Article(id=1172619968467317656, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619967393579600, articleNumber=1009-2617(2024)02-0140-07, orderNo=null, doi=10.13355/j.cnki.sfyj.2024.02.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1703433600000, receivedDateStr=2023-12-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1757503986708, onlineDateStr=2025-09-10, pubDate=1713542400000, pubDateStr=2024-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757503986708, onlineIssueDateStr=2025-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757503986708, creator=13701087609, updateTime=1757503986708, updator=13701087609, issue=Issue{id=1172619967393579600, tenantId=1146029695717560320, journalId=1146120122248306696, year='2024', volume='43', issue='2', pageStart='113', pageEnd='213', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1757503986451, creator=13701087609, updateTime=1758592810833, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1177186827904631095, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619967393579600, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1177186827904631096, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619967393579600, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=140, endPage=146, ext={EN=ArticleExt(id=1172619968702198683, articleId=1172619968467317656, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Dissolution Behavior of Valuable Elements from Dephosphorization Slag in Different Kinds of Organic Acids, columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

Dephosphorization slag contains a large amount of valuable components such as CaO, SiO2, FeO, P2O5, etc., and has the potential to be used as soil amendment and fertilizer. To promote utilization of dephosphorization slag in agriculture, it is necessary to understand its dissolution behavior in the organic acid solution. The influence of pH and organic acid type on the dissolution ratios of various valuable elements from dephosphorization slag was investigated. The results show that the main mineral phases in the dephosphorization slag are RO phase, CaFeSiO4 matrix phase, and C2S-C3P solid solution. Ca and Si elements in the slag are mainly distributed in the C2S-C3P solid solution and CaFeSiO4 matrix phase, while the P element is enriched in the C2S-C3P solid solution. Fe element is mainly distributed in the RO phase. As the pH value decreased, the dissolution of slag is significantly promoted, and most of the dephosphorization slag can be dissolved in the citric acid solution. At pH=5, the dissolution ratios of Ca, Si, Mg elements are about 90%, and the P dissolution ratio is 68.84%, achieving the dissolution of valuable elements.

, correspAuthors=null, 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, authorCompany=null, fund=null, authors=null, authorsList=Jialin JIANG, Shangbing LI, Xin WANG, Chuanming DU), CN=ArticleExt(id=1172620285942575161, articleId=1172619968467317656, tenantId=1146029695717560320, journalId=1146120122248306696, language=CN, title=脱磷渣中有价元素在不同有机酸溶液中的浸出行为, columnId=1152626641328501305, journalTitle=湿法冶金, columnName=试验研究, runingTitle=null, highlight=null, articleAbstract=脱磷渣中含有大量CaO、SiO2、FeO、P2O5等有价组元,具有作为土壤改良剂和肥料的潜力。为了推动脱磷渣在农业中的应用,有必要了解其在有机酸溶液中的浸出行为。考察了pH和有机酸类型对脱磷渣中各有价元素浸出率的影响规律。结果表明:脱磷渣中的主要矿物相为富铁相(RO相)、CaFeSiO4基体相和C2S-C3P固溶体;渣中Ca、Si元素主要分布在含磷固溶体和基体相中,P元素富集在C2S-C3P相中,Fe元素主要分布在RO相中;pH降低可明显促进脱磷渣溶解,大部分脱磷渣能在枸橼酸溶液中溶解;在pH=5时,Ca、Si、Mg元素浸出率约为90%,P浸出率达68.84%,实现了有价元素的浸出。, correspAuthors=null, authorNote=null, correspAuthorsNote=
杜传明(1988—),男,博士,副教授,主要研究方向为钢铁冶金。E-mail:
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蒋佳霖(1998—),女,满族,硕士研究生,主要研究方向为钢渣资源化利用。

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蒋佳霖(1998—),女,满族,硕士研究生,主要研究方向为钢渣资源化利用。

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蒋佳霖(1998—),女,满族,硕士研究生,主要研究方向为钢渣资源化利用。

