Article(id=1241416387671937882, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.03.025, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1735488000000, receivedDateStr=2024-12-30, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773906331222, onlineDateStr=2026-03-19, pubDate=1748707200000, pubDateStr=2025-06-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773906331222, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773906331222, creator=13701087609, updateTime=1773906331222, updator=13701087609, issue=Issue{id=1241416382559081210, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='3', pageStart='1', pageEnd='223', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773906330003, creator=13701087609, updateTime=1773908015401, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241423451685179940, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241423451685179941, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=151, endPage=157, ext={EN=ArticleExt(id=1241416387948761968, articleId=1241416387671937882, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Purification of Spherical Graphite by Alkali-Acid Method, columnId=1236276106727321817, journalTitle=Mining and Metallurgical Engineering, columnName=METALLURGY, runingTitle=null, highlight=null, articleAbstract=

To address the issues of low purity and high consumption of alkali and acid during chemical purification of graphite, Luobei spherical graphite was taken to explore the occurrence state of impurities therein and to perform tests on its purification by alkali-acid method. A novel alkali-acid method was developed, which consists of stirring with alkali under negative-positive pressure and pressure acid leaching. This purification process is conducted in the following steps with the optimized conditions: firstly leave graphite in a vacuum for 35 min with vacuum degree of -0.15 MPa, and then stir for 40 min under pressure of 0.19 MPa at 120 ℃ by adding NaOH at a concentration of 40%, with NaOH solution and spherical graphite in a liquid-to-solid ratio of 1.0 mL/g;after 120 min roasting at 550 ℃, acid leaching with HCl at a concentration of 2.5 mol/L is performed under pressure of 0.16 MPa at 118 ℃ for 90 min, with HCl solution and graphite in a liquid-to-solid ratio of 1.0 mL/g. As a result, the fixed carbon content in the purified graphite is up from 95.35% to 99.96%.

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针对石墨化学提纯过程中提纯纯度不高、碱酸用量大等问题,以萝北球形石墨为研究对象,研究球形石墨中杂质的赋存状态,开展碱酸法提纯试验研究,开发出负-正压混碱加压酸浸的碱酸法提纯工艺。结果表明,负-正压混碱加压酸浸的碱酸法提纯工艺的优化条件为:石墨在真空下静置35 min、真空度-0.15 MPa,加压搅拌时氢氧化钠浓度40%、压力0.19 MPa(加压温度120 ℃)、搅拌时间40 min、氢氧化钠溶液与球形石墨的液固比1.0 mL/g,焙烧过程中焙烧时间120 min、焙烧温度550 ℃,酸浸时HCl浓度2.5 mol/L、压力0.16 MPa(酸浸温度118 ℃)、盐酸溶液与石墨的液固比1.0 mL/g、酸浸时间90 min,该条件下石墨提纯后固定碳含量由95.35%提升至99.96%。

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邱杨率(1987—),男,湖北汉川人,博士,副教授,主要研究方向为非金属矿选矿及深加工,矿物材料制备。E-mail:
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张文学(2000—),男,云南楚雄人,硕士研究生,主要研究方向为非金属矿选矿及深加工。E-mail:

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张文学(2000—),男,云南楚雄人,硕士研究生,主要研究方向为非金属矿选矿及深加工。E-mail:

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张文学(2000—),男,云南楚雄人,硕士研究生,主要研究方向为非金属矿选矿及深加工。E-mail:

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Experimental research on the alkali-acid method purification of graphite and kinetics of desilication[D]. Wuhan: Wuhan University of Technology, 2015., articleTitle=Experimental research on the alkali-acid method purification of graphite and kinetics of desilication, refAbstract=null)], funds=[Fund(id=1241422278915846987, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, awardId=2021YFC2902902, language=CN, fundingSource=国家重点研发计划(2021YFC2902902), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241422260330885491, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, xref=1., ext=[AuthorCompanyExt(id=1241422260335079796, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, companyId=1241422260330885491, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China), 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(a)常规碱酸法;(b)负-正压混碱加压酸浸的碱酸法

