Article(id=1172169532060848753, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172169457649697117, articleNumber=1009-2617(2025)04-0503-09, orderNo=null, doi=10.13355/j.cnki.sfyj.2025.04.010, 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=1757396594299, onlineDateStr=2025-09-09, pubDate=1755619200000, pubDateStr=2025-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757396594299, onlineIssueDateStr=2025-09-09, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757396594299, creator=13701087609, updateTime=1757396594299, updator=13701087609, issue=Issue{id=1172169457649697117, tenantId=1146029695717560320, journalId=1146120122248306696, year='2025', volume='44', issue='4', pageStart='433', pageEnd='581', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1757396576558, creator=13701087609, updateTime=1757401820494, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1172191452378547078, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172169457649697117, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1172191452378547079, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172169457649697117, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=503, endPage=511, ext={EN=ArticleExt(id=1172169532543193715, articleId=1172169532060848753, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Synthesis of Mesoporous γ-AlOOH Absorbent Via Direct Aging-Ammonium Salt Substitution Combined Method and Its Adsorption Properties for Congo Red, columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

Synthesization of mesoporous γ-AlOOH adsorbent via direct aging-ammonium salt substitution combined method in the presence of a desalting agent using metallurgical alumina hydroxide as raw material was investigated,and it was used for the adsorption of Congo red in wastewater.The physical phase and microscopic morphology of mesoporous γ-AlOOH were characterized by XRD,FT-IR,SEM,BET-BJH methods.The results show that the adsorption amount of Congo red by mesoporous γ-AlOOH adsorbent can reach 586.78 mg/g and the removal rate is 97.80% under the conditions of temperature of 25 ℃,adsorbent dosage of 100 mg,Congo red mass concentration of 300 mg/L,adsorption time of 180 min and pH=4.The adsorption process is more consistent with the pseudo-second-order kinetic model and the Langmuir isothermal adsorption model.The saturated adsorption capacity of mesoporous γ-AlOOH on Congo red is 1 965.265 mg/g at room temperature,and the adsorption process is spontaneous,heat absorption and chaotic.The main adsorption mechanism is the formation of hydrogen bonding between the adsorbent and adsorbate.

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以工业氢氧化铝为原料,研究了采用直接老化-铵盐取代联合法并在脱钠剂的作用下合成介孔γ-AlOOH吸附剂,并用于吸附废水中的刚果红,通过XRD、FT-IR、SEM、TEM、BET-BJH等手段对介孔γ-AlOOH的物相、微观形貌进行表征。结果表明:在温度25 ℃、吸附剂用量100 mg、刚果红质量浓度300 mg/L、吸附时间180 min、pH=4条件下,刚果红平衡吸附量为586.78 mg/g,脱除率为97.80%;整个吸附过程更适合用准二级动力学模型和Langmuir等温吸附模型描述,在室温下介孔γ-AlOOH对刚果红的饱和吸附量为1 965.265 mg/g,吸附过程是自发、吸热和混乱的,主要吸附机制是吸附质与吸附剂之间形成氢键。

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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:
何贵香(1973—),女,博士,教授,主要研究方向为湿法冶金及环境保护。E-mail:
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=ShOVbns6VCBBZDHzvyJjGQ==, magXml=wqwJ6mpx/mv94wquZtqlzA==, pdfUrl=null, pdf=If+zE1kZOXNgjyWF2jkWdw==, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=ByumjEcqz7HTgZ78yyQZ6Q==, mapNumber=null, authorCompany=null, fund=null, authors=

李文权(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

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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
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李文权(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

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李文权(1999—),男,硕士研究生,主要研究方向为有色金属冶炼。

