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Article(id=1241406712809321434, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241406711219680205, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.06.020, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1717603200000, receivedDateStr=2024-06-06, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773904024555, onlineDateStr=2026-03-19, pubDate=1732982400000, pubDateStr=2024-12-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773904024555, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773904024555, creator=13701087609, updateTime=1773904024555, updator=13701087609, issue=Issue{id=1241406711219680205, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='6', pageStart='1', pageEnd='174', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773904024176, creator=13701087609, updateTime=1773911273793, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241437118384362345, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241406711219680205, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241437118388556650, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241406711219680205, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=94, endPage=98, ext={EN=ArticleExt(id=1241406713098728418, articleId=1241406712809321434, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Leaching Characteristics of Marine Sedimentary Manganese Deposit in Xinjiang, columnId=1236276106727321817, journalTitle=Mining and Metallurgical Engineering, columnName=METALLURGY, runingTitle=null, highlight=null, articleAbstract=

An experimental research was carried out on leaching of marine sedimentary manganese deposit from Xinjiang, and effects of acid-to-ore ratio, leaching temperature, leaching time, and ore particle size on manganese leaching rate were investigated. The results indicate that effective separation between elements of silicon and manganese in the solution can be actualized by increasing leaching temperature and prolonging leaching time, which can also benefit the formation of large-particle precipitates and enhancement of filtering speed. After manganese ores with particle size of -150 μm are leached at room temperature for 4 hours, with acid-to-ore ratio of 0.56, the manganese leaching rate can be up to 86.32% and a leaching residue rate is 61.12%, while the mass concentration of manganese ions in the manganese sulfate leachate is 41.29 g/L.

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对新疆海相沉积型锰矿进行了浸出实验研究，考察了酸矿比、浸出温度、浸出时间和矿石粒度对矿石中锰浸出率的影响。结果表明：升高浸出温度和延长浸出时间，可有效实现溶液中硅与锰元素的分离，并有利于形成大颗粒沉淀物、提高过滤速度；在矿石粒度-150 μm、酸矿比0.56、常温下浸出4 h，锰浸出率可达86.32%，浸出渣率61.12%，硫酸锰浸出液中锰离子质量浓度41.29 g/L。

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万凌云（1988—），男，新疆乌鲁木齐人，高级工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：
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周新锋（1993—），男，新疆克拉玛依人，工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：

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周新锋（1993—），男，新疆克拉玛依人，工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：

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周新锋（1993—），男，新疆克拉玛依人，工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：

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Ma——碳酸锰矿；Mc——锰绿泥石

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MnSiCaMgAlFe
28.488.846.074.522.542.32
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矿石化学成分分析结果（质量分数）

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MnSiCaMgAlFe
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锰物相质量分数/%分布率/%
碳酸锰中锰24.1784.87
氧化锰中锰1.435.02
硅酸锰中锰2.8810.11
合计28.48100.00
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锰化学物相分析结果

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碳酸锰中锰24.1784.87
氧化锰中锰1.435.02
硅酸锰中锰2.8810.11
合计28.48100.00
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酸矿比终点pH值浸出渣率/%过滤时间/min
0.324.9788.674.34
0.404.3579.956.11
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0.562.8761.1216.64
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0.721.3254.158.91
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浸出温度/℃终点pH值浸出渣率/%过滤时间/min
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252.5661.3119.33
452.8761.1216.64
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653.5161.258.45
853.5661.826.53
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浸出时间/h终点pH值浸出渣率/%过滤时间/min
22.2562.1217.21
42.3761.1216.64
62.5661.0820.01
93.0164.7132.11
123.5466.2225.11
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123.5466.2225.11
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矿石粒度/μm终点pH值浸出渣率/%过滤时间/min
1002.5160.2221.22
1502.3761.1216.64
2002.2263.5717.55
2502.2763.2222.31
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2002.2263.5717.55
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新疆海相沉积型锰矿浸出特性研究
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周新锋 1 , 万凌云 1 , 马晓磊 2 , 何利华 1, 3 , 王昊鹏 1 , 张小慧 1 , 胡馨文 1
矿冶工程杂志 | 冶金 2024,44(6): 94-98
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矿冶工程杂志 | 冶金 2024, 44(6): 94-98
新疆海相沉积型锰矿浸出特性研究
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周新锋1 , 万凌云1 , 马晓磊2, 何利华1, 3, 王昊鹏1, 张小慧1, 胡馨文1
作者信息
  • 1.新疆有色金属研究所有限公司，新疆　乌鲁木齐　830009
  • 2.阿克陶科邦锰业制造有限公司，新疆　阿克陶　845550
  • 3.中南大学　冶金与环境学院，湖南　长沙　410083

