Article(id=1148110004873326623, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1148109987349520431, articleNumber=1009-2617(2025)01-0091-09, orderNo=null, doi=10.13355/j.cnki.sfyj.2025.01.013, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1722355200000, receivedDateStr=2024-07-31, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1751660356014, onlineDateStr=2025-07-05, pubDate=1740672000000, pubDateStr=2025-02-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1751660356014, onlineIssueDateStr=2025-07-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1751660356014, creator=13701087609, updateTime=1751660356014, updator=13701087609, issue=Issue{id=1148109987349520431, tenantId=1146029695717560320, journalId=1146120122248306696, year='2025', volume='44', issue='1', pageStart='1', pageEnd='131', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1751660351836, creator=13701087609, updateTime=1758246034872, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1175732344108499276, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1148109987349520431, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1175732344108499277, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1148109987349520431, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=91, endPage=99, ext={EN=ArticleExt(id=1148110005221453887, articleId=1148110004873326623, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Preparation of γ-AlOOH Adsorbent from Aluminum Extracted from Red Mud and Its Adsorption Properties for Congo Red, columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

A hydrangea-like γ-AlOOH adsorbent with a layered structure was prepared by hydrothermal method using sodium aluminate solution obtained from acid leaching of red mud as raw material and used for the adsorption of Congo red. The effects of initial pH and initial mass concentration of Congo red on the adsorption were investigated, and the adsorption mechanism of γ-AlOOH on Congo red was discussed. The results show that the saturated adsorption amount of Congo red can reach 1 748.15 mg/g under suitable conditions. The adsorption process is more appropriately described by the quasi-second-order kinetic model and the Langmuir isothermal adsorption model, and the adsorption behaviours are mainly dominated by monolayer adsorption. The adsorption process is spontaneous, heat-absorbing and chaotic with an increasing degree of confusion. The process can provide an effective solution to solve the problem of Congo red pollution and red mud accumulation in the water body, which is in line with the green development concept of treating waste with waste and turning waste into treasure, and has certain value of popularisation and application.

, correspAuthors=Yibing LI, 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=Kecheng SHANG, Zhonglin LI, Ting ZOU, Wenquan LI, Weiguang ZHANG, Yibing LI), CN=ArticleExt(id=1148110014264374082, articleId=1148110004873326623, tenantId=1146029695717560320, journalId=1146120122248306696, language=CN, title=赤泥提铝制备γ-AlOOH吸附剂及其对刚果红的吸附性能研究, columnId=1152626641328501305, journalTitle=湿法冶金, columnName=试验研究, runingTitle=null, highlight=null, articleAbstract=研究了以赤泥酸浸所得铝酸钠溶液为原料,通过水热法制备一种具有层状结构的类绣球花状γ-AlOOH吸附剂并用于吸附刚果红。考察了溶液初始pH、刚果红初始质量浓度对吸附的影响,探究了γ-AlOOH对刚果红的吸附机制。结果表明:适宜条件下,刚果红饱和吸附量达1 748.15 mg/g;用准二阶动力学模型和Langmuir等温吸附模型描述吸附过程更合适,吸附行为主要以单层吸附为主;吸附过程是自发、吸热且混乱度增大的。该工艺可为解决水体刚果红污染和赤泥堆积提供一种有效的解决方案,符合“以废治废、变废为宝”绿色发展理念,具有一定推广应用价值。, correspAuthors=李义兵, authorNote=null, correspAuthorsNote=
李义兵(1973—),男,博士,教授级高级工程师,主要研究方向为有色金属冶炼。E-mail:
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尚柯成(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

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尚柯成(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

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尚柯成(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