, figureFileSmall=7BebpaMYGZ8Ee0j8ZuW23g==, figureFileBig=DaPChKf02iw8wyPQiYQaQA==, tableContent=null), ArticleFig(id=1241422270615319262, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Fig.11, caption=EDS spectrum of purified graphite by optimized alkali-acid method, figureFileSmall=FV8zQ3BGULXtXuLLwlXldg==, figureFileBig=eql5o0+7hExdC9n+Jdt5vg==, tableContent=null), ArticleFig(id=1241422270724371170, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=图11, caption=负-正压混碱加压酸浸的碱酸法提纯后球形石墨X射线能谱图, figureFileSmall=FV8zQ3BGULXtXuLLwlXldg==, figureFileBig=eql5o0+7hExdC9n+Jdt5vg==, tableContent=null), ArticleFig(id=1241422270846005990, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 1, caption=

Chemical composition of raw materials

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2Al2O3Fe2O3K2OClCaOTGCLOI
1.460.740.630.165 70.0090.03295.3596.95
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原料化学成分分析结果(质量分数)

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2Al2O3Fe2O3K2OClCaOTGCLOI
1.460.740.630.165 70.0090.03295.3596.95
), ArticleFig(id=1241422271147995885, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 2, caption=

EDS analysis results of cross-section of graphite

, figureFileSmall=null, figureFileBig=null, tableContent=
CSiFeAlOCa
95.401.290.870.471.830.17
), ArticleFig(id=1241422271303185135, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表2, caption=

石墨截面EDS测试结果(质量分数)

, figureFileSmall=null, figureFileBig=null, tableContent=
CSiFeAlOCa
95.401.290.870.471.830.17
), ArticleFig(id=1241422271437402865, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 3, caption=

EDS analysis results of suspected mineralization positions

, figureFileSmall=null, figureFileBig=null, tableContent=
CSiFeAlOCa
83.664.552.632.006.690.47
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疑似矿物点EDS测试结果(质量分数)

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CSiFeAlOCa
83.664.552.632.006.690.47
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Effect of mass ratio of sodium hydroxide to graphite on fixed carbon content

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氢氧化钠与石墨质量比固定碳含量/%备注
0.296.85焙烧时间90 min,焙烧温度450 ℃
0.497.55
0.697.85
0.898.07
1.098.18
1.298.20
), ArticleFig(id=1241422271949107964, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表4, caption=

氢氧化钠与石墨质量比对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
氢氧化钠与石墨质量比固定碳含量/%备注
0.296.85焙烧时间90 min,焙烧温度450 ℃
0.497.55
0.697.85
0.898.07
1.098.18
1.298.20
), ArticleFig(id=1241422273542943488, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 5, caption=

Effect of roasting time of normal alkaline roasting on fixed carbon content

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焙烧时间/min固定碳含量/%备注
3097.45焙烧温度450 ℃,氢氧化钠与石墨质量比1.0
6097.90
9098.15
12098.26
15098.26
18098.28
), ArticleFig(id=1241422273660384001, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表5, caption=

常规碱焙烧时焙烧时间对固定碳含量的影响

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焙烧时间/min固定碳含量/%备注
3097.45焙烧温度450 ℃,氢氧化钠与石墨质量比1.0
6097.90
9098.15
12098.26
15098.26
18098.28
), ArticleFig(id=1241422273761047300, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 6, caption=

Effect of roasting temperature of normal alkaline roasting on fixed carbon content

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焙烧温度/℃固定碳含量/%备注
35097.75焙烧时间120 min,氢氧化钠与石墨质量比1.0
40097.94
45098.18
50098.30
55098.31
60098.31
65098.30
70098.25
), ArticleFig(id=1241422273891070725, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表6, caption=

常规碱焙烧时焙烧温度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧温度/℃固定碳含量/%备注
35097.75焙烧时间120 min,氢氧化钠与石墨质量比1.0
40097.94
45098.18
50098.30
55098.31
60098.31
65098.30
70098.25
), ArticleFig(id=1241422274042065672, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 7, caption=

Effect of HCl concentration in normal acid leaching on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
盐酸浓度/(mol·L-1固定碳含量/%备注
1.098.59酸浸时间120 min,酸浸温度60 ℃,液固比1.0 mL/g
1.598.70
2.098.79
2.598.86
3.098.92
3.598.91
), ArticleFig(id=1241422274155311883, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表7, caption=

常规酸浸时盐酸浓度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
盐酸浓度/(mol·L-1固定碳含量/%备注
1.098.59酸浸时间120 min,酸浸温度60 ℃,液固比1.0 mL/g
1.598.70
2.098.79
2.598.86
3.098.92
3.598.91
), ArticleFig(id=1241422274318889741, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 8, caption=

