Article(id=1172615465701622255, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172615462853685818, articleNumber=1009-2617(2024)06-0665-07, orderNo=null, doi=10.13355/j.cnki.sfyj.2024.06.011, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1715270400000, receivedDateStr=2024-05-10, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1757502913165, onlineDateStr=2025-09-10, pubDate=1734624000000, pubDateStr=2024-12-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757502913165, onlineIssueDateStr=2025-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757502913165, creator=13701087609, updateTime=1757502913165, updator=13701087609, issue=Issue{id=1172615462853685818, tenantId=1146029695717560320, journalId=1146120122248306696, year='2024', volume='43', issue='6', pageStart='593', pageEnd='716', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1757502912485, creator=13701087609, updateTime=1758246000747, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1175732200986263845, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172615462853685818, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1175732200986263846, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172615462853685818, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=665, endPage=671, ext={EN=ArticleExt(id=1172615465911337459, articleId=1172615465701622255, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Preparation of Magnetic and Porous MgO and Its Adsorption Performance for U(Ⅵ), columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

The magnetic porous magnesium oxide(m-MgO) was prepared with nano-ferric oxide (Fe3O4) as the core and MgCl2 as the magnesium source, and was used for adsorption of U(Ⅵ) in aqueous solution. The physicochemical properties of MgO and m-MgO were characterized by FT-IR, XRD, VSM and Zeta potential. The effects of solution pH, temperature, and oscillation time on the adsorption of U(Ⅵ) by MgO and m-MgO were investigated. The results show that the optimal conditions for uranium adsorption by MgO and m-MgO are pH=3.5, adsorbent dosage of 10 mg, and oscillation time of 720 min. The adsorption process conforms to the pseudo-second-order kinetic model and the Sips isotherm adsorption model, with a theoretical adsorption capacity of 454.16 mg/g, and the increase of temperature is conducive to the spontaneous adsorption. Therefore, m-MgO is expected to be used to separate and recover uranium from radioactive wastewater.

, 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=Pengwang SONG, Yuqin FU, Liang ZHOU, Weiqian CAI, Lingshan XIONG, Youqun WANG), CN=ArticleExt(id=1172615832766136445, articleId=1172615465701622255, tenantId=1146029695717560320, journalId=1146120122248306696, language=CN, title=磁性多孔MgO的合成及其对U(Ⅵ)的吸附性能研究, columnId=1152626641328501305, journalTitle=湿法冶金, columnName=试验研究, runingTitle=null, highlight=null, articleAbstract=研究了以纳米四氧化三铁(Fe3O4)为内核、MgCl2为镁源,制备磁性多孔氧化镁(m-MgO),并用于吸附水溶液中的U(Ⅵ)。采用FT-IR、XRD、VSM及Zeta电位表征了MgO和m-MgO的理化性质,考察了溶液pH、吸附剂用量、振荡时间对MgO和m-MgO吸附U(Ⅵ)的影响,并探讨了吸附动力学。结果表明:m-MgO吸附铀的最优条件为溶液pH=3.5、吸附剂用量10 mg、振荡时间720 min;吸附过程符合准二级动力学模型和Sips等温吸附模型,理论吸附量为454.16 mg/g,升高温度有助于吸附自发进行。m-MgO有望用于从放射性废水中分离回收铀。, correspAuthors=null, authorNote=null, correspAuthorsNote=
王有群(1988—),男,博士,副教授,主要研究方向为核化工。E-mail:
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宋鹏旺(2000—),男,硕士研究生,主要研究方向为放射性废水处理。

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宋鹏旺(2000—),男,硕士研究生,主要研究方向为放射性废水处理。

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宋鹏旺(2000—),男,硕士研究生,主要研究方向为放射性废水处理。

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tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=CN, label=图11, caption=ln kd-1/T关系曲线, figureFileSmall=CNHGHAMBRkBabxY5zSjnAg==, figureFileBig=ohL8Sy6scOFErL2tWLdSjg==, tableContent=null), ArticleFig(id=1175865092265620361, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
材料 SBET/(m2·g-1) Vt/(cm3·g-1) Dm/nm
MgO 4.77 0.03 36.13
m-MgO 25.30 0.16 46.05
), ArticleFig(id=1175865092353700748, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=CN, label=表1, caption=