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Journal of Colloid and Interface Science, 2015,451:153-160., articleTitle=Simultaneous removal of cationic and anionic dyes by the mixed sorbent of magnetic and non-magnetic modified sugarcane bagasse, refAbstract=null), Reference(id=1175092754465047329, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, doi=null, pmid=null, pmcid=null, year=2017, volume=null, issue=null, pageStart=622, pageEnd=634, url=null, language=null, rfNumber=[23], rfOrder=24, authorNames=LIN J L, SUN P P, ZHAI P Y, journalName=Chemical Engineering Journal, refType=null, unstructuredReference=LIN J L, SUN P P, ZHAI P Y, et al. Novel application of red mud:facile hydrothermal-thermal conversion synthesis of hierarchical porous AlOOH and Al2O3 microspheres as adsorbents for dye removal[J]. 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Main chemical composition of red mud %

, figureFileSmall=null, figureFileBig=null, tableContent=
CaO SiO2 NaO Fe2O3 Al2O3 MgO K2O TiO2
2.62 3.49 3.22 68.18 17.94 0.76 0.64 3.15
), ArticleFig(id=1175092750627259125, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=CN, label=表1, caption=

赤泥的主要化学组成

, figureFileSmall=null, figureFileBig=null, tableContent=
CaO SiO2 NaO Fe2O3 Al2O3 MgO K2O TiO2
2.62 3.49 3.22 68.18 17.94 0.76 0.64 3.15
), ArticleFig(id=1175092750685979382, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=EN, label=Table 2, caption=

Mass concentration of elements in sodium aluminate solution mg/L

, figureFileSmall=null, figureFileBig=null, tableContent=
Ca Si Na Fe Al
0.758 6 0.429 3 24.03 0.034 5.12
), ArticleFig(id=1175092750761476855, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=CN, label=表2, caption=

铝酸钠溶液中元素质量浓度

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Ca Si Na Fe Al
0.758 6 0.429 3 24.03 0.034 5.12
), ArticleFig(id=1175092750883111672, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=EN, label=Table 3, caption=

Specific surface area,pore volume and pore size of γ-ALOOH adsorbent

, figureFileSmall=null, figureFileBig=null, tableContent=
比表面积/(m2·g-1) 孔隙体积/(cm3·g-1) 孔径/nm
543.07 0.58 4.24
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γ-AlOOH吸附剂的比表面积、孔隙体积及孔径

, figureFileSmall=null, figureFileBig=null, tableContent=
比表面积/(m2·g-1) 孔隙体积/(cm3·g-1) 孔径/nm
543.07 0.58 4.24
), ArticleFig(id=1175092751092826874, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=EN, label=Table 4, caption=

Kinetic fitting parameters of adsorption of Congo red by γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
qe,试验/(mg·g-1) 准一阶动力学模型 准二阶动力学模型
qe,理论/(mg·g-1) k1/min-1 R2 qe,理论/(mg·g-1) k2/(g·mg-1·min-1) R2
1 561.74 895.67 -0.007 2 0.520 2 1 617.59 0.000 2 0.999 4
), ArticleFig(id=1175092751197684475, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=CN, label=表4, caption=

γ-AlOOH吸附刚果红的动力学拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
qe,试验/(mg·g-1) 准一阶动力学模型 准二阶动力学模型
qe,理论/(mg·g-1) k1/min-1 R2 qe,理论/(mg·g-1) k2/(g·mg-1·min-1) R2
1 561.74 895.67 -0.007 2 0.520 2 1 617.59 0.000 2 0.999 4
), ArticleFig(id=1175092751277376252, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=EN, label=Table 5, caption=

Internal diffusion model fitting parameters of adsorption of Congo red by γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
第Ⅰ阶段 第Ⅱ阶段 第Ⅲ阶段
k1/
(mg·g-1·h-0.5)
C1/
(μg·g-1)
R2 k2/
(mg·g-1·h-0.5)
C2/
(μg·g-1)
R2 k3/
(mg·g-1·h-0.5)
C3/
(μg·g-1)
R2
370.958 5 -6.179 4 0.999 9 88.658 0 913.531 8 0.975 6 0.367 4 1 568.837 9 0.996 3
), ArticleFig(id=1175092751419982589, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=CN, label=表5, caption=