Effect of acid leaching temperature in normal acid leaching on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
酸浸温度/℃固定碳含量/%备注
4098.86酸浸时间120 min,盐酸浓度3.0 mol/L,液固比1.0 mL/g
5098.88
6098.92
7098.95
8098.95
9098.95
), ArticleFig(id=1241422274394387216, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表8, caption=

常规酸浸时酸浸温度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
酸浸温度/℃固定碳含量/%备注
4098.86酸浸时间120 min,盐酸浓度3.0 mol/L,液固比1.0 mL/g
5098.88
6098.92
7098.95
8098.95
9098.95
), ArticleFig(id=1241422274499244819, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 9, caption=

Effect of liquid-solid ratio in normal acid leaching on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
液固比/(mL·g-1固定碳含量/%备注
0.598.94酸浸时间120 min,盐酸浓度3.0 mol/L,酸浸温度70 ℃
1.098.93
1.598.95
2.098.94
2.598.95
3.098.98
3.598.96
), ArticleFig(id=1241422274742514454, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表9, caption=

常规酸浸时液固比对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
液固比/(mL·g-1固定碳含量/%备注
0.598.94酸浸时间120 min,盐酸浓度3.0 mol/L,酸浸温度70 ℃
1.098.93
1.598.95
2.098.94
2.598.95
3.098.98
3.598.96
), ArticleFig(id=1241422274851566359, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 10, caption=

Effect of acid leaching time in normal acid leaching on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
酸浸时间/min固定碳含量/%备注
6098.76酸浸温度70 ℃,盐酸浓度3.0 mol/L,液固比1.0 mL/g
9098.87
12098.92
15098.96
18098.95
21098.95
24098.96
), ArticleFig(id=1241422274943841051, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表10, caption=

常规酸浸时酸浸时间对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
酸浸时间/min固定碳含量/%备注
6098.76酸浸温度70 ℃,盐酸浓度3.0 mol/L,液固比1.0 mL/g
9098.87
12098.92
15098.96
18098.95
21098.95
24098.96
), ArticleFig(id=1241422275061281565, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 11, caption=

Effect of NaOH solution concentration in alkaline roasting at atmospheric pressure on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
氢氧化钠溶液浓度/%固定碳含量/%备注
1098.12液固比1.0 mL/g,焙烧温度450 ℃,焙烧时间90 min
2098.97
3099.23
4099.32
5099.33
), ArticleFig(id=1241422275195499297, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表11, caption=

常压碱焙烧时氢氧化钠溶液浓度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
氢氧化钠溶液浓度/%固定碳含量/%备注
1098.12液固比1.0 mL/g,焙烧温度450 ℃,焙烧时间90 min
2098.97
3099.23
4099.32
5099.33
), ArticleFig(id=1241422275291968289, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 12, caption=

Effect of liquid-solid ratio in alkaline roasting at atmospheric pressure on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
液固比/(mL·g-1固定碳含量/%备注
0.599.04氢氧化钠溶液浓度40%,焙烧温度450 ℃,焙烧时间90 min
1.099.31
1.599.39
2.099.39
2.599.40
), ArticleFig(id=1241422275405214499, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表12, caption=

常压碱焙烧时液固比对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
液固比/(mL·g-1固定碳含量/%备注
0.599.04氢氧化钠溶液浓度40%,焙烧温度450 ℃,焙烧时间90 min
1.099.31
1.599.39
2.099.39
2.599.40
), ArticleFig(id=1241422275497489191, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 13, caption=

Effect of roasting time in alkaline roasting at atmospheric pressure on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧时间/min固定碳含量/%备注
6099.26氢氧化钠溶液浓度40%,液固比1.5 mL/g,焙烧温度450 ℃
3099.18
9099.34
12099.43
15099.42
18099.43
), ArticleFig(id=1241422275602346792, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表13, caption=

常压碱焙烧时焙烧时间对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧时间/min固定碳含量/%备注
6099.26氢氧化钠溶液浓度40%,液固比1.5 mL/g,焙烧温度450 ℃
3099.18
9099.34
12099.43
15099.42
18099.43
), ArticleFig(id=1241422275719787308, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 14, caption=