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articleId=1172169532060848753, language=EN, label=Fig.8, caption=Fitting curve of intergranular diffusion kinetics of Congo red adsorbed by mesoporous γ-AlOOH, figureFileSmall=w20OODC6+nktUs/qgb7pFQ==, figureFileBig=eEDoSnT2rpgYVvgf+3uspg==, tableContent=null), ArticleFig(id=1172190260646761168, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=图8, caption=介孔γ-AlOOH吸附刚果红的颗粒内扩散动力学拟合曲线, figureFileSmall=w20OODC6+nktUs/qgb7pFQ==, figureFileBig=eEDoSnT2rpgYVvgf+3uspg==, tableContent=null), ArticleFig(id=1172190260705481425, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Fig.9, caption=Relationship between Congo red removal rate and adsorption capacity to equilibrium mass concentration, figureFileSmall=CW+jqbQMAsrMmyLCrW9kJQ==, figureFileBig=RRPAdsULAuGsfgi/PezT3g==, tableContent=null), ArticleFig(id=1172190260768395986, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=图9, caption=刚果红脱除率和吸附量与平衡质量浓度的关系曲线, figureFileSmall=CW+jqbQMAsrMmyLCrW9kJQ==, figureFileBig=RRPAdsULAuGsfgi/PezT3g==, tableContent=null), ArticleFig(id=1172190260822921939, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Fig.10, caption=Langmuir and Freundlich isothermal adsorption fitting curves for Congo red adsorption by mesoporous γ-AlOOH, figureFileSmall=CN+xHvFDRpUX0FjUTde6Ow==, figureFileBig=Ry9/G8bAUNJDfkh/MjzNGQ==, tableContent=null), ArticleFig(id=1172190260894225108, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=图10, caption=介孔γ-AlOOH吸附刚果红的Langmuir、Freundlich等温吸附拟合曲线, figureFileSmall=CN+xHvFDRpUX0FjUTde6Ow==, figureFileBig=Ry9/G8bAUNJDfkh/MjzNGQ==, tableContent=null), ArticleFig(id=1172190260952945365, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Fig.11, caption=Cyclic regeneration performance test results of mesoporous γ-AlOOH, figureFileSmall=PqTQuDXEoNe1f5M7jDy6DQ==, figureFileBig=3zinWQtvdNHyAJ3Oi7XlJg==, tableContent=null), ArticleFig(id=1172190261015859926, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=图11, caption=介孔γ-AlOOH的循环再生性能测试结果, figureFileSmall=PqTQuDXEoNe1f5M7jDy6DQ==, figureFileBig=3zinWQtvdNHyAJ3Oi7XlJg==, tableContent=null), ArticleFig(id=1172190261070385879, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Fig.12, caption=Infrared spectra of Congo red before and after adsorption by mesoporous γ-AlOOH, figureFileSmall=yzEkigFDM2un92/uEMfo2A==, figureFileBig=hnGwoQdVjxx52w3o2OMOwA==, tableContent=null), ArticleFig(id=1172190261133300440, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=图12, caption=介孔γ-AlOOH吸附刚果红前、后的红外光谱, figureFileSmall=yzEkigFDM2un92/uEMfo2A==, figureFileBig=hnGwoQdVjxx52w3o2OMOwA==, tableContent=null), ArticleFig(id=1172190261183632089, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Table 1, caption=

Main chemical composition of industrial Al(OH)3 %

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2 Fe2O3 Na2O ZnO Al(OH)3
0.67 1.59 0.36 0.66 96.72
), ArticleFig(id=1172190261238158042, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=表1, caption=

工业Al(OH)3的主要化学组成

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2 Fe2O3 Na2O ZnO Al(OH)3
0.67 1.59 0.36 0.66 96.72
), ArticleFig(id=1172190261301072603, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Table 2, caption=

Specific surface area and pore structure parameters of mesoporous γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
比表面积/(m2·g-1) 孔隙体积/(m3·g-1) 孔径/nm
131.26 0.23 5.87
), ArticleFig(id=1172190261368181468, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=表2, caption=

介孔γ-AlOOH的比表面积和孔结构参数

, figureFileSmall=null, figureFileBig=null, tableContent=
比表面积/(m2·g-1) 孔隙体积/(m3·g-1) 孔径/nm
131.26 0.23 5.87
), ArticleFig(id=1172190261447873245, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Table 3, caption=