γ-AlOOH吸附刚果红的内扩散模型拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
第Ⅰ阶段 第Ⅱ阶段 第Ⅲ阶段
k1/
(mg·g-1·h-0.5)
C1/
(μg·g-1)
R2 k2/
(mg·g-1·h-0.5)
C2/
(μg·g-1)
R2 k3/
(mg·g-1·h-0.5)
C3/
(μg·g-1)
R2
370.958 5 -6.179 4 0.999 9 88.658 0 913.531 8 0.975 6 0.367 4 1 568.837 9 0.996 3
), ArticleFig(id=1175092751491285758, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=EN, label=Table 6, caption=

Langmuir and Freundlich isothermal adsorption fitting parameters of adsorption of Congo red by γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
Langmuir等温吸附模型 Freundlich等温吸附模型
qm/(mg·g-1) kL/(L·mg-1) R2 kF/(mg1-1/n·L1/n·g-1) n R2
1 706.22 0.657 0 0.999 9 904.50 7.116 9 0.761 7
), ArticleFig(id=1175092751566783231, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=CN, label=表6, caption=

γ-AlOOH吸附刚果红的Langmuir和Freundlich等温吸附拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
Langmuir等温吸附模型 Freundlich等温吸附模型
qm/(mg·g-1) kL/(L·mg-1) R2 kF/(mg1-1/n·L1/n·g-1) n R2
1 706.22 0.657 0 0.999 9 904.50 7.116 9 0.761 7
), ArticleFig(id=1175092751742944000, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=EN, label=Table 7, caption=

Thermodynamic parameters of adsorption of Congo red by γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
T/K Δg/
(kJ·mol-1)
ΔH/
(J·mol-1)
ΔS/
(J·mol-1·K-1)
298 -5.592 100.8 19.1
308 -5.782
318 -5.973
), ArticleFig(id=1175092751851995905, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1148110004873326623, language=CN, label=表7, caption=

γ-AlOOH吸附刚果红的热力学参数

, figureFileSmall=null, figureFileBig=null, tableContent=
T/K Δg/
(kJ·mol-1)
ΔH/
(J·mol-1)
ΔS/
(J·mol-1·K-1)
298 -5.592 100.8 19.1
308 -5.782
318 -5.973
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赤泥提铝制备γ-AlOOH吸附剂及其对刚果红的吸附性能研究
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尚柯成 1, 2 , 李中林 1, 2 , 邹婷 1, 2 , 李文权 1, 2 , 张伟光 1, 2 , 李义兵 1, 2
湿法冶金 | 试验研究 2025,44(1): 91-99
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湿法冶金 | 试验研究 2025, 44(1): 91-99
赤泥提铝制备γ-AlOOH吸附剂及其对刚果红的吸附性能研究
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尚柯成1, 2, 李中林1, 2, 邹婷1, 2, 李文权1, 2, 张伟光1, 2, 李义兵1, 2
作者信息
  • 1 桂林理工大学 材料科学与工程学院, 广西 桂林 541004
  • 2 桂林理工大学 有色金属与材料加工新技术教育部重点实验室, 广西 桂林 541004
  • 尚柯成(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

通讯作者:

李义兵(1973—),男,博士,教授级高级工程师,主要研究方向为有色金属冶炼。E-mail:
Preparation of γ-AlOOH Adsorbent from Aluminum Extracted from Red Mud and Its Adsorption Properties for Congo Red
Kecheng SHANG1, 2, Zhonglin LI1, 2, Ting ZOU1, 2, Wenquan LI1, 2, Weiguang ZHANG1, 2, Yibing LI1, 2
Affiliations
  • 1 Department of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China
  • 2 Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, Ministry of Education,Guilin University of Technology, Guilin 541004, China
出版时间: 2025-02-28 doi: 10.13355/j.cnki.sfyj.2025.01.013
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研究了以赤泥酸浸所得铝酸钠溶液为原料,通过水热法制备一种具有层状结构的类绣球花状γ-AlOOH吸附剂并用于吸附刚果红。考察了溶液初始pH、刚果红初始质量浓度对吸附的影响,探究了γ-AlOOH对刚果红的吸附机制。结果表明:适宜条件下,刚果红饱和吸附量达1 748.15 mg/g;用准二阶动力学模型和Langmuir等温吸附模型描述吸附过程更合适,吸附行为主要以单层吸附为主;吸附过程是自发、吸热且混乱度增大的。该工艺可为解决水体刚果红污染和赤泥堆积提供一种有效的解决方案,符合“以废治废、变废为宝”绿色发展理念,具有一定推广应用价值。
赤泥  /  铝  /  γ-AlOOH  /  吸附剂  /  制备  /  刚果红  /  吸附