Effect of roasting temperature in alkaline roasting at atmospheric pressure on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧温度/℃固定碳含量/%备注
35099.21氢氧化钠溶液浓度40%,液固比1.5 mL/g,焙烧时间120 min
40099.29
45099.39
50099.48
55099.52
60099.51
65099.51
70099.32
), ArticleFig(id=1241422275858199343, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表14, caption=

常压碱焙烧时焙烧温度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧温度/℃固定碳含量/%备注
35099.21氢氧化钠溶液浓度40%,液固比1.5 mL/g,焙烧时间120 min
40099.29
45099.39
50099.48
55099.52
60099.51
65099.51
70099.32
), ArticleFig(id=1241422275992417076, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 15, caption=

Effect of NaOH solution concentration in pressure alkaline roasting on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
氢氧化钠溶液浓度/%固定碳含量/%备注
1098.83压力0.14 MPa(加压温度110 ℃),液固比1.5 mL/g
2099.26
3099.46
4099.58
5099.59
), ArticleFig(id=1241422276076303159, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表15, caption=

加压碱焙烧时氢氧化钠溶液浓度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
氢氧化钠溶液浓度/%固定碳含量/%备注
1098.83压力0.14 MPa(加压温度110 ℃),液固比1.5 mL/g
2099.26
3099.46
4099.58
5099.59
), ArticleFig(id=1241422276176966459, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 16, caption=

Effect of pressure in pressure alkaline roasting on fixed carbon content

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压力/MPa固定碳含量/%备注
0.1099.47氢氧化钠溶液浓度40%,液固比1.5 mL/g
0.1499.56
0.1999.63
0.2799.64
0.3699.64
), ArticleFig(id=1241422276269241147, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表16, caption=

加压碱焙烧时压力对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
压力/MPa固定碳含量/%备注
0.1099.47氢氧化钠溶液浓度40%,液固比1.5 mL/g
0.1499.56
0.1999.63
0.2799.64
0.3699.64
), ArticleFig(id=1241422276382487358, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 17, caption=

Effect of liquid-solid ratio in pressure alkaline roasting on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
液固比/(mL·g-1固定碳含量/%备注
0.599.45氢氧化钠溶液浓度40%,压力0.19 MPa(加压温度120 ℃)
1.099.60
1.599.64
2.099.65
2.599.65
), ArticleFig(id=1241422276470567743, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表17, caption=

加压碱焙烧时液固比对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
液固比/(mL·g-1固定碳含量/%备注
0.599.45氢氧化钠溶液浓度40%,压力0.19 MPa(加压温度120 ℃)
1.099.60
1.599.64
2.099.65
2.599.65
), ArticleFig(id=1241422278035043137, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 18, caption=

Effect of HCl concentration in pressure acid leaching on fixed carbon content

, figureFileSmall=null, figureFileBig=null, tableContent=
盐酸浓度/(mol·L-1固定碳含量/%备注
1.099.83酸浸时间120 min,压力0.16 MPa(酸浸温度118 ℃)
1.599.91
2.099.94
2.599.95
3.099.97
3.599.98
), ArticleFig(id=1241422278177649474, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表18, caption=

加压酸浸时盐酸浓度对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
盐酸浓度/(mol·L-1固定碳含量/%备注
1.099.83酸浸时间120 min,压力0.16 MPa(酸浸温度118 ℃)
1.599.91
2.099.94
2.599.95
3.099.97
3.599.98
), ArticleFig(id=1241422278269924164, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 19, caption=

Effect of pressure in pressure acid leaching on fixed carbon content

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压力/MPa固定碳含量/%备注
0.1099.91酸浸时间120 min,盐酸浓度2.5 mol/L
0.1299.92
0.1499.94
0.1699.95
0.1899.97
0.2099.98
), ArticleFig(id=1241422278391558981, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表19, caption=

加压酸浸时压力对固定碳含量的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
压力/MPa固定碳含量/%备注
0.1099.91酸浸时间120 min,盐酸浓度2.5 mol/L
0.1299.92
0.1499.94
0.1699.95
0.1899.97
0.2099.98
), ArticleFig(id=1241422278563525446, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=EN, label=Table 20, caption=