Kinetic fitting parameters of Congo red adsorption by mesoporous 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/min-1 R2
586.78 179.693 0 -0.035 3 0.870 39 595.238 1 0.001 68 0.999 76
), ArticleFig(id=1172190261498204894, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=表3, caption=

介孔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/min-1 R2
586.78 179.693 0 -0.035 3 0.870 39 595.238 1 0.001 68 0.999 76
), ArticleFig(id=1172190261565313759, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Table 4, caption=

Fitting parameters of in-particle diffusion model of Congo red adsorbed by mesoporous γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
吸附过程 kdi/(mg·g-1·min-0.5) ci/(μg·g-1) R2
第1阶段 166.123 33 -3.122 62 0.992 69
第2阶段 11.963 71 477.564 57 0.983 35
第3阶段 0.064 67 585.940 92 0.936 65
), ArticleFig(id=1172190261649199840, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=表4, caption=

介孔γ-AlOOH吸附刚果红的颗粒内扩散模型拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
吸附过程 kdi/(mg·g-1·min-0.5) ci/(μg·g-1) R2
第1阶段 166.123 33 -3.122 62 0.992 69
第2阶段 11.963 71 477.564 57 0.983 35
第3阶段 0.064 67 585.940 92 0.936 65
), ArticleFig(id=1172190261712114401, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Table 5, caption=

Langmuir and Freundlich isothermal adsorption fitting parameters for Congo red adsorption by mesoporous 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
1 992.989 0.024 115 0.999 38 362.749 3.710 988 0.720 87
), ArticleFig(id=1172190261779223266, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=表5, caption=

介孔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
1 992.989 0.024 115 0.999 38 362.749 3.710 988 0.720 87
), ArticleFig(id=1172190261846332131, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=EN, label=Table 6, caption=

Thermodynamic parameters of Congo red adsorption by mesoporous γ-AlOOH

, figureFileSmall=null, figureFileBig=null, tableContent=
T/K ΔG/
(kJ·mol-1)
ΔH/
(J·mol-1)
ΔS/
(J·mol-1·K-1)
298 -2.496 37 8.5
308 -2.581
318 -2.666
), ArticleFig(id=1172190261913440996, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172169532060848753, language=CN, label=表6, caption=

介孔γ-AlOOH对刚果红吸附过程的热力学参数

, figureFileSmall=null, figureFileBig=null, tableContent=
T/K ΔG/
(kJ·mol-1)
ΔH/
(J·mol-1)
ΔS/
(J·mol-1·K-1)
298 -2.496 37 8.5
308 -2.581
318 -2.666
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直接老化-铵盐取代联合法合成介孔γ-AlOOH及其对刚果红的吸附性能
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李文权 1, 2, 3 , 李中林 1, 2 , 尚柯成 1, 2 , 邹婷 1, 2 , 何贵香 3 , 李义兵 1, 2
湿法冶金 | 试验研究 2025,44(4): 503-511
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湿法冶金 | 试验研究 2025, 44(4): 503-511
直接老化-铵盐取代联合法合成介孔γ-AlOOH及其对刚果红的吸附性能
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李文权1, 2, 3, 李中林1, 2, 尚柯成1, 2, 邹婷1, 2, 何贵香3 , 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
  • 3 桂林理工大学(南宁分校) 冶金与资源工程系,广西 南宁 530000
  • 李文权(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:
何贵香(1973—),女,博士,教授,主要研究方向为湿法冶金及环境保护。E-mail:
Synthesis of Mesoporous γ-AlOOH Absorbent Via Direct Aging-Ammonium Salt Substitution Combined Method and Its Adsorption Properties for Congo Red
Wenquan LI1, 2, 3, Zhonglin LI1, 2, Kecheng SHANG1, 2, Ting ZOU1, 2, Guixiang HE3 , 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
  • 3 Department of Metallurgical and Resources Engineering,Guilin University of Technology (Nanning Campus),Nanning 530000,China
出版时间: 2025-08-20 doi: 10.13355/j.cnki.sfyj.2025.04.010
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以工业氢氧化铝为原料,研究了采用直接老化-铵盐取代联合法并在脱钠剂的作用下合成介孔γ-AlOOH吸附剂,并用于吸附废水中的刚果红,通过XRD、FT-IR、SEM、TEM、BET-BJH等手段对介孔γ-AlOOH的物相、微观形貌进行表征。结果表明:在温度25 ℃、吸附剂用量100 mg、刚果红质量浓度300 mg/L、吸附时间180 min、pH=4条件下,刚果红平衡吸附量为586.78 mg/g,脱除率为97.80%;整个吸附过程更适合用准二级动力学模型和Langmuir等温吸附模型描述,在室温下介孔γ-AlOOH对刚果红的饱和吸附量为1 965.265 mg/g,吸附过程是自发、吸热和混乱的,主要吸附机制是吸附质与吸附剂之间形成氢键。