A hydrangea-like γ-AlOOH adsorbent with a layered structure was prepared by hydrothermal method using sodium aluminate solution obtained from acid leaching of red mud as raw material and used for the adsorption of Congo red. The effects of initial pH and initial mass concentration of Congo red on the adsorption were investigated, and the adsorption mechanism of γ-AlOOH on Congo red was discussed. The results show that the saturated adsorption amount of Congo red can reach 1 748.15 mg/g under suitable conditions. The adsorption process is more appropriately described by the quasi-second-order kinetic model and the Langmuir isothermal adsorption model, and the adsorption behaviours are mainly dominated by monolayer adsorption. The adsorption process is spontaneous, heat-absorbing and chaotic with an increasing degree of confusion. The process can provide an effective solution to solve the problem of Congo red pollution and red mud accumulation in the water body, which is in line with the green development concept of treating waste with waste and turning waste into treasure, and has certain value of popularisation and application.

red mud  /  aluminum  /  γ-AlOOH  /  adsorbent  /  preparation  /  Congo red  /  adsorption
尚柯成, 李中林, 邹婷, 李文权, 张伟光, 李义兵. 赤泥提铝制备γ-AlOOH吸附剂及其对刚果红的吸附性能研究. 湿法冶金, 2025 , 44 (1) : 91 -99 . DOI: 10.13355/j.cnki.sfyj.2025.01.013
Kecheng SHANG, Zhonglin LI, Ting ZOU, Wenquan LI, Weiguang ZHANG, Yibing LI. Preparation of γ-AlOOH Adsorbent from Aluminum Extracted from Red Mud and Its Adsorption Properties for Congo Red[J]. Hydrometallurgy of China, 2025 , 44 (1) : 91 -99 . DOI: 10.13355/j.cnki.sfyj.2025.01.013