Effect of acid leaching time in pressure acid leaching on fixed carbon content

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酸浸时间/min固定碳含量/%备注
6099.90盐酸浓度2.5 mol/L,压力0.16 MPa(酸浸温度118 ℃)
9099.96
12099.96
15099.97
18099.98
21099.98
24099.98
), ArticleFig(id=1241422278668383047, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416387671937882, language=CN, label=表20, caption=

加压酸浸时酸浸时间对固定碳含量的影响

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酸浸时间/min固定碳含量/%备注
6099.90盐酸浓度2.5 mol/L,压力0.16 MPa(酸浸温度118 ℃)
9099.96
12099.96
15099.97
18099.98
21099.98
24099.98
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碱酸法提纯球形石墨试验研究
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张文学 1 , 邱杨率 1, 2 , 张凌燕 1, 2
矿冶工程杂志 | 冶金 2025,45(3): 151-157
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矿冶工程杂志 | 冶金 2025, 45(3): 151-157
碱酸法提纯球形石墨试验研究
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张文学1 , 邱杨率1, 2 , 张凌燕1, 2
作者信息
  • 1.武汉理工大学 资源与环境工程学院,湖北 武汉 430070
  • 2.矿物资源与加工湖北省重点实验室,湖北 武汉 430070
  • 张文学(2000—),男,云南楚雄人,硕士研究生,主要研究方向为非金属矿选矿及深加工。E-mail:

通讯作者:

邱杨率(1987—),男,湖北汉川人,博士,副教授,主要研究方向为非金属矿选矿及深加工,矿物材料制备。E-mail:
Purification of Spherical Graphite by Alkali-Acid Method
Wenxue ZHANG1 , Yangshuai QIU1, 2 , Lingyan ZHANG1, 2
Affiliations
  • 1.School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China
  • 2.Hubei Key Laboratory of Mineral Resources Processing and Environment, Wuhan 430070, Hubei, China
出版时间: 2025-06-01 doi: 10.3969/j.issn.0253-6099.2025.03.025
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针对石墨化学提纯过程中提纯纯度不高、碱酸用量大等问题,以萝北球形石墨为研究对象,研究球形石墨中杂质的赋存状态,开展碱酸法提纯试验研究,开发出负-正压混碱加压酸浸的碱酸法提纯工艺。结果表明,负-正压混碱加压酸浸的碱酸法提纯工艺的优化条件为:石墨在真空下静置35 min、真空度-0.15 MPa,加压搅拌时氢氧化钠浓度40%、压力0.19 MPa(加压温度120 ℃)、搅拌时间40 min、氢氧化钠溶液与球形石墨的液固比1.0 mL/g,焙烧过程中焙烧时间120 min、焙烧温度550 ℃,酸浸时HCl浓度2.5 mol/L、压力0.16 MPa(酸浸温度118 ℃)、盐酸溶液与石墨的液固比1.0 mL/g、酸浸时间90 min,该条件下石墨提纯后固定碳含量由95.35%提升至99.96%。

球形石墨  /  碱酸法  /  酸浸  /  碱焙烧  /  石墨提纯

To address the issues of low purity and high consumption of alkali and acid during chemical purification of graphite, Luobei spherical graphite was taken to explore the occurrence state of impurities therein and to perform tests on its purification by alkali-acid method. A novel alkali-acid method was developed, which consists of stirring with alkali under negative-positive pressure and pressure acid leaching. This purification process is conducted in the following steps with the optimized conditions: firstly leave graphite in a vacuum for 35 min with vacuum degree of -0.15 MPa, and then stir for 40 min under pressure of 0.19 MPa at 120 ℃ by adding NaOH at a concentration of 40%, with NaOH solution and spherical graphite in a liquid-to-solid ratio of 1.0 mL/g;after 120 min roasting at 550 ℃, acid leaching with HCl at a concentration of 2.5 mol/L is performed under pressure of 0.16 MPa at 118 ℃ for 90 min, with HCl solution and graphite in a liquid-to-solid ratio of 1.0 mL/g. As a result, the fixed carbon content in the purified graphite is up from 95.35% to 99.96%.