老化-铵盐取代联合法  /  制备  /  吸附剂  /  γ-AlOOH  /  刚果红  /  吸附

Synthesization of mesoporous γ-AlOOH adsorbent via direct aging-ammonium salt substitution combined method in the presence of a desalting agent using metallurgical alumina hydroxide as raw material was investigated,and it was used for the adsorption of Congo red in wastewater.The physical phase and microscopic morphology of mesoporous γ-AlOOH were characterized by XRD,FT-IR,SEM,BET-BJH methods.The results show that the adsorption amount of Congo red by mesoporous γ-AlOOH adsorbent can reach 586.78 mg/g and the removal rate is 97.80% under the conditions of temperature of 25 ℃,adsorbent dosage of 100 mg,Congo red mass concentration of 300 mg/L,adsorption time of 180 min and pH=4.The adsorption process is more consistent with the pseudo-second-order kinetic model and the Langmuir isothermal adsorption model.The saturated adsorption capacity of mesoporous γ-AlOOH on Congo red is 1 965.265 mg/g at room temperature,and the adsorption process is spontaneous,heat absorption and chaotic.The main adsorption mechanism is the formation of hydrogen bonding between the adsorbent and adsorbate.

direct aging-ammonium salt substitution combined method  /  synthesization  /  adsorbent  /  γ-AlOOH  /  Congo red  /  adsorption
李文权, 李中林, 尚柯成, 邹婷, 何贵香, 李义兵. 直接老化-铵盐取代联合法合成介孔γ-AlOOH及其对刚果红的吸附性能. 湿法冶金, 2025 , 44 (4) : 503 -511 . DOI: 10.13355/j.cnki.sfyj.2025.04.010
Wenquan LI, Zhonglin LI, Kecheng SHANG, Ting ZOU, Guixiang HE, Yibing LI. Synthesis of Mesoporous γ-AlOOH Absorbent Via Direct Aging-Ammonium Salt Substitution Combined Method and Its Adsorption Properties for Congo Red[J]. Hydrometallurgy of China, 2025 , 44 (4) : 503 -511 . DOI: 10.13355/j.cnki.sfyj.2025.04.010