赤泥是用拜耳法从铝土矿中提取氧化铝后的红褐色强碱性固体废物,从铝土矿中提取1 t氧化铝会产生1~2.5 t赤泥[1],2023年我国赤泥产生量为1.07亿t[2]。目前,赤泥的处置方法主要以露天堆放为主,一方面由于产量巨大会占用大量土地资源,另一方面,在土壤、地下水和空气等环境中会造成严重的碱性污染。因此,对赤泥进行合理处置对于环境保护具有重要意义。目前,赤泥在建筑填充材料、混凝剂和土壤修复等领域应用广泛[3-6],但直接利用生产成本较高,因此将赤泥中剩余有价金属离子转化为功能材料,逐渐成为了实现赤泥高值化应用的有效策略。
勃姆石(γ-AlOOH)因具有较大的比表面积、特殊的多孔结构体系、活性相分散度高和无毒等优点,广泛应用于阻燃材料、涂层、电池隔膜、缓蚀剂、吸附材料的制备[7-8]。赤泥中仍含15%~30%的铝元素[9],一方面可将这些铝元素进行有效提取制备高级含铝环保产品,另一方面由于提铝残渣主要成分为氢氧化铁,可重新应用于铁冶炼回收铁元素,从而实现“以废治废、变废为宝”的赤泥绿色发展理念。
有机染料广泛应用于纺织、皮革、造纸和食品加工等行业[10],未经处理的染料废水直接排放至自然界中会对土壤和水体环境造成严重影响。刚果红是常见的一种联苯胺偶氮染料,在水体中不易降解,同时会被太阳光或生物酶代谢为致癌物[11],严重威胁水体生物和人类的安全。目前,在多种染料废水处理方法中,膜分离法因生产安装成本高难以普及,离子交换法因需要定期更换吸附树脂局限较大,而吸附法因具有操作简单、成本低、对环境友好等优点,成为了最常用的方法之一[12],而吸附剂是该法的关键。因此,试验研究了采用酸浸法提取赤泥中铝元素制备铝酸钠溶液,再采用水热法合成类绣球花状γ-AlOOH吸附剂,并用于吸附废水中的刚果红。采用XRD、SEM等方法分析该吸附剂的微观结构,通过建立等温吸附、颗粒内扩散模型分析γ-AlOOH对刚果红的吸附机制。
赤泥:来源于中国铝业广西分公司,主要化学组成见表1
主要试剂:氢氧化钠(NaOH,分析纯)、盐酸(HCl,分析纯)、尿素(CH4N2O,分析纯)、刚果红(Congo red,分析纯)、无水乙醇(高纯99.99%),试验配制溶液用水均为高纯水。
1)铝酸钠溶液的制备。称取适量块状赤泥放入干燥箱中,于60 ℃下干燥12 h后放入破壁机粉碎,粉碎完全后过200目筛;称取40 g赤泥粉末倒入烧杯中,加入480 mL浓度为4 mol/L的盐酸;将烧杯置于水浴锅中,设定温度为100 ℃,水浴加热2 h,之后在转速4 000 r/min下离心10 min;取上清液(铝酸钠溶液),加入4 mol/L NaOH调节溶液pH至13,使沉淀完全析出。铝酸钠溶液中元素质量浓度见表2。对比表1可知,赤坭中的杂质离子已基本去除完全。
2)γ-AlOOH的合成。取2.52 g尿素及50 mL所制备铝酸钠溶液放入烧杯中搅拌;待溶解完全后移入反应釜,于150 ℃下水热反应12 h;待温度降至室温后,用去离子水和无水乙醇洗涤数次,洗涤干净后放入60 ℃干燥箱内干燥,得类绣球花状γ-AlOOH吸附剂。
利用X’PertPRO型X射线衍射仪(XRD)分析吸附剂材料的物相及晶型特征,X射线为Cu Ka,测试衍射角范围为5°~80°;通过S-4800型扫描电子显微镜观察材料的表面微观结构;通过NoVA 1200e型比表面积与孔隙度分析仪分析并绘制吸附剂材料的氮气吸附—脱附等温曲线以分析其比表面积和孔结构;用Nani-ZS型Zeta电位分析仪(Zeta)测定材料的表面电位值;用Q 500型热重分析仪(TG)检测材料的热稳定性。
首先配制不同质量浓度的刚果红溶液200 mL,用浓度均为1 mol/L的盐酸和氢氧化钠调节溶液pH,然后分别加入50 mg的γ-AlOOH粉末,在室温下进行吸附试验。设置搅拌速度500 r/min,在不同的时间点取样,使用离心机在4 000 r/min下离心分离后取上清液,用UV-9000S型紫外分光光度仪(Shimazu)在最大吸收波长497 nm下测定其吸光度[13],计算刚果红吸附量qe及去除率η。计算公式如下:
qe=$\frac{({\rho }_{0}-{\rho }_{e})V}{m}$;
η=$\frac{{\rho }_{0}-{\rho }_{e}}{{\rho }_{0}}$×100%。