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a—甲酸;b—乙酸;c—枸橼酸;d—草酸。

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a—枸橼酸;b—草酸。

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CaO SiO2 FeO MnO P2O5 MgO Na2O
33.45 22.31 27.21 7.97 3.03 2.03 4.00
), ArticleFig(id=1177334306092494952, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172619968467317656, language=CN, label=表1, caption=

脱磷渣的化学组成 %

, figureFileSmall=null, figureFileBig=null, tableContent=
CaO SiO2 FeO MnO P2O5 MgO Na2O
33.45 22.31 27.21 7.97 3.03 2.03 4.00
), ArticleFig(id=1177334306151215209, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172619968467317656, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
矿物相 CaO SiO2 FeO P2O5 MgO Na2O
点1 0.50 0.17 95.43 0.03 3.61 0.26
点2 32.68 33.68 27.82 1.34 3.99 0.49
点3 47.95 22.03 6.42 16.72 0.54 6.34
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脱磷渣中各物相的化学成分 %

, figureFileSmall=null, figureFileBig=null, tableContent=
矿物相 CaO SiO2 FeO P2O5 MgO Na2O
点1 0.50 0.17 95.43 0.03 3.61 0.26
点2 32.68 33.68 27.82 1.34 3.99 0.49
点3 47.95 22.03 6.42 16.72 0.54 6.34
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残渣类型 矿物相 Ca Si Fe P Mn C 矿物相
枸橼酸浸出残渣 点1 0.97 0.72 87.79 0.00 0.11 0.00 RO相
点2 31.14 10.69 28.47 0.37 0.43 0.00 CaFeSiO4基体相
草酸浸出残渣 点1 0.80 0.72 55.72 0.00 3.79 3.49 RO相
点2 19.43 13.59 17.59 0.89 2.91 1.99 CaFeSiO4基体相
点3 18.98 0.00 1.20 0.00 0.00 21.01 CaC2O4
), ArticleFig(id=1177334306415456364, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172619968467317656, language=CN, label=表3, caption=

脱磷渣浸出后中表面矿物相的化学成分 %

, figureFileSmall=null, figureFileBig=null, tableContent=
残渣类型 矿物相 Ca Si Fe P Mn C 矿物相
枸橼酸浸出残渣 点1 0.97 0.72 87.79 0.00 0.11 0.00 RO相
点2 31.14 10.69 28.47 0.37 0.43 0.00 CaFeSiO4基体相
草酸浸出残渣 点1 0.80 0.72 55.72 0.00 3.79 3.49 RO相
点2 19.43 13.59 17.59 0.89 2.91 1.99 CaFeSiO4基体相
点3 18.98 0.00 1.20 0.00 0.00 21.01 CaC2O4
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脱磷渣中有价元素在不同有机酸溶液中的浸出行为
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蒋佳霖 1 , 李尚兵 2 , 王鑫 1 , 杜传明 1
湿法冶金 | 试验研究 2024,43(2): 140-146
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湿法冶金 | 试验研究 2024, 43(2): 140-146
脱磷渣中有价元素在不同有机酸溶液中的浸出行为
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蒋佳霖1, 李尚兵2, 王鑫1, 杜传明1
作者信息
  • 1 东北大学 冶金学院, 辽宁 沈阳 110819
  • 2 江苏永钢集团有限公司, 江苏 张家港 215600
  • 蒋佳霖(1998—),女,满族,硕士研究生,主要研究方向为钢渣资源化利用。

通讯作者:

杜传明(1988—),男,博士,副教授,主要研究方向为钢铁冶金。E-mail:
Dissolution Behavior of Valuable Elements from Dephosphorization Slag in Different Kinds of Organic Acids
Jialin JIANG1, Shangbing LI2, Xin WANG1, Chuanming DU1
Affiliations
  • 1 School of Metallurgy, Northeastern University, Shenyang 110819, China
  • 2 Jiangsu yonggang Group Co., Ltd., Z hangjiagang 215600, China
出版时间: 2024-04-20 doi: 10.13355/j.cnki.sfyj.2024.02.005
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脱磷渣中含有大量CaO、SiO2、FeO、P2O5等有价组元,具有作为土壤改良剂和肥料的潜力。为了推动脱磷渣在农业中的应用,有必要了解其在有机酸溶液中的浸出行为。考察了pH和有机酸类型对脱磷渣中各有价元素浸出率的影响规律。结果表明:脱磷渣中的主要矿物相为富铁相(RO相)、CaFeSiO4基体相和C2S-C3P固溶体;渣中Ca、Si元素主要分布在含磷固溶体和基体相中,P元素富集在C2S-C3P相中,Fe元素主要分布在RO相中;pH降低可明显促进脱磷渣溶解,大部分脱磷渣能在枸橼酸溶液中溶解;在pH=5时,Ca、Si、Mg元素浸出率约为90%,P浸出率达68.84%,实现了有价元素的浸出。
脱磷渣  /  土壤改良剂  /  有价元素  /  浸出  /  有机酸

Dephosphorization slag contains a large amount of valuable components such as CaO, SiO2, FeO, P2O5, etc., and has the potential to be used as soil amendment and fertilizer. To promote utilization of dephosphorization slag in agriculture, it is necessary to understand its dissolution behavior in the organic acid solution. The influence of pH and organic acid type on the dissolution ratios of various valuable elements from dephosphorization slag was investigated. The results show that the main mineral phases in the dephosphorization slag are RO phase, CaFeSiO4 matrix phase, and C2S-C3P solid solution. Ca and Si elements in the slag are mainly distributed in the C2S-C3P solid solution and CaFeSiO4 matrix phase, while the P element is enriched in the C2S-C3P solid solution. Fe element is mainly distributed in the RO phase. As the pH value decreased, the dissolution of slag is significantly promoted, and most of the dephosphorization slag can be dissolved in the citric acid solution. At pH=5, the dissolution ratios of Ca, Si, Mg elements are about 90%, and the P dissolution ratio is 68.84%, achieving the dissolution of valuable elements.