spherical graphite  /  alkali-acid method  /  acid leaching  /  alkali roasting  /  graphite purification
张文学, 邱杨率, 张凌燕. 碱酸法提纯球形石墨试验研究. 矿冶工程杂志, 2025 , 45 (3) : 151 -157 . DOI: 10.3969/j.issn.0253-6099.2025.03.025
Wenxue ZHANG, Yangshuai QIU, Lingyan ZHANG. Purification of Spherical Graphite by Alkali-Acid Method[J]. Mining and Metallurgical Engineering, 2025 , 45 (3) : 151 -157 . DOI: 10.3969/j.issn.0253-6099.2025.03.025
石墨作为一种重要战略矿产资源,因具有化学稳定性好、强度高、导电性好等优点被广泛应用于机械、电子、材料等领域。近年随着新能源行业的快速发展,锂离子电池需求量呈爆发式增长,作为锂离子电池四大组件之一的负极材料产量也急剧增加。相比于人造石墨负极材料,天然石墨负极材料具有成本低、安全性高、来源广泛等优点,其市场占比正在逐步提升[1]。球形石墨提纯是制作高性能天然石墨负极材料的重要一环,现有球形石墨提纯方法为氢氟酸法,主要原理是氢氟酸及其他种类的酸与石墨中杂质反应,生成可溶性物质或者挥发物,再通过洗涤将可溶性杂质从石墨中去除从而提高石墨的纯度[2-4],该方法工艺简单、成本较低,但由于氟对环境危害较大,且含氟废水及废渣处理难度大,其发展受限。碱酸法也是石墨提纯的传统方法,主要包括碱熔和酸浸两个过程:碱熔过程是将石墨和氢氧化钠混合均匀后,在高温下熔融态的氢氧化钠与石墨中杂质反应,生成可溶性化合物,再经洗涤从石墨中去除,碱熔洗碱过程对硅酸盐、硅铝酸盐、石英等杂质矿物的去除效果较好[5-7];酸浸过程将经过碱熔焙烧后的石墨与酸混合搅拌均匀,酸将硅酸盐外的大部分杂质溶解,生成可溶性物质,经过洗涤从石墨中去除。虽然碱酸法工艺较氢氟酸法略复杂,但其废水只需进行中和处理后即可达标排放或回用,具有较好的发展前景。碱酸法目前未推广使用的主要原因在于其提纯产品纯度不够高、碱酸用量大。本文对传统碱酸法工艺进行优化,提出了负-正压混碱加压酸浸的碱酸法提纯新工艺,以求满足新能源领域对高纯石墨的需求,开发更环保、高效的石墨提纯技术。
以黑龙江萝北球形石墨为原料进行提纯试验。原料化学成分分析结果见表1,原料X射线衍射分析、粒度分布检测和扫描电镜观察结果见图13
表1可知,球形石墨固定碳(TGC)含量为95.35%,烧失量(LOI)为96.95%,其他杂质成分为SiO2、Al2O3、Fe2O3以及少量的K2O、CaO等。
图1可知,球形石墨原矿主要矿物组成为石墨、石英、云母。由图2可知,球形石墨原矿粒度较细,D50=15.34 μm。由图3可知,球形石墨球形较完整,整体呈现为球形或类球形,从图3(b)可以看出球形石墨中有明显的杂质(图中方框内),说明部分杂质与球形石墨已解离,游离于球形石墨外部,但部分脉石矿物可能包裹于球形石墨内部。
试验用试剂氢氧化钠、盐酸均为分析纯,购自成都市科隆化学品有限公司。
主要仪器设备包括:高温箱式电阻炉、电子天平、双层不锈钢反应釜、鼓风干燥箱、单槽浮选机、恒温水浴锅、真空压滤机等。
采用常规碱酸法提纯石墨原矿,工艺流程见图4。首先,将石墨与氢氧化钠固体混匀,然后焙烧一段时间,将焙烧后石墨水洗至中性,然后加入盐酸进行酸浸,酸浸完成后水洗至中性即得到提纯产品。
常规碱酸法提纯工艺产品纯度不高的主要原因是氢氧化钠与杂质反应不充分,为了提高氢氧化钠与杂质反应效率,增加氢氧化钠与杂质直接接触概率,对常规碱酸法工艺进行优化:将氢氧化钠固体配制成氢氧化钠溶液,溶液中的离子更容易进入石墨鳞片层间,有利于提高焙烧过程中的反应效率。在此基础上通过升温加压,强化碱液由石墨颗粒外部渗入颗粒内部石墨鳞片间,提高碱液与石墨层间包裹杂质接触概率,使反应更加彻底。同理,通过加压,使盐酸与球形石墨颗粒内部杂质接触更加充分,提高酸浸反应效率。