MgO和m-MgO的比表面积及孔结构参数

, figureFileSmall=null, figureFileBig=null, tableContent=
材料 SBET/(m2·g-1) Vt/(cm3·g-1) Dm/nm
MgO 4.77 0.03 36.13
m-MgO 25.30 0.16 46.05
), ArticleFig(id=1175865092487918478, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
吸附剂 qe,试验/(mg·g-1) 准一级动力学模型 准二级动力学模型
qe,理论/(mg·g-1) k1/(min-1) R2 qe,理论/(mg·g-1) k2/(g·mg-1·min-1) R2
MgO 116.57 104.60 0.065 0.79 111.12 8.76×10-4 0.94
m-MgO 218.32 204.92 0.034 0.97 230.80 2.18×10-4 0.99
), ArticleFig(id=1175865092685050768, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=CN, label=表2, caption=

MgO和m-MgO吸附U(Ⅵ)的准一级和准二级动力学拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
吸附剂 qe,试验/(mg·g-1) 准一级动力学模型 准二级动力学模型
qe,理论/(mg·g-1) k1/(min-1) R2 qe,理论/(mg·g-1) k2/(g·mg-1·min-1) R2
MgO 116.57 104.60 0.065 0.79 111.12 8.76×10-4 0.94
m-MgO 218.32 204.92 0.034 0.97 230.80 2.18×10-4 0.99
), ArticleFig(id=1175865092777325458, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
吸附剂 Langmuir Freundlich Sips
qm/
(mg·g-1)
kL/
(L·mg-1)
R2 n kF/
(L1/n·mg1-1/n·g-1)
R2 qm/
(mg·g-1)
kS/
(Lβ·mg1-β·g-β)
β R2
MgO 521.56 6.20×10-2 0.99 0.44 64.84 0.94 492.97 0.07 1.10 0.94
m-MgO 587.92 4.01×10-2 0.95 0.44 65.45 0.85 454.16 0.07 1.95 0.99
), ArticleFig(id=1175865092886377365, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=CN, label=表3, caption=

MgO和m-MgO吸附U(Ⅵ)的等温吸附拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
吸附剂 Langmuir Freundlich Sips
qm/
(mg·g-1)
kL/
(L·mg-1)
R2 n kF/
(L1/n·mg1-1/n·g-1)
R2 qm/
(mg·g-1)
kS/
(Lβ·mg1-β·g-β)
β R2
MgO 521.56 6.20×10-2 0.99 0.44 64.84 0.94 492.97 0.07 1.10 0.94
m-MgO 587.92 4.01×10-2 0.95 0.44 65.45 0.85 454.16 0.07 1.95 0.99
), ArticleFig(id=1175865092987040663, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
吸附剂 ΔH/
(kJ·mol-1)
ΔS/
(J·mol-1·K-1)
ΔG/(kJ·mol-1)
298 K 303 K 308 K
MgO 37.4 207.9 -24.6 -25.6 -26.6
m-MgO 51.5 241.1 -20.3 -21.6 -22.8
), ArticleFig(id=1175865093054149529, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172615465701622255, language=CN, label=表4, caption=

MgO和m-MgO吸附铀的热力学参数

, figureFileSmall=null, figureFileBig=null, tableContent=
吸附剂 ΔH/
(kJ·mol-1)
ΔS/
(J·mol-1·K-1)
ΔG/(kJ·mol-1)
298 K 303 K 308 K
MgO 37.4 207.9 -24.6 -25.6 -26.6
m-MgO 51.5 241.1 -20.3 -21.6 -22.8
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磁性多孔MgO的合成及其对U(Ⅵ)的吸附性能研究
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宋鹏旺 1 , 付玉琴 2 , 周亮 3 , 蔡为钱 1 , 熊玲珊 1 , 王有群 1
湿法冶金 | 试验研究 2024,43(6): 665-671
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湿法冶金 | 试验研究 2024, 43(6): 665-671
磁性多孔MgO的合成及其对U(Ⅵ)的吸附性能研究
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宋鹏旺1, 付玉琴2, 周亮3, 蔡为钱1, 熊玲珊1, 王有群1
作者信息
  • 1 东华理工大学 核资源与环境国家重点实验室, 江西 南昌 330013
  • 2 江西省地质调查勘查院基础地质调查所实验测试中心, 江西 南昌 330000
  • 3 江西省地质局物化探大队实验测试中心, 江西 南昌 330201
  • 宋鹏旺(2000—),男,硕士研究生,主要研究方向为放射性废水处理。