式中:ρ0—溶液中刚果红初始质量浓度,mg/L;ρe—吸附平衡时溶液中刚果红质量浓度,mg/L;V—溶液体积,L;m—吸附剂质量,g。
图1γ-AlOOH吸附剂的微观形貌及元素分布。由图1(a)、(b)看出:γ-AlOOH吸附剂的主要形貌的主要特征为类绣球花状结构,其直径主要分布在2~3 μm之间。形成机制为:在高压条件下,合成γ-AlOOH材料的过程加入的尿素会产生大量的二氧化碳,易诱导纤维状γ-AlOOH水解后自组装产生球状γ-AlOOH;且尿素易于水解产生较多的氢氧根离子,当溶液中的Al3+和OH-过饱和时,形成花瓣状纳米片[14]。图中类绣球花状结构的微观形貌亦可说明此形成机制。由图1(c)、(d)看出,Al、O元素均匀地分布在材料表面。
图2γ-AlOOH的XRD图谱。可以看出:在14.37°、28.05°、38.2°、49.02°、55.08°、60.4°、64.82°、67.37°和71.89°等处的衍射峰分别对应于勃姆石(JCPDS21-1307)的(020)、(120)、(031)、(200)、(151)、(080)、(002)、(171)和(251)晶面[15],且图谱中并未出现其他杂质衍射峰,说明γ-AlOOH材料制备成功。
图3γ-AlOOH的FT-IR光谱。可以看出:在483 cm-1及628 cm-1附近的吸收峰由(OH)—A1══O的弯曲振动引起,749 cm-1的吸收峰是由Al—O—Al的拉伸振动引起[16],而1 067 cm-1的吸收峰是由Al—OH的对称弯曲振动所致,1 636 cm-1处的吸收峰可归因于H2O分子的H—O—H弯曲振动[17],而3 100~3 315 cm-1的峰为H2O分子—OH的拉伸振动导致。以上分析表明,通过该工艺可成功合成γ-AlOOH,这与之前XRD的分析结论基本一致。
图4(a)(b)分别为类绣球花状γ-AlOOH的N2吸附—脱附等温线和孔径分布曲线。由图4(a)看出:γ-AlOOH的吸附—脱附等温线为Ⅳ型,具有明显的H3型吸附—脱附回滞环[18],此回滞环常见于介孔材料,说明所合成的γ-AlOOH为介孔材料,而介孔材料往往具有较大的孔结构,在实际应用中有利于促进吸附。由图4(b)看出:材料的孔径主要分布在2~15 nm,亦可证明此吸附剂为介孔材料。
根据BET和BJH计算模型得出的吸附剂比表面积、孔隙体积及孔径见表3。可以看出:γ-AlOOH的比表面积、孔隙体积和孔径分别为543.07 m2/g、0.58 cm3/g、4.24 nm。相比其他合成方法制备的勃姆石,γ-AlOOH吸附剂材料的比表面积及孔隙率均较高,对于吸附剂而言,较大的表面积可以增大材料表面活化能,提升材料表面活性,使得吸附剂与吸附质分子更易结合。同时,高孔隙率有利于刚果红分子在γ-AlOOH表面孔道之间的传质效应[19]。综上认为,合成的类绣球状γ-AlOOH吸附剂对于刚果红具有极其优异的吸附量和吸附速率。
图5γ-AlOOH的Zeta电位。可以看出:γ-AlOOH的电位在+20.8 mV左右,所携带电荷为正,表明该材料在水溶液中具有良好的分散性[20];而刚果红表面具有丰富的阴离子—SO3基团,易和表面带正电的γ-AlOOH发生静电作用,从侧面反应出类绣球状γ-AlOOH对刚果红具有良好的吸附效果。
图6γ-AlOOH的热重分析结果,测试温度范围为25~800 ℃,升温速率为10 ℃/min。可以看出:温度从室温升至100 ℃时,质量损失约为5%,是物理吸附水的蒸发所致;100~500 ℃范围内,质量损失较大,主要是勃姆石分解生成γ-Al2O3所致;温度高于534 ℃时,质量损失很小,归因于残留羟基的消除及γ-Al2O3的晶型转变。综上,总质量损失为23.68%,表明所制备的γ-AlOOH具有良好的热稳定性[21]
按照1.4的试验方法,取初始质量浓度为300 mg/L的刚果红溶液200 mL,用1 mol/L HCl和NaOH溶液调节溶液pH,加入50 mg γ-AlOOH样品,在室温下用磁力搅拌器搅拌4 h,考察溶液初始pH对刚果红吸附量和去除率的影响,试验结果如图7所示。