dephosphorization slag  /  soil amendment  /  valuable elements  /  leaching  /  organic acid
蒋佳霖, 李尚兵, 王鑫, 杜传明. 脱磷渣中有价元素在不同有机酸溶液中的浸出行为. 湿法冶金, 2024 , 43 (2) : 140 -146 . DOI: 10.13355/j.cnki.sfyj.2024.02.005
Jialin JIANG, Shangbing LI, Xin WANG, Chuanming DU. Dissolution Behavior of Valuable Elements from Dephosphorization Slag in Different Kinds of Organic Acids[J]. Hydrometallurgy of China, 2024 , 43 (2) : 140 -146 . DOI: 10.13355/j.cnki.sfyj.2024.02.005
渣是钢铁冶炼过程中产生的主要副产物之一,含有大量CaO、SiO2、FeO、MgO、P2O5等有价组元。其中CaO可改善土壤酸性,硅元素会提高磷酸盐在土壤中的生物有效性[1],磷元素是作物生长所必需的营养元素之一[2],铁元素可促进植物叶绿素合成,增加作物产量[3]。此外,钢渣能够吸附土壤中的Ni、Cr及Pb等重金属,对重金属污染土壤起到一定的修复作用[4]。因此,钢渣作为土壤改良剂和农业肥料具有一定应用潜力,日益受到广泛关注。
近年来,低品位铁矿石用量不断加大,为了满足洁净钢生产要求[5],转炉脱磷工艺正逐步被钢铁企业采用,采用该工艺时,会产生脱磷渣。相比于普通转炉钢渣,脱磷渣碱度较低,一般为1.6左右[6],但P2O5含量更高,若脱磷渣能作为土壤改良剂再利用,不仅能解决冶炼渣堆积引发的一系列环境问题,还能实现脱磷渣的高效资源化利用。
为了推动钢渣在农业中的应用,须了解钢渣中有价元素的浸出行为。近年来,酸浸法被广泛应用于钢渣中磷等元素的回收。国内外研究学者主要研究了钢渣在无机酸溶液中的浸出行为[7],发现有价元素的溶解不充分,在弱酸性条件下磷元素浸出率仅为10%左右,且这些研究仅考虑到单一元素磷的浸出,而未考虑其他有价元素的浸出。有机酸对于植物生长和土壤肥力有着重要的影响,除了植物根部分泌的有机酸之外,土壤中的动植物残体及微生物也能够产生大量的有机酸。研究人员[8-9]对土壤进行了色谱分析,发现每百克土壤中含甲酸0.51~0.87 mg和乙酸0.74~1.01 mg,且通过质谱分析测定出大麦和小麦根部分泌有一定量的草酸等有机酸。此外,植物吸收有价元素主要依靠各矿物质在有机酸环境中的溶解,土壤中草酸、枸橼酸、甲酸和乙酸的含量远大于其他种类的有机酸[10]。国内有学者研究了高碱度转炉渣中磷元素在多种有机酸中的浸出行为,发现磷在部分有机酸溶液中能有效浸出,浸出率先升高后降低[11]
为验证脱磷渣用作土壤改良剂的可行性,须研究脱磷渣中多种有价元素在有机酸环境中的浸出行为。综上所述,针对低碱度的脱磷渣,采用不同种类的有机酸来模拟植物根系的弱酸性环境进行浸出试验,考察pH和有机酸类型对渣中各有价元素浸出率的影响规律,并分析了溶解机制,旨在为脱磷渣在农业中的应用提供理论依据。
根据实际渣成分,试验以CaO、SiO2、FeO、MgO和MnO等分析纯试剂为原料来合成脱磷渣,并加入少量Na2O以促进钢渣中磷的浸出[12]。P2O5和Na2O分别以Ca3(PO4)2和Na2SiO3形式加入。首先将充分混均后的试剂加入到纯铁坩埚中,在氩气气氛下加热至1 723 K并保温30 min,形成液态渣;然后将熔渣以5 K/min的冷却速率冷却至1 573 K,以促进各矿物相的结晶析出;最后,冷却至1 273 K时从炉中取出钢渣,在空气中冷却。脱磷渣合成时的加热制度如图1所示。利用电感耦合等离子体发射光谱仪(ICP-OES)分析钢渣的化学成分,结果见表1,利用扫描电子显微镜(SEM-EDS)和X射线衍射仪(XRD)分析钢渣的矿物相形貌和组成。