    • 周新锋（1993—），男，新疆克拉玛依人，工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：

通讯作者:

万凌云（1988—），男，新疆乌鲁木齐人，高级工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：
Leaching Characteristics of Marine Sedimentary Manganese Deposit in Xinjiang
Xinfeng ZHOU1 , Lingyun WAN1 , Xiaolei MA2, Lihua HE1, 3, Haopeng WANG1, Xiaohui ZHANG1, Xinwen HU1
Affiliations
  • 1.Xinjiang Nonferrous Metals Research Institute Co., Ltd., Urumqi 830009, Xinjiang, China
  • 2.Akto Kebang Manganese Industry Manufacturing Co., Ltd., Akto 845550, Xinjiang, China
  • 3.School of Metallurgy and Environment, Central South University, Changsha 410083, Hunan, China
出版时间: 2024-12-01 doi: 10.3969/j.issn.0253-6099.2024.06.020
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摘要
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对新疆海相沉积型锰矿进行了浸出实验研究，考察了酸矿比、浸出温度、浸出时间和矿石粒度对矿石中锰浸出率的影响。结果表明：升高浸出温度和延长浸出时间，可有效实现溶液中硅与锰元素的分离，并有利于形成大颗粒沉淀物、提高过滤速度；在矿石粒度-150 μm、酸矿比0.56、常温下浸出4 h，锰浸出率可达86.32%，浸出渣率61.12%，硫酸锰浸出液中锰离子质量浓度41.29 g/L。

海相沉积型锰矿  /  碳酸锰  /  浸出  /  锰  /  锰硅分离

An experimental research was carried out on leaching of marine sedimentary manganese deposit from Xinjiang, and effects of acid-to-ore ratio, leaching temperature, leaching time, and ore particle size on manganese leaching rate were investigated. The results indicate that effective separation between elements of silicon and manganese in the solution can be actualized by increasing leaching temperature and prolonging leaching time, which can also benefit the formation of large-particle precipitates and enhancement of filtering speed. After manganese ores with particle size of -150 μm are leached at room temperature for 4 hours, with acid-to-ore ratio of 0.56, the manganese leaching rate can be up to 86.32% and a leaching residue rate is 61.12%, while the mass concentration of manganese ions in the manganese sulfate leachate is 41.29 g/L.

