Article(id=1322161648685659119, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322161562689847927, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1727193600000, receivedDateStr=2024-09-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793157501621, onlineDateStr=2026-10-28, pubDate=1756051200000, pubDateStr=2025-08-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793157501621, onlineIssueDateStr=2026-10-28, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793157501621, creator=13701087609, updateTime=1793157501621, updator=13701087609, issue=Issue{id=1322161562689847927, tenantId=1146029695717560320, journalId=1225396423026438145, year='2025', volume='45', issue='8', pageStart='1', pageEnd='278', issueExtLink='null', onlineDate='null', pubDate='1756051200000', pubDateStr='2025-08-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793157481119, creator='13701087609', updateTime=1793158854568, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322167323411198934, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322161562689847927, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322167323411198935, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322161562689847927, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=178, endPage=185, ext={EN=ArticleExt(id=1322161648870208497, articleId=1322161648685659119, tenantId=1146029695717560320, journalId=1225396423026438145, language=EN, title=Study on the Improvement of Bioretention Facilities by Vanadium-Titanium Magnetite Tailings Substrate, columnId=null, journalTitle=Mining Research and Development, columnName=null, runingTitle=null, highlight=null, articleAbstract=

In order to improve the operation efficiency of bioretention facilities and expand the resource utilization of vanadium-titanium magnetite tailings, vanadium-titanium magnetite tailings were used as the substrate modifier of bioretention facilities to explore the feasibility and decontamination effect of vanadium-titanium magnetite tailings substrate to improve the bioretention facilities. The results show that the leaching toxicity of main heavy metal ions (Cr, Mn, Zn, Cu) in vanadium-titanium magnetite tailings is lower than the standard limit. The adsorption of TP, NH3 and by vanadium-titanium magnetite tailings substrate to the Freundlich adsorption isotherm model. The adsorption process of TP and NH3 is dominated by chemical adsorption, which is controlled by liquid film diffusion and intraparticle diffusion, while the adsorption process of is dominated by physical adsorption. The removal rates of TP, NH3 and by vanadium-titanium magnetite tailings substrate are 97.2%, 91.4% and 70.5%, respectively. The average effluent concentration meets the Class Ⅱ, Class Ⅳ and Class V water standards respectively in the Surface Water Environmental Quality Standard (GB 3838-2002).

, authors=Wei ZHANG1, 2, 3, Wanqiu YANG1, 2, 3, Xiaoqing CHEN1, 2, 3, Kaixuan LI1, 2, 3, Liqian SONG1, 2, 3, Luhua XU1, 2, 3, Zicheng QIU1, 2, 3, Simin LI1, 2, 3, authorsList=Wei ZHANG, Wanqiu YANG, Xiaoqing CHEN, Kaixuan LI, Liqian SONG, Luhua XU, Zicheng QIU, Simin LI, authorCompany=null, correspAuthors=Simin 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, fund=null), CN=ArticleExt(id=1322161658626158680, articleId=1322161648685659119, tenantId=1146029695717560320, journalId=1225396423026438145, language=CN, title=钒钛磁铁尾矿基质改良生物滞留设施的研究, columnId=1226462295417598973, journalTitle=矿业研究与开发, columnName=矿山安全与环保, runingTitle=null, highlight=null, articleAbstract=

为改善生物滞留设施运行效能和拓展钒钛磁铁尾矿资源化途径,以钒钛磁铁尾矿作为生物滞留设施的基质改良剂,探究钒钛磁铁尾矿基质改良生物滞留设施的可行性及除污效果。结果表明,钒钛磁铁尾矿主要重金属离子(Cr、Mn、Zn、Cu)浸出毒性低于标准限值;钒钛磁铁尾矿基质对TP、NH3和的吸附符合Freundlich吸附等温模型,TP和NH3吸附过程以化学吸附为主,受液膜扩散和颗粒内扩散共同控制,吸附过程则以物理吸附为主;钒钛磁铁尾矿基质对TP、NH3和的去除率分别为97.2%、91.4%、70.5%,出水平均浓度分别满足《地表水环境质量标准》(GB3838—2002)中Ⅱ类、Ⅳ类和Ⅴ类水体标准。