随着纺织业的快速发展,对染料的需求急剧增加。有机物染料具有毒性大、色度高、难降解等特点,此类染料废水若未经处理而大量排放会造成水体污染,严重威胁人体健康[1]。刚果红是应用广泛的有机物染料之一,具有极强的水溶性,极易在水中残留,即使浓度很低也会对水生生物和食物链造成影响[2];此外,其还会在厌氧条件下降解为可致癌的联苯胺,对人体健康造成危害[3]。因此,从废水中去除有机物染料十分必要。目前,从废水中去除有机物染料的方法已有很多,包括浊点萃取法[4]、离子交换法[5]、膜滤法[6-7]、吸附法[8-12]、光催化降解法[13-14]等。其中,吸附法因具有操作简便、处理成本低、效率高、效果优异等诸多优势,逐渐成为了主流办法之一。
勃姆石(γ-AlOOH)比表面积大,斜方结构稳定,表面活化能高,具有优异的吸附性能,且无毒,广泛应用于吸附领域。为了控制勃姆石微观形貌、比表面积、孔结构参数、颗粒大小和结晶性质等特征,研究人员对其制备方法进行了大量研究和改进,目前已经成功采用水热法[15]、溶胶-凝胶法[16]等不同方法合成了不同形貌的勃姆石。采用这些方法所制备的勃姆石具有优异的吸附性能,但还存在产率低、设备要求高等问题,导致工业上大规模应用受限。
试验以工业Al(OH)3为原料,采用直接老化-铵盐取代联合法制备一种介孔γ-AlOOH吸附材料,并用于吸附染料废水中的刚果红。通过XRD、SEM、TEM等手段对该吸附材料的物相、微观形貌进行了表征,并探究了其对刚果红的吸附性能、吸附动力学和热力学。
铝源来自中国某铝业公司生产的工业Al(OH)3,主要化学组成见表1
主要试剂:刚果红(化学纯)、碳酸铵(分析纯)、氢氧化钠(分析纯)、盐酸(36~38%)、无水乙醇(99.99%)等,均购自广东西陇科学股份有限公司。
制备原理:采用溶解—再结晶法制备吸附材料,即先用强碱重溶工业Al(OH)3制得偏铝酸钠(NaAl(OH)4)溶液,之后再通过调节溶液pH使Al3+重新结晶为γ-AlOOH沉淀。将沉淀老化一定时间,待晶体结构稳定后,再将其放入脱钠剂(碳酸铵水溶液)中,使 N H 4 +取代杂质Na+而被γ-AlOOH吸附;之后取出,干燥,在此过程中,   N H 4 +会以氨气形式逸出,从而使γ-AlOOH表面积和孔隙率增大,提高其吸附性能[17]
介孔γ-AlOOH的制备:制备过程如图1所示。首先量取400 mL预先配制好的13.7 mol/LNaOH溶液放入烧杯中,再加入281.4 g工业Al(OH)3,在95 ℃水热条件下搅拌2 h,得到NaAl(OH)4溶液;之后继续在30 ℃水浴条件下将盐酸缓慢加入NaAl(OH)4溶液中,调节pH至10.0;在60 ℃下,采用9 mm搅拌子以900 r/min的速度进行搅拌,老化2 h;将得到的胶体物质离心,并用超纯水洗涤至中性;最后将胶体物质分散在200 mL的60 g/L碳酸铵水溶液中进行铵盐取代,以300 r/min的速度搅拌30 min后,放入120 ℃的鼓风电热恒温干燥箱中干燥12 h,获得介孔γ-AlOOH粉末。
采用X射线荧光光谱分析仪(XRF-1800型)测定工业Al(OH)3的元素含量(Al、Si、Fe、Na、Zn);采用用紫外—可见分光光度计(UV-9000S型)对吸附后溶液中残留的刚果红的浓度进行测定;采用5.0 kV扫描电子显微镜(S-4800型)和场发射扫描透射电子显微镜(talos F200X型)观察材料的微观形貌;采用X射线衍射仪(X'Pert PRO型,以Cu Kα作为射线源,λ=0.154 18 nm,管电压为40 kV,管电流为80 mA,扫描范围为5°~80°)分析材料的物相;采用比表面积与孔隙度分析仪(NoVA 1200e型)分析材料的比表面积和孔结构参数;采用FT-IR光谱分析仪(Nexus 470 FT-IR型)分析其结构和化学键。
根据染料废水成份,配制质量浓度为300 mg/L的刚果红溶液,取200 mL,以恒定速度进行搅拌,缓慢滴加稀HCl调节溶液pH至4;再加入100 mg介孔γ-AlOOH粉末,间隔一定时间用移液器取样,离心,取上清液测定刚果红浓度。按照式(1)、(2)分别计算介孔γ-AlOOH对刚果红的吸附量qt和脱除率η
q t = ( ρ 0 - ρ t ) V m ;