marine sedimentary manganese deposits  /  manganese carbonate  /  leaching  /  manganese  /  separation of manganese and silicon
周新锋, 万凌云, 马晓磊, 何利华, 王昊鹏, 张小慧, 胡馨文. 新疆海相沉积型锰矿浸出特性研究. 矿冶工程杂志, 2024 , 44 (6) : 94 -98 . DOI: 10.3969/j.issn.0253-6099.2024.06.020
Xinfeng ZHOU, Lingyun WAN, Xiaolei MA, Lihua HE, Haopeng WANG, Xiaohui ZHANG, Xinwen HU. Leaching Characteristics of Marine Sedimentary Manganese Deposit in Xinjiang[J]. Mining and Metallurgical Engineering, 2024 , 44 (6) : 94 -98 . DOI: 10.3969/j.issn.0253-6099.2024.06.020
正文
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锰是一种重要的工业原料，在冶金、化工、电子、电池、农业等领域广泛应用[1-2]。我国锰矿资源主要分为海相沉积型、沉积变质型和风化壳型锰矿床，其中海相沉积型锰矿占全国锰矿资源量的80%以上[3]。我国锰矿资源的特点是富矿少、贫矿多，且物质组分、矿石结构较为复杂，平均品位仅21%左右。富锰矿是指品位25%以上的氧化锰矿和碳酸锰矿，但富锰矿资源储量很少，仅占我国锰矿资源的6.3%。针对我国锰矿资源特点，研发锰矿高效浸出技术与工艺、减少生产投资和环境污染，已成为矿山企业关注的重点[4-5]。
近年，在新疆阿克陶县发现了玛尔坎苏锰成矿带，该成矿带以石炭系细碎屑岩-碳酸盐岩沉积建造为主，属于典型的海相沉积型锰矿[6]，矿石矿物以碳酸锰矿为主，品位25%以上，属于优质富锰矿石。充分利用该锰矿资源，开发高附加值、高利用率的锰基材料，对锰冶炼产业具有重要意义[7-8]。
1　实验原料与方法
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1.1　实验原料
某海相沉积型锰矿石取自新疆某厂，为灰色、蚕豆大小的粒状物料，经干燥、磨粉后作为实验原料，其X射线衍射图谱、化学元素分析、锰化学物相分析结果分别如图1、表1、表2所示。矿石主要矿物组成为MnCO3、SiO2、CaCO3、（Mg，Fe）3Si2O5（OH）4；矿石中锰含量（质量分数，下同）高达28.48%，属于优质富锰矿石，其中硅、钙和镁元素含量较高；矿石中锰主要以碳酸锰和硅酸锰形式存在，分别占总锰的84.87%和10.11%，也有少量锰以氧化锰形式存在。
海相沉积型锰矿石嵌布特征如图2所示。部分碳酸锰矿石呈团粒状集合体，粒间夹杂有细小锰绿泥石；另一部分碳酸锰矿石呈半自形粒状集合体，粒度粗大的颗粒连续分布形成短脉状，细小碎粒呈浸染状密集分布于锰绿泥石基底中。
实验试剂包括浓硫酸（98%，分析纯）和阳极液（H2SO4质量浓度38～41 g/L、Mn质量浓度14～17 g/L）。
1.2　实验设备
实验设备包括DZKW-S-4水浴锅、SHA-DⅢ循环水式真空泵、DZF-6050干燥箱、PHS-3C型pH计以及搅拌器等。
1.3　实验原理及方法
1.3.1　实验原理
根据物相分析结果，锰元素主要以碳酸锰、氧化锰和硅酸锰形式赋存于矿石中，浸出过程中，锰主要与溶液中的H+发生反应[9]：
1.3.2　实验方法
在烧杯中加入一定量阳极液，再按照一定酸矿比补加相应的浓硫酸，在搅拌条件下升温至实验温度，加入矿石粉末，反应一定时间后结束浸出反应。液固分离后，分别收集滤液和滤渣，记录滤液体积和滤渣质量，滤液取样分析Mn、Mg、Fe、Si、Ca、Al、K、Na含量及pH值，滤渣经110 ℃干燥8 h后，计算滤渣含水率及浸出渣率。
1.4　分析方法
采用ICP-OES法检测滤液中Mn、Mg、Fe、Si、Ca、Al、K、Na含量。采用溶样消解-ICP法测定浸出渣中锰质量浓度。采用PHS-3C型pH计测量滤液pH值。
2　实验结果与讨论
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2.1　酸矿比的影响