将渣样破碎研磨至粒径小于53 μm。为了模拟土壤环境,将1 g渣样放入300 mL去离子水中进行机械搅拌,同时通过蠕动泵将有机酸加入溶液中,以控制其pH恒定,试验装置如图2所示。试验用有机酸分别为枸橼酸、甲酸、草酸、乙酸。浸出条件:温度298 K,固液质量体积比1/300,浸出时间90 min。反应90 min后,抽取5 mL溶液并进行过滤,利用ICP-OES分析各元素浓度。利用铁氰化钾滴定法测定溶液中的Fe2+离子浓度。将剩余溶液过滤,收集残渣干燥后称量,通过XRD和SEM-EDS分析残渣的矿物相组成及形貌。根据溶液中各元素浓度和溶液体积,利用式(1)计算渣中各元素浸出率xM:
${x}_{M}=\frac{{\rho }_{M}V}{{m}_{M}}$
式中:ρM—元素M质量浓度,mg/L;V—溶液体积,L;mM—1 g钢渣中元素M质量,mg。
图3为脱磷渣中各矿物相的微观形貌,各矿物相的平均化学成分见表2。可以看出:脱磷渣主要由3种矿物相组成,白色椭圆状矿物相(点1)中FeO质量分数为95.43%,还有少量MgO,为RO相,几乎不含P2O5;浅灰色矿物相(点2)中CaO、SiO2、FeO质量分数分别为32.68%、33.68%和27.82%,为CaFeSiO4基体相,该相中含有少量MgO和P2O5;深灰色矿物相(点3)主要由CaO、SiO2、P2O5组成,其中P2O5质量分数为16.72%,远高于其他矿物相中的含量,FeO含量极低,该相为C2S-C3P相,即P2O5的富集相。Na元素主要分布在C2S-C3P相中,表明Na2O与P2O5易结合,这有利于钢渣中P的浸出。渣中一部分FeO分布在RO相中,另外一部分存在于CaFeSiO4基体相中。图4为脱磷渣的XRD图谱,可以看出:该渣主要由RO相、含磷固溶体和CaFeSiO4相组成,与上述的扫描电镜结果基本一致。
钢渣在酸溶液中溶解时,其主要元素的浸出率与酸耗量呈正相关性[13],因此,可通过浸出时酸耗量变化来评价元素浸出速率。图5为不同有机酸溶液(pH=5)浸出脱磷渣时酸耗量随时间的变化关系,可以看出:在反应前20 min内,各有机酸耗量急剧上升,说明钢渣浸出速率较快;而反应40 min后,酸耗量变化较小,表明钢渣溶解速率较慢,溶解反应趋于平衡。相比于其他酸溶液,枸橼酸溶液的耗量最大。
图6为脱磷渣中主要元素在4种有机酸溶液中的浸出率。
图6看出:在不同有机酸溶液中,Ca、Si、Mg、Mn浸出率较高,而P和Fe元素浸出率相对较低。pH=6时,脱磷渣在枸橼酸溶液中的溶解效果最好,各元素浸出率远高于在其他有机酸溶液中的浸出率,其中Si浸出率最高,达66.02%,P、Fe浸出率分别为23.60%、15.10%。pH降低显著促进脱磷渣的溶解,使各元素浸出率提高,在pH=5.5的枸橼酸溶液中,Fe、P浸出率分别升至27.43%、44.84%。pH=5.5时,在甲酸和草酸溶液中,P、Fe浸出率仍较低,均小于10%,而在乙酸溶液中P、Fe浸出率分别为19.05%、10.45%。pH降至5时,大部分脱磷渣能在枸橼酸溶液中溶解,Ca、Si、Mg浸出率均超过90%,P浸出率达68.84%。在乙酸溶液中,Si元素几乎都溶解,Ca、Mg、Mn浸出率均超过70%,P浸出率达28.73%。而在甲酸和草酸溶液中,各元素浸出率相对较低,其中P、Fe浸出率均低于20%。在不同pH条件下,脱磷渣中主要元素在枸橼酸溶液中的浸出效果最好,在乙酸和甲酸中的浸出效果次之,在草酸溶液中的浸出效果最差。其结果与图5中各有机酸耗量相对应,元素浸出率越高,反应过程中酸耗量也越多。
脱磷渣中含磷的C2S-C3P相在稀酸溶液中易溶解,CaFeSiO4基体相溶解相对较差,而含铁的RO相难以溶解[14],因此在各有机酸溶液中脱磷渣中的Ca、Si等浸出率远高于Fe浸出率。浸出过程中主要发生反应(2)和(3)。此外,对浸出液使用铁氰化钾滴定分析Fe2+离子含量,结果表明,溶液中铁大部分为Fe2+,Fe3+含量极低,故后续主要考虑Fe2+与溶液中其他离子的反应。脱磷渣中大部分C2S-C3P相被溶解,但P浸出率低于Ca和Si浸出率。主要原因是在弱酸性条件下,溶液中磷酸根离子极易与Ca2+、Fe2+等金属离子反应,生成磷酸盐沉淀,从而降低P浸出率[15]。矿物相的溶解须消耗有机酸中解离出的H+[16],随pH降低,溶液中H+浓度增加,可促进反应(2)、(3)的正向进行,提高各元素浸出率。