基于石墨与氢氧化钠固体难以混合均匀的问题,对传统碱酸法进行优化,开发了负-正压混碱加压酸浸的碱酸法提纯工艺,主要工艺流程见图5。首先称取一定质量球形石墨置于反应釜内,抽真空后静置35 min,真空度-0.15 MPa,随后利用反应釜中负压吸入一定量氢氧化钠溶液,随后加压搅拌均匀后,将球形石墨与氢氧化钠混合浆料置于不锈钢坩埚中于马弗炉内进行焙烧,待焙烧完成后,将焙烧后物料水洗至中性,再进行加压酸浸,最后将酸浸后物料用去离子水清洗至中性,烘干后得到提纯产品。
测试方法:采用燃烧法[8](GB/T 3518—2023)测定石墨固定碳含量;采用X射线荧光光谱仪分析原料成分;采用FIB-SEM-EDS对球形石墨进行切割并使用扫描电子显微镜对其切割面进行面扫和点扫,得到材料内部微观形貌及元素成分含量;采用JSM-IT300型扫描电子显微镜观察提纯前后球形石墨整体形貌,对比提纯前后差异及压力对矿物的影响。
球形石墨杂质可能的存在形式主要有两种[9]:一是与石墨完全单体解离,这部分杂质易于去除;二是存在于石墨鳞片层间,这部分杂质难以去除。
取一定量萝北球形石墨进行煮胶制片,将制得的片切成薄片(通常在几十微米到几百微米之间),然后研磨至标准厚度30 μm薄片,对薄片进行抛光制作成光片,在显微镜下进行观察,结果如图6所示。从图6可知,石墨呈球形或椭球形,部分黄铁矿游离分布于球形石墨外部,部分脉石矿物可能被包裹在球形石墨内部无法观察到,需要采用电子显微镜进一步观察。
采用聚焦离子束对球形石墨进行切割,对切面整个区域和特殊的点进行扫描并进行能谱分析,确定球形石墨内部杂质赋存状态,结果见图78表23。由图78可知,球形石墨内部有部分微小颗粒疑似杂质,未发现大颗粒状杂质。由表23可知,整个截面以C元素为主(质量分数为95.40%),另外还含有少量杂质元素。疑似矿物点EDS分析结果显示,该点的脉石矿物可能为石英、黄铁矿、方解石和褐铁矿等。由FIB-SEM-EDS测试结果可知,部分脉石矿物被包裹于球形石墨鳞片层间,较难除去。
取一定量石墨与氢氧化钠混合,进行常规碱焙烧试验,氢氧化钠与石墨质量比、焙烧时间和焙烧温度对石墨固定碳含量的影响如表46所示。由表46可知,随着氢氧化钠与石墨质量比、焙烧时间和焙烧温度提高,提纯产品固定碳含量呈现上升趋势。综合考虑,常规碱焙烧优化试验条件为:氢氧化钠与石墨质量比1.0、焙烧时间120 min、焙烧温度550 ℃,此时提纯后球形石墨固定碳含量达到98.31%。
以常规碱焙烧优化试验条件下得到的石墨为原料进行酸浸试验,探索盐酸浓度、酸浸温度、液固比和酸浸时间对石墨纯度的影响,结果如表710所示。由表710可知,常规酸浸工艺优化试验条件为:盐酸浓度3.0 mol/L、酸浸温度70 ℃、液固比1.0 mL/g、酸浸时间150 min。此时球形石墨固定碳含量由98.31%提高至98.96%。
取一定量石墨原矿与氢氧化钠溶液混合,搅拌40 min,然后进行负-正压混碱加压酸浸新工艺的常压碱焙烧试验,氢氧化钠溶液浓度、液固比(氢氧化钠溶液与石墨的质量比)、焙烧时间和焙烧温度对石墨固定碳含量的影响如表1114所示。由表1114可知,随着氢氧化钠溶液浓度、液固比、焙烧时间和焙烧温度增加,提纯产品固定碳含量呈现上升趋势。综合考虑,适宜的试验条件为:氢氧化钠溶液浓度40%、液固比1.5 mL/g、焙烧时间120 min、焙烧温度550 ℃,该条件下石墨固定碳含量由95.35%提高至99.52%。
将石墨放置在反应釜中抽真空静置一段时间后,将氢氧化钠溶液与石墨混合溶液进行加热,通过升温进行加压,使更多的氢氧化钠溶液进入石墨层间。
石墨在反应釜内真空静置35 min,真空度为-0.15 MPa,将石墨与氢氧化钠溶液混合,搅拌时间40 min,焙烧温度550 ℃,焙烧时间120 min,研究氢氧化钠溶液浓度、压力(加压温度)、液固比对提纯效果的影响,提纯结果见表1517。由表1517可知,加压碱焙烧适宜的试验条件为:氢氧化钠溶液浓度40%、压力0.19 MPa(加压温度120 ℃)、液固比1.0 mL/g,该条件下石墨固定碳含量由95.35%提高至99.60%。