在矿石浸出过程中，酸耗是一个非常关键的指标。矿场中堆放的矿石锰品位存在一定差异，使得生产过程中酸耗差异较大。因此，探索合适的酸矿比十分重要[10-11]。这里定义酸矿比为阳极液中余酸质量（阳极液体积×阳极液中余酸质量浓度）与新加入浓硫酸质量之和与锰矿质量之比。
根据电解锰合格液对锰含量的要求，称取50 g粒度-150 μm的矿石粉末，加入500 mL阳极液，按不同酸矿比补加浓硫酸，将烧杯放入水浴锅中，浸出温度45 ℃、浸出6 h，考察酸矿比对锰矿中Mn、Mg、Fe、Si、Ca、Al、K、Na浸出行为以及浸出渣率和终点pH值的影响，结果如图3～4及表3所示。
由图3可以看出，酸矿比从0.32增至0.56，浸出液中锰离子质量浓度迅速从27.36 g/L增至41.31 g/L，锰浸出率从44.68%增至86.45%；之后随着酸矿比进一步增加，锰浸出率增长速度变缓。酸矿比对溶液中镁质量浓度影响较小，镁质量浓度稳定在9～10 g/L。
由图4可以看出，酸矿比0.32～0.72范围内，酸矿比对钾、钠和钙的浸出影响较小，甚至酸度升高时浸出液中钙质量浓度稍有下降。酸矿比小于0.40时，酸矿比对铁、铝和硅的浸出影响较小；酸矿比超过0.40后，铁、铝和硅浸出量迅速增加。与铁和铝的浸出情况不同，酸矿比超过0.56后，硅浸出增长速度变缓，表明硅在浸出液中的溶解度趋于饱和。
由表3可以看出，随着酸矿比增加，浸出渣率和终点pH值迅速下降，酸矿比超过0.56后，终点pH值持续降低，但浸出渣率的下降速度减慢。结合图3～4可以发现，当前条件下锰浸出率并未得到明显提升，浸出渣率降低主要是由于矿石中的铁和铝元素被大量溶解出来。过滤时间呈先增加后减小的趋势。酸矿比0.48时所得浸出料液过滤时间最长，此时终点pH值为3.26。过滤速度变慢的原因可能是在这个pH值附近，铁离子开始发生絮凝沉淀，形成大量胶体[12-13]。
综合考虑，可将酸矿比控制在0.56，在确保锰浸出率的同时最大限度地抑制杂质铁、铝离子进入溶液中，此外，这也避开了过滤时间较长造成生产效率降低的问题。
2.2　浸出温度的影响
控制酸矿比0.56，其他条件不变，考察浸出温度（0代表无外源加热）对矿石中Mn、Mg、Fe、Si、Ca、Al、K、Na浸出行为以及浸出渣率和终点pH值的影响，结果如图5～6及表4所示。
由图5可以看出，随着浸出温度升高，锰浸出率一直保持在86%左右，并且溶液中锰和镁质量浓度变化不大。因此，对于该矿石来说，浸出过程中无需额外加热。利用浓硫酸稀释过程和浸出过程的放热效应足以保证锰的高浸出率。
由图6可以看出，浸出温度对钾、钠、钙、铝和铁等杂质质量浓度影响较小，但对硅的浸出影响十分显著。浸出温度从45 ℃升至65 ℃，浸出液中硅质量浓度从742 mg/L降至212 mg/L；之后进一步升高浸出温度，硅质量浓度缓慢减少。
由表4可以看出，随着浸出温度升高，终点pH值逐步提高，浸出渣率略微增加，结合图6可以发现，随着浸出温度升高，溶液中硅离子开始发生沉淀，浸出渣率增加。过滤时间逐渐减少，是由于低温下所得沉淀物为细颗粒胶体，其过滤性能较差，高温有利于得到大颗粒沉淀渣，过滤速度加快。
2.3　浸出时间的影响
浸出时间对制液时间、电解锰产能和工作强度都有重要影响。选择合适的浸出时间可以提高生产效率。矿石粉末-150 μm，在酸矿比0.56、常温浸出条件下，考察了浸出时间对锰矿中Mn、Mg、Fe、Si、Ca、Al、K、Na浸出行为以及浸出渣率和终点pH值的影响，结果如图7～8及表5所示。
由图7可以看出：浸出时间从2 h延长到4 h，锰浸出率从74.41%增加至86.32%，溶液中锰离子质量浓度从37.91 g/L增加至41.29 g/L；之后进一步延长浸出时间，锰浸出率变化很小。这表明矿石反应活性较好，在较短时间内已经完成了碳酸锰矿中锰的浸出。浸出时间4 h足以保证锰的高浸出率。
由图8可以看出，随着浸出时间延长，浸出液中钾、钠、钙质量浓度变化不大，但硅、铝、铁质量浓度逐步降低，特别是硅，降幅显著，浸出2 h时，浸出液中硅质量浓度高达861 mg/L，浸出时间延长至12 h，浸出液中硅质量浓度可降至115 mg/L。
由表5可以看出，随着浸出时间延长，终点pH值逐渐上升，浸出渣率先减小后增加，结合图8可以发现，浸出渣率增加主要是溶液中铁、铝、硅水解沉淀所致。浸出渣率增加并未对过滤速度带来持续的不利影响，浸出时间9 h以内时，随着浸出时间延长，过滤时间先减少后增加；浸出时间超过9 h后，过滤时间减小。尽管延长浸出时间对锰的浸出没有明显作用，但延长浸出时间有利于硅、铝、铁水解沉淀物的絮凝长大，有利于改善过滤性能。