通讯作者:

王有群(1988—),男,博士,副教授,主要研究方向为核化工。E-mail:
Preparation of Magnetic and Porous MgO and Its Adsorption Performance for U(Ⅵ)
Pengwang SONG1, Yuqin FU2, Liang ZHOU3, Weiqian CAI1, Lingshan XIONG1, Youqun WANG1
Affiliations
  • 1 State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China
  • 2 Experimental Testing Center of the Basic Geological Survey Institute of Jiangxi Geological Survey and Exploration Institute, Nanchang 330000, China
  • 3 Experimental Testing Center of Physical and Chemical Exploration Brigade of Jiangxi Provincial Geological Bureau, Nanchang 330201, China
出版时间: 2024-12-20 doi: 10.13355/j.cnki.sfyj.2024.06.011
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研究了以纳米四氧化三铁(Fe3O4)为内核、MgCl2为镁源,制备磁性多孔氧化镁(m-MgO),并用于吸附水溶液中的U(Ⅵ)。采用FT-IR、XRD、VSM及Zeta电位表征了MgO和m-MgO的理化性质,考察了溶液pH、吸附剂用量、振荡时间对MgO和m-MgO吸附U(Ⅵ)的影响,并探讨了吸附动力学。结果表明:m-MgO吸附铀的最优条件为溶液pH=3.5、吸附剂用量10 mg、振荡时间720 min;吸附过程符合准二级动力学模型和Sips等温吸附模型,理论吸附量为454.16 mg/g,升高温度有助于吸附自发进行。m-MgO有望用于从放射性废水中分离回收铀。
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The magnetic porous magnesium oxide(m-MgO) was prepared with nano-ferric oxide (Fe3O4) as the core and MgCl2 as the magnesium source, and was used for adsorption of U(Ⅵ) in aqueous solution. The physicochemical properties of MgO and m-MgO were characterized by FT-IR, XRD, VSM and Zeta potential. The effects of solution pH, temperature, and oscillation time on the adsorption of U(Ⅵ) by MgO and m-MgO were investigated. The results show that the optimal conditions for uranium adsorption by MgO and m-MgO are pH=3.5, adsorbent dosage of 10 mg, and oscillation time of 720 min. The adsorption process conforms to the pseudo-second-order kinetic model and the Sips isotherm adsorption model, with a theoretical adsorption capacity of 454.16 mg/g, and the increase of temperature is conducive to the spontaneous adsorption. Therefore, m-MgO is expected to be used to separate and recover uranium from radioactive wastewater.