以上述碱焙烧试验得到的石墨为原料,在液固比1.0 mL/g时,改变盐酸浓度、压力(酸浸温度)和酸浸时间来进行加压酸浸试验,结果见表1820。由表1820可知,加压酸浸工艺优化条件为:HCl浓度2.5 mol/L、压力0.16 MPa(酸浸温度118 ℃)、酸浸时间90 min,该条件下球形石墨固定碳含量由99.60%提高到99.96%。
负-正压混碱加压酸浸的碱酸法提纯不仅显著提升了提纯效果,而且减少了酸碱用量。
对负-正压混碱加压酸浸的碱酸法提纯后的球形石墨进行X射线衍射分析,结果见图9。由图9可知,加入氢氧化钠溶液焙烧,水洗前样品有一些杂峰,水洗和酸浸后,这些杂峰消失,杂质已被去除。最终石墨成品的衍射峰没有发生改变,石墨的晶体结构没有被破坏。
图10为不同方法提纯后的球形石墨扫描电镜照片,图11为使用负-正压混碱加压酸浸的碱酸法提纯后的球形石墨X射线能谱图。由图1011可知,常规碱酸法和负-正压混碱加压酸浸的碱酸法提纯后石墨的结构没有被破坏,球形完整,压力对球形石墨的形貌和结构没有影响;从X射线能谱图看到,负-正压混碱加压酸浸的碱酸法提纯后球形石墨中看不到杂质,提纯效果较好。
1)对萝北球形石墨原矿进行杂质赋存状态分析可知,部分脉石矿物被包裹于球形石墨鳞片层间,较难除去。
2)常规碱酸法优化工艺条件为:氢氧化钠与石墨质量比1.0、焙烧时间120 min、焙烧温度550 ℃,HCl浓度3 mol/L、酸浸温度70 ℃、酸浸液固比1.0 mL/g、酸浸时间150 min,该条件下固定碳含量由95.35%提升至98.96%。
3)负-正压混碱加压酸浸的碱酸法优化工艺条件为:石墨在真空下静置35 min、真空度-0.15 MPa,加压搅拌时氢氧化钠浓度40%、压力0.19 MPa(加压温度120 ℃)、搅拌时间40 min、液固比1.0 mL/g,焙烧过程中焙烧时间120 min、焙烧温度550 ℃,酸浸时HCl浓度2.5 mol/L、压力0.16 MPa(酸浸温度118 ℃)、酸浸液固比1.0 mL/g、酸浸时间90 min,该条件下固定碳含量由95.35%提升至99.96%。
4)负-正压混碱加压酸浸的碱酸法与常规碱酸法对比,氢氧化钠和盐酸用量减少,酸浸时间缩短。负-正压混碱加压酸浸的碱酸法不改变石墨晶体结构,石墨产品纯度达到99.95%以上,可应用于新能源领域。
  • 国家重点研发计划(2021YFC2902902)
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2025年第45卷第3期
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doi: 10.3969/j.issn.0253-6099.2025.03.025
  • 接收时间:2024-12-30
  • 首发时间:2026-03-19
  • 出版时间:2025-06-01
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  • 收稿日期:2024-12-30
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国家重点研发计划(2021YFC2902902)
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    1.武汉理工大学 资源与环境工程学院,湖北 武汉 430070
    2.矿物资源与加工湖北省重点实验室,湖北 武汉 430070

通讯作者:

邱杨率(1987—),男,湖北汉川人,博士,副教授,主要研究方向为非金属矿选矿及深加工,矿物材料制备。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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