2.4　矿石粒度的影响
矿石的浸出过程属于固液反应，矿石粒度直接影响矿石与硫酸溶液的反应面积，同时也会影响硫酸扩散进入矿石粉末内部的速度[14-15]。酸矿比0.56、常温浸出4 h条件下，考察了矿石粒度对锰矿中Mn、Mg、Fe、Si、Ca、Al、K、Na等元素的浸出行为以及浸出渣率和终点pH值的影响，结果如图9～10及表6所示。
由图9可以看出，随着矿石粒度增加，锰浸出率逐渐降低。这是因为较细粒度的矿粉更容易与硫酸充分接触，反应更彻底。随着矿石粒度变化，浸出液中锰质量浓度差异较小，可能是因为原料中总锰质量分数存在一定差异。综合考虑磨矿能耗以及锰浸出率等，选择粒度-150 μm的矿粉作为浸出原料更为合理。
由图10可以看出，矿石粒度对矿石中杂质浸出无明显影响，不同粒度矿粉所得浸出液中硅、铝、铁、钾、钠、钙等杂质含量相差不大。
由表6可以看出，随着矿石粒度降低，所得浸出液终点pH值偏高，表明酸耗相对较高，而酸耗与锰的浸出有一定相关性，这意味着细颗粒碳酸锰矿浸出效果更好一些，因此粒度较小的矿粉浸出渣率相对较低。
2.5　综合实验
实际生产过程中，在保证锰被充分浸出的前提下，通过控制酸矿比、浸出时间、矿石粒度等生产条件，最大程度抑制溶液中杂质元素被浸出。在矿石粒度为-150 μm、酸矿比0.56、常温下浸出4 h条件下，锰浸出率可达86.32%，浸出渣率61.12%，硫酸锰浸出液中锰离子质量浓度41.29 g/L，钙、铁、铝、钾、钠、硅等杂质元素在溶液中质量浓度分别为620 mg/L、251 mg/L、291 mg/L、108 mg/L、657 mg/L、822 mg/L。
3　结论
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1）随着浸出温度升高，溶液中硅质量浓度迅速下降，能实现硅与锰元素的分离。同时，高温有利于获得大颗粒沉淀渣、加快过滤速度。
2）随着浸出时间延长，硅、铝、铁质量浓度逐步降低，特别是硅，降幅显著。
3）针对海相沉积型锰矿，适宜的浸出条件为：矿石粒度-150 μm、酸矿比0.56、常温下浸出4 h。该条件下，锰浸出率可达86.32%，浸出渣率61.12%，硫酸锰浸出液中锰离子质量浓度41.29 g/L。
基金
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  • 新疆维吾尔自治区重点研发计划(2022B01040-1)
文献
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2024年第44卷第6期
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doi: 10.3969/j.issn.0253-6099.2024.06.020
  • 接收时间：2024-06-06
  • 首发时间：2026-03-19
  • 出版时间：2024-12-01
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  • 收稿日期：2024-06-06
基金
新疆维吾尔自治区重点研发计划(2022B01040-1)
作者信息
    1.新疆有色金属研究所有限公司，新疆　乌鲁木齐　830009
    2.阿克陶科邦锰业制造有限公司，新疆　阿克陶　845550
    3.中南大学　冶金与环境学院，湖南　长沙　410083

通讯作者:

万凌云（1988—），男，新疆乌鲁木齐人，高级工程师，硕士，主要研究方向为锰基新材料的开发与应用。E-mail：
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https://castjournals.cast.org.cn/joweb/kygczz/CN/10.3969/j.issn.0253-6099.2024.06.020
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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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