uranium  /  magnetism  /  adsorption  /  magnesium oxide  /  porous  /  separation  /  recycle  /  removing
宋鹏旺, 付玉琴, 周亮, 蔡为钱, 熊玲珊, 王有群. 磁性多孔MgO的合成及其对U(Ⅵ)的吸附性能研究. 湿法冶金, 2024 , 43 (6) : 665 -671 . DOI: 10.13355/j.cnki.sfyj.2024.06.011
Pengwang SONG, Yuqin FU, Liang ZHOU, Weiqian CAI, Lingshan XIONG, Youqun WANG. Preparation of Magnetic and Porous MgO and Its Adsorption Performance for U(Ⅵ)[J]. Hydrometallurgy of China, 2024 , 43 (6) : 665 -671 . DOI: 10.13355/j.cnki.sfyj.2024.06.011
在当前全球能源需求持续增长、传统能源资源日益匮乏形势下,世界各国均将铀资源的勘探、开发和利用置于高度优先的战略地位[1],但与此同时,铀污染给人体和环境带来的潜在危害也不容忽视。铀在人体内的过量积累可能导致严重的健康问题,包括癌症、畸形等多种疾病[2];铀矿开采和水冶及转化等过程中产生的含铀放射性废水,未经过妥善处理排放会严重污染土地、水源和空气,破坏生态环境。此外,铀污染还具有隐蔽性、持久性和累积性[3]。因此,采取有效措施对含铀废水进行处理具有十分重要的意义。
目前,低浓度含铀废水的处理方法主要包括化学沉淀法[4]、离子交换法、溶剂萃取法[5]、膜分离法[6]和吸附法[7]等,其中,吸附法因具有高效、快速和操作方便等优点而备受青睐[8]。吸附剂作为吸附法的关键,其性能直接影响处理效果。MgO是一种典型的碱金属氧化物,原料易得,安全无毒。目前,Mg-MOF-74衍生的多孔MgO/碳复合材料[9]、多孔氧化镁泡沫[10]、超亲水表面纳米氧化镁生物碳复合材料均可高效吸附铀[11]。由于纳米MgO尺寸较小,存在难以回收的问题[12],但将磁性纳米材料与MgO结合则能同时达到磁性分离与增大比表面积的目的。因此,研究了以Fe3O4为磁核、MgCl2为镁源,采用溶胶-凝胶法制备m-MgO,并用于去除水溶液中的U(Ⅵ)。通过FT-IR、XRD、VSM及Zeta电位表征了MgO和m-MgO的理化性质,系统探讨了影响吸附的主要因素、动力学、等温线和热力学,推测了m-MgO与U(Ⅵ)相互作用机制。
原料:铀标准溶液(1 000 mg/L),购于上海麦克林生化科技股份有限公司,不同铀初始质量浓度(20~200 mg/L)的溶液由铀标准溶液稀释得到。
试剂:氯化镁(AR)、盐酸(37%)、硝酸(68%),购于国药化学试剂有限公司;氢氧化钠(AR)、2,4-二硝基苯酚(AR),购于西陇化工股份有限公司;十六烷基三甲基溴化铵(CTAB,AR),购于山东国化化学有限公司;氯乙酸(AR)、偶氮胂(Ⅲ)(AR)、乙酸钠(AR),购于上海阿拉丁生化科技股份有限公司。
主要仪器设备:电热恒温鼓风干燥箱(DHG-9073BS-III,天津泰斯特仪器有限公司),紫外-可见分光光度计(SP-721E,上海光谱仪器公司),红外光谱仪(FTS-65A,美国Bio-RAD公司),Zeta电位仪(Stabino PMX 400,美国Microtrac公司),振动样品磁强计(8600系列,Lake Shore公司),多晶X射线衍射仪(D8 advance,德国布鲁克公司),孔隙率仪(V-Sorb 4800P,北京金埃谱科技有限公司)。
将5.76 g无水乙酸钠和2.16 g氯化铁溶解在80 mL乙二醇中,200 ℃溶剂热法反应10 h,将产物取出,用去离子水清洗后,于60 ℃下干燥,记为Fe3O4
