4氧化对黄铁矿抑制作用较为显著,随着氧化时间和氧化剂用量增大,抑制效果更强烈。
2)红外光谱分析结果表明:4种氧化剂对黄铁矿与捕收剂间作用的影响程度大小排序为:HNO3>KMnO4>H2O2>H2SO4;以H2SO4、HNO3、H2O2为氧化剂时,氧化浮选中的促进上浮现象可能是由于黄铁矿氧化后自身表面生成疏水物质,当黄铁矿表面的疏水物质继续被氧化后,氧化剂的促进效果减弱;KMnO4为氧化剂可能使矿物发生钝化,生成亲水的金属羟基化合物,进而抑制矿物上浮。
3)电化学特征分析结果表明:氧化剂H2SO4和HNO3对黄铁矿表面氧化效果较为显著;氧化剂溶液浓度在5×10-4 mol/L以上时,随着氧化剂浓度增大,H2SO4、HNO3、KMnO4对应的循环伏安曲线阳极电流值逐渐提高,而H2O2对应的循环伏安曲线阳极电流值没有明显变化。黄铁矿与丁基黄药作用后表面生成的双黄药会被H2O2溶液氧化,黄铁矿表面疏水层被破坏,进而致使黄铁矿可浮性下降。
  • 国家自然科学基金(52174254)
  • 2024年辽宁省教育厅高校基本科研项目(LJ212410146034)
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2025年第45卷第2期
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doi: 10.3969/j.issn.0253-6099.2025.02.011
  • 接收时间:2024-11-01
  • 首发时间:2026-03-19
  • 出版时间:2025-04-01
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  • 收稿日期:2024-11-01
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国家自然科学基金(52174254)
2024年辽宁省教育厅高校基本科研项目(LJ212410146034)
作者信息
    1.辽宁科技大学 化学工程学院,辽宁 鞍山 114051
    2.辽宁科技大学 矿业工程学院,辽宁 鞍山 114051

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代淑娟(1967—),女,辽宁新民人,博士,教授,研究方向为难处理金选冶及菱镁矿选矿研究。E-mail:
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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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