2CaO·SiO2-3CaO·P2O5+8H+═══════5Ca2++H2SiO3+2H2$\mathrm{PO}_{4}^{-}$+H2O;
CaO-SiO2-FeO+4H+═══════Ca2++H2SiO3+Fe2++H2O。
枸橼酸是三元酸,也是一种优良的螯合剂,枸橼酸根(C6H5$\mathrm{O}_{7}^{3-}$)离子能与Ca2+、Fe2+发生螯合反应,如反应(4)~(6)所示,生成CaC6H5$\mathrm{O}_{7}^{-}$、FeC6H5${O}_{7}^{-}$等金属配合物,这不仅更易破坏矿物相的晶体结构,提高各元素浸出率,也能减少溶液中自由Ca2+、Fe2+含量,从而抑制磷酸盐沉淀的形成。因此,脱磷渣中主要元素在枸橼酸溶液中的浸出效果最好,在pH=5时大部分元素都能被溶解。稀枸橼酸溶液也常用来测试磷肥的枸溶性[17]
甲酸和乙酸都属于一元羧酸,其中乙酸为二聚体结构,含有1个甲基和1个羧基。当乙酸溶于水中,二聚体间的氢键会很快断裂与钢渣发生反应,故在乙酸溶液中钢渣主要元素的浸出效果略优于甲酸溶液[18]。在草酸溶液中,从脱磷渣中溶解的Ca2+会与草酸根离子($\mathrm{C}_{2} \mathrm{O}_{4}^{2-}$)发生反应(6),生成CaC2O4草酸钙沉淀,导致Ca浸出率几乎为0。浸出过程中$\mathrm{C}_{2} \mathrm{O}_{4}^{2-}$离子与Ca2+和Fe2+生成的草酸盐沉淀会附着在脱磷渣颗粒表面,从而阻碍脱磷渣中矿物相与溶液中H+接触,抑制主要元素的浸出[19],导致浸出率较低。
Fe2++C6H5$\mathrm{O}_{7}^{3-}$═══════FeC6H5$\mathrm{O}_{7}^{-}$;
C6H5$\mathrm{O}_{7}^{3-}$+Ca2+═══════CaC6H5$\mathrm{O}_{7}^{-}$;
H2C2O4+Ca2+═══════CaC2O4↓+2H+
在pH=5.5时,脱磷渣在枸橼酸和草酸溶液中浸出后残渣的微观形貌及主要元素的分布如图7所示。残渣中主要矿物相中的化学成分见表3。可以看出:在枸橼酸溶液中浸出后残渣主要由2种矿物相组成,白色矿物相(点1)主要含有FeOx,为RO相;灰色矿物相(点2和3)中P2O5含量较低,为CaFeSiO4基体相;未明显发现富含磷的矿物相,说明大部分C2S-C3P固溶体被溶解分离;但在元素面扫描分析中,发现了P元素的富集区域,其中Ca、Si元素含量也较高,为未溶解的C2S-C3P固溶体。在草酸溶液中浸出后,残渣也主要由RO相和CaFeSiO4基体相,表面未发现C2S-C3P固溶体;此外,还存在很多棒状的矿物相(点3),主要由Ca和C元素组成,为沉淀析出的草酸钙沉淀,这与图6(d)中Ca元素浸出率结果相对应。浸出的Ca以沉淀形式留在残渣中,导致浸出液中几乎不含Ca元素。
图8为脱磷渣及在pH=5.5的不同有机酸溶液中浸出所得残渣的XRD图谱。脱磷渣主要由C2S-C3P固溶体、CaFeSiO4基体相、RO相组成,与扫描电镜分析结果一致。浸出后,C2S-C3P相和CaFeSiO4基体相中的特征峰强度减弱,而RO相峰值强度变化较小,这说明含Ca和Si的矿物相较易溶解。结合图6看出:Fe浸出率在相同条件下低于其他有价元素,特别是在枸橼酸溶液中溶解后,C2S-C3P相和CaFeSiO4相的特征峰强度明显减弱,说明浸出效果较好。在草酸和甲酸溶液中溶解后,残渣中各矿物相的特征峰强度与脱磷渣的类似,说明矿物相的溶解效果较差。此外,在草酸溶液中溶解后的残渣中还出现少量草酸钙相的特征峰,这与上述扫描电镜结果一致。