η = ρ 0 - ρ t ρ 0 × 100 %
式中:qt—刚果红吸附量,mg/L;η—刚果红脱除率,%;V—溶液体积,L;m—吸附剂质量,mg;ρ0—溶液中刚果红初始质量浓度,mg/L;ρt—吸附t时间后溶液中刚果红质量浓度,mg/L。
图2为样品和勃姆石标准卡片(JCPDS21-1307)的XRD图谱。可以看出:介孔γ-AlOOH样品的特征峰与勃姆石标准卡片JCPDS21-1307一致,无其他杂质峰,这表明此样品为γ-AlOOH。为进一步讨论产物结晶度,用Scherrer公式计算样品单晶尺寸D:
D = k λ β c o s θ
式中:k—Scherrer常数;β—衍射峰的半峰宽(FWHM),rad;θ—衍射角,(°);λ—X射线波长,nm。
FWHM可用于测定结晶度和确定样品的定向方向,FWHM值越低,结晶度越高。从图2可知,样品最尖锐的峰为(020)晶面,该峰的β=3.05 rad,经计算得出D020=2.596 nm。
图3为介孔γ-AlOOH的红外光谱。可以看出:3 315、3 100 cm-1附近出现了—OH的伸缩振动峰;1 644 cm-1附近出现了—OH的弯曲振动峰[18];1 070 cm-1附近出现了Al—O—H的弯曲振动峰;738、628和483 cm-1处检测到的吸收峰是由AlOOH中Al—O振动引起[19],这表明样品的红外光谱所检测到的峰均与介孔γ-AlOOH的峰一致,说明试验成功合成了介孔γ-AlOOH。
介孔γ-AlOOH的SEM和TEM分析结果如图4所示。可以看出:介孔γ-AlOOH微观形貌整体呈絮状,粒径为200~400 nm。这是由于老化过程产生的γ-AlOOH晶粒尺寸较小,随老化时间延长,晶体之间的作用力增强,晶体粘连团聚,形成块状团聚物;此时由于晶体粘连,少部分Na+被吸附在介孔γ-AlOOH表面,当进行铵盐取代后,残留在介孔γ-AlOOH表面上的Na+会被 N H 4 +取代,最后以NH3形式释放,并在块状团聚物表面形成絮状结构[17]
介孔材料的比表面积、孔径和表面孔隙率在一定程度上决定了其吸附性能。γ-AlOOH对氮气的吸附—脱附循环曲线和孔径分布如图5表2所示。可以看出:γ-AlOOH对氮气的吸附—脱附等温线呈Ⅳ型,且伴有H2型回滞环,表明γ-AlOOH为介孔材料[20];其比表面积、孔隙体积、孔径大小分别为131.26 m2/g、0.23 m3/g、5.87 nm,比表面积较高,介孔结构较大。对于介孔材料而言,高比表面积和大的介孔结构不仅可以提供大量的活性位点,还可以有效促进吸附质内扩散[21]
在温度25 ℃条件下,用介孔γ-AlOOH吸附pH=4.0、初始质量浓度为300 mg/L的刚果红溶液,吸附时间对其吸附性能的影响如图6所示。
图6可知,在吸附的前20 min,介孔γ-AlOOH对刚果红的吸附速率较快,吸附量大幅升高,这是由于介孔γ-AlOOH表面活化能较高,表面存在大量活性位点,且刚果红浓度较高,刚果红分子极易扩散到介孔γ-AlOOH表面;吸附20 min后,吸附速率逐渐减慢,吸附量升幅较小,这是由于介孔γ-AlOOH外表面的刚果红分子通过介孔向内扩散速度变慢,表面的活性位点逐渐饱和,难以占据剩余的孔隙[22];吸附120 min后达到吸附平衡状态,平衡吸附量为586.78 mg/g,脱除率达97.80%。
采用准一阶动力学模型、准二阶动力学模型和颗粒内扩散模型[23]对动力学试验数据进行拟合,拟合结果见图78表34
准一阶动力学模型:
l n ( q e - q t ) = l n   q e - k 1 t ;
准二阶动力学模型:
t q t = 1 k 2 q e 2 + t q e ;
颗粒内扩散模型:
q t = k d i t 0.5 + c i
式中:qe—刚果红平衡吸附量,mg/g;qt—吸附t时间时刚果红吸附量,mg/g;k1—准一级动力学吸附速率常数,min-1;t—吸附时间,min;k2—准二级动力学吸附速率常数,g·mg-1·min-1;kdi—吸附过程中时段i的内扩散模型吸附速率常数,mg·g-1·min-1/2;ci—颗粒内扩散模型常数,μg/g,反映边界层效应。