配制浓度为8.9×10-4 mol/L的含CTAB溶液,取10 mL作为阳离子表面活性剂;在恒定搅拌条件下,加入500 mL浓度为1 mol/L的MgCl2溶液,继续搅拌1 h;然后,滴加浓度1 mol/L的氨水溶液,直至澄清溶液产生微量Mg(OH)2溶胶(pH=10.0);将溶胶搅拌2 h后放置2 d,使溶胶缩合成固体凝胶纳米颗粒;过滤收集凝胶颗粒并用蒸馏水洗涤数次,直至滤液中无氯离子;将纳米颗粒在100 ℃下干燥24 h,并在500 ℃高温炉中煅烧3 h,以诱导MgO纳米颗粒结晶;最后,将适量Fe3O4纳米颗粒悬浮在50 mL蒸馏水中,加入适量上述MgO颗粒,超声处理溶液30 min,过滤,滤渣在100 ℃下干燥24 h,记为m-MgO。
称取一定量m-MgO于不同锥形瓶中,分别加入50 mL一定浓度的铀标准溶液,在一定温度下振荡一定时间,移取振荡后溶液于2 mL离心管中离心,再移取一定体积的离心液于25 mL容量瓶中,采用偶氮胂Ⅲ分光光度法测定吸附后溶液中铀浓度,计算吸附量qt。计算公式为
qt=$\frac{({\rho }_{0}-{\rho }_{t})V}{m}$。
式中:qt—m-MgO对铀的吸附量,mg/g;ρ0—溶液中铀初始质量浓度,mg/L;ρt—吸附t时间时溶液中铀质量浓度,mg/L;V—溶液体积,L;m—m-MgO质量,g。
图1(a)为MgO、m-MgO和吸附铀的m-MgO(m-MgO+U)的FT-IR图谱。在592、1 385 和1 622 cm-1出现的峰分别是Mg—O—MgO和O—Mg—O伸缩和弯曲振动峰;在3 450 cm-1处出现了O—H吸收峰,可能是由煅烧后样品中残留Mg(OH)2或样品吸附水引起;在2 120 cm-1处出现了Fe—O的特征吸收峰,说明Fe3O4成功负载至MgO表面;在908 cm-1处出现了$\mathrm{UO}_{2}^{2+}$的特征吸收峰,表明m-MgO已成功吸附U(Ⅵ)[13]
图1(b)为Fe3O4、MgO、m-MgO和m-MgO+U的XRD图谱。在37°、42°和62°处出现的峰为MgO的特征衍射峰,分别对应MgO的(111)、(200)和(220)晶面;对于m-MgO、m-MgO+U和Fe3O4在30°、35°、52°和57°出现的衍射峰分别对应Fe3O4的(220)、(311)、(422)和(511)晶面,说明MgO与Fe3O4成功复合,且m-MgO吸附U(Ⅵ)后的结构未发生改变。
使用振动样品磁强计(VSM)测定m-MgO在磁场强度为-3 000~3 000 kA/m范围内的比饱和磁化强度,结果如图2所示。可以看出:Fe3O4与m-MgO的比饱和磁化强度分别为43.0、22.5 (A·m2)/kg,表明Fe3O4与MgO成功复合。
称取少量m-MgO材料分散于去离子水中进行磁分离试验,结果如图3所示。可以看出,在外加磁场作用下,m-MgO材料会定向移动至磁铁一侧,使溶液变得澄清,说明m-MgO可借助外加磁场快速实现固液分离。
不同pH下Fe3O4、MgO、m-MgO的Zeta电位如图4所示。可以看出:Fe3O4、MgO和m-MgO的Zeta电位随pH升高而降低,等电点的pH分别是4.7、5.3和3.7,表明MgO与Fe3O4复合后,m-MgO的等电点处pH负移,在pH较低时表面带负电。
图5为m-MgO和MgO的N2吸附—脱附等温线。可以看出:2条吸附—脱附等温线均为第Ⅲ类吸附等温线[14],吸附气体量随组分分压增加而上升;曲线下凹是因为N2之间的相互作用比N2与m-MgO和MgO之间的相互作用更强,导致初期N2较难于吸附,吸附速率较慢,但随吸附继续进行,出现了自加速现象。
m-MgO和MgO的比表面积及孔结构参数见表1。可以看出:MgO和m-MgO的比表面积(SBET)分别为4.77和25.30 m2/g,总孔容(Vt)分别为0.03和0.16 cm3/g,孔径(Dm)分别为36.13和46.05 nm。这表明,MgO与Fe3O4复合后,比表面积和总孔容均增大,有利于U(Ⅵ)的吸附[14]