图7看出:当溶液初始pH从2升至4,γ-AlOOH对刚果红的吸附量基本稳定在1 200 mg/g不变;而pH超过4时,平衡吸附量开始下降,pH=10时降至746.26 mg/g;去除率也随pH升高而降低,pH=4时为99.8%,pH=10时降至43.2%。造成此现象的主要原因是pH升高使γ-AlOOH表面去质子化,并带有大量负电荷,抑制了γ-AlOOH对刚果红的吸附[22]
按照1.4的试验方法,配制200 mL不同质量浓度的刚果红溶液,加入50 mg γ-AlOOH粉末样品,在室温下用磁力搅拌器搅拌4 h,考察刚果红初始质量浓度对吸附量及去除率的影响,试验结果如图8所示。
图8看出:随刚果红初始质量浓度增大,吸附量快速升高,去除率较稳定,最高为97%;刚果红质量浓度增至500 mg/L时,吸附量升高幅度开始变缓并逐渐趋于平衡,去除率也明显下降;刚果红质量浓度增至700 mg/L时,刚果红吸附量为1 748.15 mg/g,说明此时刚果红吸附量已达到饱和,去除率降至60%左右。
为深入探究所制备γ-AlOOH对刚果红的吸附机制,将试验所得动态吸附数据分别通过准一阶、准二阶动力学模型和颗粒内扩散模型进行线性拟合,结果见图9~10,表4~5。准一阶、准二阶动力学、颗粒内扩散模型计算公式如下:
准一阶动力学模型:
ln(qe-qt)=ln qe-k1t;
准二阶动力学模型:
$\frac{t}{{q}_{t}}$=$\frac{1}{{k}_{2}{q}_{e}^{2}}$+$\frac{t}{{q}_{e}}$;
颗粒内扩散模型:
qt=kdit0.5+C
式中:qe—平衡吸附量,mg/g;qt—吸附t时刻的吸附量,mg/g;k1—准一阶动力学反应速率常数,min-1;k2—准二阶动力学反应速率常数,g/(mg·min);kdi—内扩散模型速率常数,mg/(g·h0.5);t—吸附时间,min;C—截距,μg/g。
图9表4看出:准一阶动力学模型的拟合相关系数为0.520 2,理论吸附量为895.67 mg/g;准二阶动力学模型的拟合相关系数为0.999 4,理论吸附量为1 617.59 mg/g。相比较而言,准二阶动力学模型的吸附量理论值与试验值1 561.74 mg/g更为接近,且其拟合相关系数也远高于准一阶动力学模型,说明该模型更适合描述γ-AlOOH 对刚果红的吸附过程,属于化学吸附。
图10γ-AlOOH吸附刚果红的颗粒内扩散模型拟合曲线,表5为相关拟合参数。
根据颗粒内扩散模型可知,如粒子内扩散控制了γ-AlOOH对刚果红分子的吸附速率,则qtt0.5呈现线性关系,且该扩散曲线通过原点。由图10看出:γ-AlOOH对刚果红的吸附过程呈现3个阶段而非线性关系,且均不经过原点,第Ⅰ阶段为快速吸收阶段,主要由于初始溶液中刚果红浓度较高,有利于γ-AlOOH对刚果红的吸附;第Ⅱ阶段为缓慢吸收阶段,这是因为经过一段时间吸附后,刚果红浓度下降,粒子扩散速率降低,导致吸附速率变缓;第Ⅲ阶段为吸附饱和阶段,该阶段γ-AlOOH吸附量达到饱和,吸附达到平衡。由表5看出:3个阶段的扩散速率k1>k2>k3,说明γ-AlOOH吸附刚果红过程主要为表层扩散为主[23];同时0<C1<C2<C3,表明颗粒内扩散不是吸附过程中的唯一限速机制,吸附过程中的其他条件均有可能改变吸附速率。
为进一步探究γ-AlOOH对刚果红的吸附机制,采用Langmuir和Freundlich等温吸附模型对试验数据进行拟合,图11γ-AlOOH吸附刚果红的等温吸附拟合曲线,表6为相关拟合参数。Langmuir和Freundlich等温吸附模型计算表达式如下:
Langmuir等温吸附模型:
$\frac{{\rho }_{e}}{{q}_{e}}$=$\frac{{\rho }_{e}}{{q}_{m}}$+$\frac{1}{{k}_{L}{q}_{m}}$;
Freundlich等温吸附模型:
ln qe=ln kF+$\frac{1}{n}$ln ρe