表3看出,与准一阶动力学模型的拟合相关系数(R2=0.870 39)相比,准二阶动力学模型的拟合相关系数(R2=0.999 76)更接近于1,且准二阶动力学模型的理论吸附量(595.238 1 mg/g)比准一阶动力学模型的理论吸附量(179.693 0 mg/g)更接近实际吸附量(586.78 mg/g)。说明介孔γ-AlOOH对刚果红的吸附过程更符合准二阶动力学模型,吸附过程属于化学吸附。
颗粒内扩散模型能更深层次地描述刚果红分子在介孔γ-AlOOH表面上的吸附过程。由图8表4可知,qtt0.5之间的关系分为3个线性阶段。第1阶段为瞬时吸附,也称为外部传递过程,此时吸附速率很快,kd1=166.123 33 mg/(g·min),c1=-3.122 62 μg/g。这主要归因于两个方面:一是初始时刚果红浓度较高,浓度梯度较大,使得大量刚果红分子从溶液中向介孔γ-AlOOH表面扩散;二是介孔γ-AlOOH具有较高的表面活化能,能迅速捕获并吸附扩散到其表面的刚果红分子。第2阶段相对缓慢,被称为孔内传递过程(内扩散),此过程是刚果红分子从表面经孔隙向颗粒内扩散的过程,kd2=11.963 71 mg/(g·min),c2=477.564 57 μg/g,这是因为随反应进行,溶液中刚果红浓度逐渐下降,且介孔γ-AlOOH外表面的活性位点也逐渐减少,导致刚果红分子扩散速率变慢。第3阶段为吸附平衡阶段,此时kd3=0.064 67 mg/(g·min),c3=585.940 92 μg/g。3个阶段的截距均不为0,表明介孔γ-AlOOH对刚果红的吸附过程涉及颗粒内扩散,但不是吸附过程的唯一限速机制,反应过程中同时出现的其他条件也有可能控制反应速率。
吸附等温线能揭示平衡浓度与吸附量之间的相互关系。介孔γ-AlOOH对刚果红的吸附脱除率和吸附量与平衡质量浓度的关系曲线如图9所示。可以看出,随刚果红平衡质量浓度升高,吸附量逐渐升高,最后保持在1 965.265 mg/g,达到了吸附饱和,而脱除率则逐渐降低。
吸附热力学模型是描述在吸附剂表面吸附物质分布的数学模型[24-25]。用Langmuir[26]和Frendlich[27]等温吸附模型对试验数据进行拟合,可判断介孔γ-AlOOH对刚果红的吸附行为是单分子层吸附还是多分子层吸附。
Langmuir等温吸附模型:
q e = q m k L ρ e 1 + k L ρ e ;
Freundlich等温吸附模型:
l n   q e = l n   k F + l n   ρ e n
式中:ρe—吸附平衡时刚果红质量浓度,mg/L;qm—饱和吸附量,mg/g;kL—Langmuir等温吸附模型常数,L/mg。kF—Freundlich等温吸附模型常数,mg1-1/n·L1/n·g-1,n—Freundlich吸附强度。
图10是介孔γ-AlOOH吸附刚果红的Langmuir、Freundlich等温吸附拟合曲线,拟合参数见表5
表5看出:Langmuir等温吸附模型的相关系数R2(0.999 38)大于Freundlich等温吸附模型的相关系数R2(0.720 87);根据Langmuir等温吸附模型计算得出,室温下介孔γ-AlOOH对刚果红的饱和吸附量(qm)为1 992.989 mg/g,与试验值(1 965.265 mg/g)更相近。综上,Langmuir等温吸附模型能更好地拟合介孔γ-AlOOH对刚果红的吸附行为,说明吸附过程属于单分子层吸附。
为了深入探究吸附过程的热力学,根据式(9)~(11)计算吉布斯自由能变(ΔG)、焓变(ΔH)和熵变(ΔS)。计算结果见表6
Δ G = - R T l n   k d ;
l n   k d = Δ S R - Δ H R T ;
Δ G = Δ H - T Δ S
式中:R—理想气体常数,8.314 J/(mol·K);T—热力学温度,K;kd—分配系数。
表6看出:在选定的温度范围内,ΔG均为负值,证明吸附过程是自发的,且ΔG随温度升高而减小,说明温度升高对介孔γ-AlOOH捕获刚果红分子有促进作用;ΔH>0,证明吸附过程是吸热的;ΔS>0,说明固液界面的混乱程度增加。综上可知,介孔γ-AlOOH对刚果红的吸附是自发、吸热且混乱的。