在铀初始质量浓度50 mg/L、温度25 ℃、振荡时间720 min、吸附剂用量10 mg条件下,考察溶液pH对MgO和m-MgO吸附U(Ⅵ)的影响,试验结果如图6所示。可以看出:溶液pH在1.0~5.0之间时,随pH升高,m-MgO对U(Ⅵ)的吸附量先增大后减小。这是因为当pH<3.5时,MgO和m-MgO表面带正电,此时溶液中U(Ⅵ)主要形态为$\mathrm{UO}_{2}^{2+}$(见图7),材料表面的正电荷与带正电荷的铀酰离子产生静电排斥,同时,由于大量存在的H+与铀竞争吸附位点,导致材料的吸附能力较差;随pH升高,暴露出更多的吸附位点,使得材料对铀的吸附能力进一步增强[15],并在pH=3.5时吸附量达最大(223.10 mg/g);当pH>3.5时,U(Ⅵ)以UO2OH+、(UO2)2$\mathrm{(OH)}_{2}^{2+}$及(UO2)3$\mathrm{(OH)}_{5}^{+}$等形式存在于溶液中,空间位阻增大,导致吸附量下降。由图6还可看出:pH在3.5~5.0范围内时,MgO对U(Ⅵ)有较强的吸附能力,吸附量随pH变化较小,基本维持在119.15 mg/g左右,表明MgO对U(Ⅵ)的吸附主要为表面配合作用[16]。因此,确定MgO和m-MgO对U(Ⅵ)吸附的最佳pH为3.5。
在铀初始质量浓度50 mg/L、温度25 ℃、溶液pH=3.5和吸附剂用量10 mg条件下,考察反应时间对MgO和m-MgO吸附U(Ⅵ)的影响,试验结果如图8所示。可以看出:随反应时间延长,MgO和m-MgO对U(Ⅵ)的吸附量逐渐增大,在吸附720 min后增大趋势变缓。因此,确定最佳反应时间为720 min。
为研究MgO和m-MgO对U(Ⅵ)的吸附机制,分别采用准一级(PFO)和准二级(PSO)吸附动力学模型[17]分析吸附过程。PFO和PSO的动力学拟合曲线如图8所示,拟合参数见表2。PFO和PSO的表达式如下:
$q_{t}=q_{\mathrm{e}}\left(1-\mathrm{e}^{-k_{1} t}\right) ;$
$q_{t}=\frac{q_{\mathrm{e}}^{2} k_{2} t}{1+q_{\mathrm{e}}^{2} k_{2} t} 。$
式中:k1—PFO吸附速率常数,min-1;k2—PSO吸附速率常数,g/(mg·min);qt—吸附t时间时的吸附量,mg/g;qe—平衡吸附量,mg/g。
表2看出:MgO和m-MgO吸附U(Ⅵ)铀的准二级动力学模型拟合线性相关度R2均高于准一级动力学的R2;准二级动力学模型拟合的理论平衡吸附量与试验值更为接近。说明MgO和m-MgO对U(Ⅵ)的吸附更符合准二级动力学模型,吸附主要是由化学作用控制。
浓度是影响吸附剂去除U(Ⅵ)的重要因素,在溶液pH=3.5、温度25 ℃、振荡时间720 min、吸附剂用量10 mg条件下,考察溶液中U(Ⅵ)初始质量浓度对MgO和m-MgO吸附U(Ⅵ)的影响,试验结果如图9所示。
图9看出:随溶液中U(Ⅵ)初始质量浓度升高,MgO和m-MgO对U(Ⅵ)的吸附量先增大后趋于平衡,这是因为随U(Ⅵ)质量浓度升高,固相与液相之间的浓度梯度也逐步增大,使得吸附作用逐渐增强;但随U(Ⅵ)质量浓度持续升高,m-MgO的吸附位点逐渐被占据,无法吸附更多的U(Ⅵ),吸附量增幅减缓,最终达到吸附饱和状态。
为进一步确定吸附材料与吸附质之间的相互作用机制,试验分别采用Langmuir、Freundlich和Sips等温吸附模型对吸附过程进行拟合分析。
Langmuir等温吸附模型假设吸附为单分子层吸附,吸附剂表面性质均一。其非线性表达方程[18]见式(4):
qe=$\frac{{k}_{L}{q}_{m}{\rho }_{e}}{1+{k}_{L}{\rho }_{e}}$。
式中:kL—Langmuir等温吸附平衡常数,L/mg,与吸附能量有关,数值越大,吸附亲和力越大;qm—最大吸附量,mg/g。
Freundlich等温吸附模型假设吸附为多分子层吸附,吸附位点分布不均匀,其非线性表达式见式(5):
qe=kF${\rho }_{e}^{1/n}$。
式中:n—与吸附强度和吸附量相关参数;kF—Freundlich等温吸附平衡常数,mg1-1/n·L1/n·g-1,与吸附强度和吸附量相关。
Sips等温吸附模型假设吸附质分子在固体表面上的吸附可以是单层也可以是多层的,但每一层的吸附都遵循Langmuir等温吸附的规律,其非线性表达式见式(6):
qe=$\frac{{q}_{m}k{ }_{S}{\rho }_{e}^{\beta }}{1+{k}_{S}{\rho }_{e}^{\beta }}$。
式中:qm—最大吸附量,mg/g;ks—吸附能量相关参数,Lβ·mg1-β·g-β;β—吸附强度相关参数。