根据脱磷渣化学成分和矿物相成分,通过式(7)计算渣中各矿物相的质量分数。
∑{w(MO)i×Xi}=w(MO)s;
Xi=1。
式中:w(MO)i—钢渣i相中氧化物MO质量分数,%;Xi—i相的质量分数,%;w(MO)s—脱磷渣中氧化物MO总质量分数,%。
脱磷渣中各矿物相质量分数及在pH=5的不同有机酸溶液中浸出所得残渣质量分数如图9所示。可以看出:钢渣中C2S-C3P固溶体的质量分数最高,为43.71%,其次是CaFeSiO4基体相,RO相质量分数较低,仅为16.83%。大部分脱磷渣在枸橼酸溶液中被溶解,剩余残渣质量分数为33.07%。在乙酸溶液中,约52.19%的脱硫渣可被溶解;而在甲酸溶液中,仅有38.48%的脱磷渣被溶解。由于在草酸溶液中会生成草酸钙沉淀,导致残渣质量略大于加入的脱磷渣量。
在弱酸性条件下,脱磷渣中主要元素均能有效浸出。在乙酸和甲酸溶液中Ca、Si、Mg元素的浸出率在60%左右,但浸出过程中有磷酸盐沉淀产生造成P浸出率较低。在草酸溶液中产生的草酸钙沉淀抑制了其他有价元素的浸出,浸出效果不理想。脱磷渣在枸橼酸溶液中有价元素的浸出效果最好。玉米、大豆等作物根系会分泌大量枸橼酸,因此将脱磷钢渣施加到种植这些作物的土壤中,渣中大部分有价元素能有效浸出,发挥较好的肥料效果。
为推进脱磷渣作为土壤改良剂在农业中的应用,考察了pH和有机酸类型对脱磷渣中有价元素浸出行为的影响,得出以下结论:
1)脱磷渣中主要矿物相为RO相、CaFeSiO4基体相和C2S-C3P固溶体。渣中Ca、Si元素主要分布在含磷固溶体和基体相中,P元素富集在C2S-C3P相中。Fe元素主要分布在RO相中,少量存在于基体相中。在各有机酸溶液中浸出后,残渣主要由RO相和CaFeSiO4基体相组成,说明大部分含磷固溶体被溶解。
2)pH降低显著促进脱磷渣的溶解。pH=5时在枸橼酸溶液中Ca和Si浸出率分别为89.61%和99.57%,P浸出率达68.84%,实现了脱磷渣中多种有价元素的浸出。在乙酸和甲酸溶液中Ca、Si、Mg元素浸出率在60%左右,但P浸出率较低。在草酸溶液中产生的草酸钙沉淀抑制了其他有价元素的浸出。
3)pH=5.5时在枸橼酸溶液中溶解的脱磷渣质量分数为66.7%;在甲酸和乙酸中,溶解的渣质量分数仅为38.48%和52.19%。因此,将脱磷钢渣施加到种植玉米、大豆等作物中的土壤中,大部分有价元素能被溶解,发挥较好的肥料效果。
  • 国家自然科学基金资助项目(52104326)
  • 中国博士后科学基金资助项目(2022M721415)
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doi: 10.13355/j.cnki.sfyj.2024.02.005
  • 接收时间:2023-12-25
  • 首发时间:2025-09-10
  • 出版时间:2024-04-20
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  • 收稿日期:2023-12-25
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国家自然科学基金资助项目(52104326)
中国博士后科学基金资助项目(2022M721415)
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    1 东北大学 冶金学院, 辽宁 沈阳 110819
    2 江苏永钢集团有限公司, 江苏 张家港 215600

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杜传明(1988—),男,博士,副教授,主要研究方向为钢铁冶金。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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