为了测试介孔γ-AlOOH对刚果红的循环吸附性能,进行吸附—脱附试验(解吸液为1 mol/L NaOH溶液)。在相同温度、pH条件下,用循环再生的介孔γ-AlOOH处理相同体积、浓度的刚果红溶液,重复5次,结果如图11所示。
图11看出:5次再生后,γ-AlOOH对刚果红的吸附量仍保持在484.8 mg/g,仅下降17.64%,说明该吸附剂经过5次再生后对刚果红仍具有较好的吸附性能。
为探讨介孔γ-AlOOH对刚果红分子的主要吸附机制,用傅里叶变换红外光谱仪分析了介孔γ-AlOOH吸附刚果红前、后的结构,如图12所示。可知:刚果红在3 447 cm-1处出现的吸收峰是由N—H的伸缩振动引起,而介孔γ-AlOOH吸附刚果红后,该吸收峰移至3 400 cm-1处;介孔γ-AlOOH吸附刚果红前,在3 315和3 100 cm-1处的—OH伸缩振动峰的强度在吸附后明显减弱,表明介孔γ-AlOOH的—OH与刚果红分子的—NH2之间形成了氢键[28];同时刚果红在1 129 cm-1处出现的吸收峰属于—SO3,γ-AlOOH吸附刚果红后—SO3吸收峰出现,且强度减弱,说明刚果红中的—SO3参与了吸附[29];介孔γ-AlOOH吸附刚果红后,在1 070 cm-1处的A1—O—H键与738、622 和483 cm-1处的A1—O键的峰强度较吸附前都明显减弱,表明它们可能参与了吸附[30]。综上推断,介孔γ-AlOOH的主要吸附机制是介孔γ-AlOOH的—OH与刚果红分子的—NH2和—SO3形成氢键。
以工业氢氧化铝为原料,采用直接老化-铵盐取代联合法,在脱钠剂的作用下成功合成了介孔γ-AlOOH吸附剂。在25 ℃下,用100 mg的介孔γ-AlOOH吸附pH=4.0、初始质量浓度为300 mg/L刚果红溶液,平衡吸附量为586.78 mg/g,去除率为97.80%。吸附过程符合准二级动力学模型和Langmuir等温吸附模型,在室温下介孔γ-AlOOH对刚果红的饱和吸附量为1 965.265 mg/g;整个吸附过程是自发、吸热和混乱的,主要吸附机制是吸附质与吸附剂之间形成氢键。5次循环吸附—脱附后的介孔γ-AlOOH对刚果红的吸附量仍能保持在82.36%。
与传统方法相比,该合成方法成本低、产量高,所制备吸附剂对刚果红具有良好的吸附性能,后续还可通过复合、改性等方法改善其表面性能,从而进一步提高吸附性能。
  • 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)
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2025年第44卷第4期
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doi: 10.13355/j.cnki.sfyj.2025.04.010
  • 接收时间:2024-07-31
  • 首发时间:2025-09-09
  • 出版时间:2025-08-20
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  • 收稿日期:2024-07-31
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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
    3 桂林理工大学(南宁分校) 冶金与资源工程系,广西 南宁 530000

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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:
何贵香(1973—),女,博士,教授,主要研究方向为湿法冶金及环境保护。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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