式中:qe—平衡吸附量,mg/g;qm—最大吸附量,mg/g;kL—Langmuir等温吸附模型吸附常数,L/mg;ρe—吸附平衡时溶液中刚果红质量浓度,mg/L;kF—Freundlich等温吸附模型吸附常数,mg1-1/n·L1/n·g-1;n—吸附强度。
表6看出:Langmuir等温吸附模型的拟合相关系数R2为0.999 9,最大吸附量为1 706.22 mg/g;Freundlich等温吸附模型的的拟合相关系数R2为0.761 7,最大吸附量为904.50 mg/g。说明Langmuir等温线模型的吸附数据拟合程度更高,γ-AlOOH与刚果红之间主要为单分子层吸附。
为了探究γ-AlOOH对刚果红吸附过程中的能量变化、吸附特性和吸附自发进行的可行性,对γ-AlOOH在不同温度下的吸附试验数据进行热力学分析。热力学参数与分配系数kd中间的关系如下:
kd=$\frac{{q}_{e}}{{\rho }_{e}}$;
Δg=-RTln kd;
ln kd=$\frac{\Delta S}{R}$-$\frac{\Delta H}{RT}$;
Δg=ΔH-TΔS
式中:T—热力学温度,K;R—理想气体常数,8.314 J/(mol·K)。
所制备γ-AlOOH吸附刚果红的热力学参数见表7。可以看出:在不同温度下,Δg均小于0,说明吸附过程在所选择温度条件下均可自发进行;且Δg随温度升高而逐渐降低,表明升高温度有利于刚果红分子在γ-AlOOH表面扩散;ΔH大于0,推断γ-AlOOH对于刚果红分子的捕获行为属于吸热反应;ΔS大于0,表明吸附后固液界面混乱度增加。综上分析可知,类绣球花状γ-AlOOH对刚果红的吸附行为是自发、吸热且熵增的。
采用水热法,用赤泥酸浸除杂制备的铝酸钠溶液成功合成了一种可吸附刚果红的类绣球花状γ-AlOOH吸附剂。该吸附剂具有较高的比表面积、较大的孔径及空隙体积,材料表面带有正电荷。适宜条件下,γ-AlOOH对刚果红的饱和吸附量达1 748.15 mg/g。吸附过程符合准二阶动力学模型和Langmuir等温吸附模型,主要为化学吸附和单分子层扩散。吸附热力学表明,类绣球花状γ-AlOOH吸附剂对于刚果红分子的吸附行为是自发、吸热且混乱度增大的。
采用的刚果红溶液为实验室配制而非实际废水,对废水中其他离子对类绣球花状γ-AlOOH吸附剂吸附刚果红的影响还有待进一步研究。
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doi: 10.13355/j.cnki.sfyj.2025.01.013
  • 接收时间:2024-07-31
  • 首发时间:2025-07-05
  • 出版时间:2025-02-28
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  • 收稿日期:2024-07-31
基金
国家自然科学基金-联合基金-重点支持项目(U23A20557)
广西科技计划项目重大专项(桂科AA23023033-1)
广西科技计划项目重大专项(桂科AA22067077)
作者信息
    1 桂林理工大学 材料科学与工程学院, 广西 桂林 541004
    2 桂林理工大学 有色金属与材料加工新技术教育部重点实验室, 广西 桂林 541004

通讯作者:

李义兵(1973—),男,博士,教授级高级工程师,主要研究方向为有色金属冶炼。E-mail:
参考文献
分享链接
https://castjournals.cast.org.cn/joweb/sfyj/CN/10.13355/j.cnki.sfyj.2025.01.013
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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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