通过计算试验数据,以qeρe作图,得到Langmuir、Freundlich和Sips等温吸附模型的拟合曲线(见图9)。根据曲线的斜率和截距计算相关拟合参数,结果见表3
表3看出:m-MgO吸附U(Ⅵ)的Sips等温吸附拟合相关系数R2为0.99,略高于Langmuir和Freundlich模型,且最大吸附量为454.16 mg/g,与试验值(439.1 mg/g)接近,说明m-MgO吸附过程更符合Sips等温吸附模型,材料表面的活性位点为非均匀分布,U(Ⅵ)在m-MgO材料表面的吸附过程为非均相吸附;MgO吸附U(Ⅵ)的Langmuir等温吸附拟合相关系数R2高于Sips和Freundlich等温吸附模型,说明MgO吸附U(Ⅵ)的过程更符合Langmuir等温吸附模型,属于单层均一吸附。
在铀初始质量浓度为50 mg/g、溶液pH=3.5、振荡时间720 min、吸附剂用量10 mg条件下,考察温度条件对MgO和m-MgO吸附U(Ⅵ)的影响,试验结果如图10所示。
图10看出:随温度升高,m-MgO对U(Ⅵ)的吸附量逐渐增大,升高温度有利于m-MgO对U(Ⅵ)的吸附。结合其他对吸附过程影响较大的因素,综合考虑,选择25 ℃(298 K)为最适宜温度。采用热力学函数进一步考察温度对m-MgO吸附U(Ⅵ)的影响。通过计算吉布斯自由能变(ΔG)、焓变(ΔH)、熵变(ΔS,判断吸附类型[19]。吸附反应的ΔG、ΔH、ΔS与热力学平衡常数kd之间的关系见式(6)~(8)。
kd=$\frac{{q}_{e}}{{\rho }_{e}}$;
ln kd=$\frac{\Delta S}{R}$-$\frac{\Delta H}{RT}$;
ΔGH-TΔS
式中:kd—热力学平衡常数,L/g;R—理想气体摩尔常数,8.314 J/(K·mol);ΔH—焓变,J/mol;ΔG—吉布斯自由能变,J/mol;ΔS—熵变,J/(mol·K)。
ln kd-1/T关系曲线如图11所示,热力学参数计算结果见表4。可以看出:m-MgO吸附铀的ΔH>0、ΔS>0、ΔG<0,证实吸附是吸热熵增自发的过程,且随温度升高,ΔG值逐渐减小,表明升高温度有利于吸附的自发进行。
以Fe3O4为内核、MgCl2为镁源成功制备了可用于吸附铀的复合磁性氧化镁(m-MgO)吸附材料,m-MgO的比表面积较MgO有大幅增加。m-MgO对U(Ⅵ)的最佳吸附条件为:溶液pH=3.5,吸附剂用量10 mg,吸附时间720 min。m-MgO对U(Ⅵ)的吸附符合准二级动力学模型和Sips等温吸附模型,理论吸附量为454.16 mg/g,吸附过程是熵增自发进行,升高温度有助于吸附。m-MgO吸附材料有望用于从放射性废水中分离回收铀。
  • 江西省自然科学基金青年项目(20202BABL213026)
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2024年第43卷第6期
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doi: 10.13355/j.cnki.sfyj.2024.06.011
  • 接收时间:2024-05-10
  • 首发时间:2025-09-10
  • 出版时间:2024-12-20
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  • 收稿日期:2024-05-10
基金
江西省自然科学基金青年项目(20202BABL213026)
作者信息
    1 东华理工大学 核资源与环境国家重点实验室, 江西 南昌 330013
    2 江西省地质调查勘查院基础地质调查所实验测试中心, 江西 南昌 330000
    3 江西省地质局物化探大队实验测试中心, 江西 南昌 330201

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王有群(1988—),男,博士,副教授,主要研究方向为核化工。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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