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张炜(1981—),男,河北邯郸人,硕士,教授,主要从事海绵城市建设理论与技术方面的研究。E-mail:

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李思敏(1968—),男,陕西咸阳人,教授,博士研究生导师,主要从事雨水利用及资源化方面的研究。E-mail:
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Journal of Cleaner Production, 2023, 395:136457., articleTitle=Enhanced nutrient removal of agricultural waste-pyrite bioretention system for stormwater pollution treatment, refAbstract=null)], funds=[Fund(id=1322161668138840264, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, awardId=2021YFC1910601, language=CN, fundingSource=国家重点研发计划项目(2021YFC1910601), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1322161658923954266, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, xref=1., ext=[AuthorCompanyExt(id=1322161658936537179, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, companyId=1322161658923954266, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.Hebei Technology Innovation Center for Water Pollution Control and Water Ecological Remediation, Hebei University of Engineering, 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language=EN, label=Table 1, caption=

Main physicochemical properties

, figureFileSmall=null, figureFileBig=null, tableContent=
介质含湿率ω/%pH电导率σ/(μS/cm)渗透速率K/(mm/h)
种植土0.868.29108.8018
钒钛磁铁尾矿0.138.5699.15279
钒钛磁铁尾矿基质0.588.45114.70138
), ArticleFig(id=1322161667463557314, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, language=CN, label=表1, caption=

主要理化性质

, figureFileSmall=null, figureFileBig=null, tableContent=
介质含湿率ω/%pH电导率σ/(μS/cm)渗透速率K/(mm/h)
种植土0.868.29108.8018
钒钛磁铁尾矿0.138.5699.15279
钒钛磁铁尾矿基质0.588.45114.70138
), ArticleFig(id=1322161667560026307, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, language=EN, label=Table 2, caption=

Fitting parameters of adsorption kinetic model

, figureFileSmall=null, figureFileBig=null, tableContent=
指标准一级动力学方程准二级动力学方程颗粒内扩散模型
qe/(mg/kg)K1R2qe/(mg/kg)K2R2cKtR2
TP45.940.4110.96652.940.0100.9928.2410.420.880
NH381.380.3310.99095.400.0040.99510.5518.730.855
29.660.1520.98440.250.0050.9790.986.090.946
), ArticleFig(id=1322161667690049732, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, language=CN, label=表2, caption=

吸附动力学模型拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
指标准一级动力学方程准二级动力学方程颗粒内扩散模型
qe/(mg/kg)K1R2qe/(mg/kg)K2R2cKtR2
TP45.940.4110.96652.940.0100.9928.2410.420.880
NH381.380.3310.99095.400.0040.99510.5518.730.855
29.660.1520.98440.250.0050.9790.986.090.946
), ArticleFig(id=1322161667803295941, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, language=EN, label=Table 3, caption=

Fitting parameters for isotherm adsorption model

, figureFileSmall=null, figureFileBig=null, tableContent=
指标Langmuir 模型Freundlich 模型
KLqmax/(mg/kg)R2KF1/nR2
TP0.0222420.9101.1870.6540.992
NH30.0175090.93617.2540.1150.994
0.0152920.9008.8300.7240.982
), ArticleFig(id=1322161667916542151, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322161648685659119, language=CN, label=表3, caption=

等温吸附模型拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
指标Langmuir 模型Freundlich 模型
KLqmax/(mg/kg)R2KF1/nR2
TP0.0222420.9101.1870.6540.992
NH30.0175090.93617.2540.1150.994
0.0152920.9008.8300.7240.982
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钒钛磁铁尾矿基质改良生物滞留设施的研究
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张炜 1, 2, 3 , 杨婉秋 1, 2, 3 , 陈晓晴 1, 2, 3 , 李凯旋 1, 2, 3 , 宋立乾 1, 2, 3 , 徐露华 1, 2, 3 , 邱子诚 1, 2, 3 , 李思敏 1, 2, 3
矿业研究与开发 | 矿山安全与环保 2025,45(8): 178-185
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矿业研究与开发 |矿山安全与环保 2025 , 45 (8) : 178 -185
钒钛磁铁尾矿基质改良生物滞留设施的研究
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张炜1, 2, 3 , 杨婉秋1, 2, 3, 陈晓晴1, 2, 3, 李凯旋1, 2, 3, 宋立乾1, 2, 3, 徐露华1, 2, 3, 邱子诚1, 2, 3, 李思敏1, 2, 3
作者信息
  • 1.河北工程大学 河北省水污染控制与水生态修复技术创新中心,河北 邯郸市 056038
  • 2.河北工程大学 污水处理及资源化利用河北省工程研究中心,河北 邯郸市 056038
  • 3.河北工程大学 邯郸市水利用技术重点实验室,河北 邯郸市 056038
通讯作者:
李思敏(1968—),男,陕西咸阳人,教授,博士研究生导师,主要从事雨水利用及资源化方面的研究。E-mail:
作者简介:

张炜(1981—),男,河北邯郸人,硕士,教授,主要从事海绵城市建设理论与技术方面的研究。E-mail:

Study on the Improvement of Bioretention Facilities by Vanadium-Titanium Magnetite Tailings Substrate
Wei ZHANG1, 2, 3 , Wanqiu YANG1, 2, 3, Xiaoqing CHEN1, 2, 3, Kaixuan LI1, 2, 3, Liqian SONG1, 2, 3, Luhua XU1, 2, 3, Zicheng QIU1, 2, 3, Simin LI1, 2, 3
Affiliations
  • 1.Hebei Technology Innovation Center for Water Pollution Control and Water Ecological Remediation, Hebei University of Engineering, Handan, Hebei 056038, China
  • 2.Hebei Engineering Research Center of Sewage Treatment and Resource Utilization, Hebei University of Engineering, Handan, Hebei 056038, China
  • 3.Handan Key Laboratory of Water Utilization Technology, Hebei University of Engineering, Handan, Hebei 056038, China
出版时间: 2025-08-25
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为改善生物滞留设施运行效能和拓展钒钛磁铁尾矿资源化途径,以钒钛磁铁尾矿作为生物滞留设施的基质改良剂,探究钒钛磁铁尾矿基质改良生物滞留设施的可行性及除污效果。结果表明,钒钛磁铁尾矿主要重金属离子(Cr、Mn、Zn、Cu)浸出毒性低于标准限值;钒钛磁铁尾矿基质对TP、NH3和的吸附符合Freundlich吸附等温模型,TP和NH3吸附过程以化学吸附为主,受液膜扩散和颗粒内扩散共同控制,吸附过程则以物理吸附为主;钒钛磁铁尾矿基质对TP、NH3和的去除率分别为97.2%、91.4%、70.5%,出水平均浓度分别满足《地表水环境质量标准》(GB3838—2002)中Ⅱ类、Ⅳ类和Ⅴ类水体标准。

生物滞留设施  /  钒钛磁铁尾矿基质  /  可行性分析  /  吸附特性  /  除污效果

In order to improve the operation efficiency of bioretention facilities and expand the resource utilization of vanadium-titanium magnetite tailings, vanadium-titanium magnetite tailings were used as the substrate modifier of bioretention facilities to explore the feasibility and decontamination effect of vanadium-titanium magnetite tailings substrate to improve the bioretention facilities. The results show that the leaching toxicity of main heavy metal ions (Cr, Mn, Zn, Cu) in vanadium-titanium magnetite tailings is lower than the standard limit. The adsorption of TP, NH3 and by vanadium-titanium magnetite tailings substrate to the Freundlich adsorption isotherm model. The adsorption process of TP and NH3 is dominated by chemical adsorption, which is controlled by liquid film diffusion and intraparticle diffusion, while the adsorption process of is dominated by physical adsorption. The removal rates of TP, NH3 and by vanadium-titanium magnetite tailings substrate are 97.2%, 91.4% and 70.5%, respectively. The average effluent concentration meets the Class Ⅱ, Class Ⅳ and Class V water standards respectively in the Surface Water Environmental Quality Standard (GB 3838-2002).

Bioretention facility  /  Vanadium-titanium magnetite tailings substrate  /  Feasibility analysis  /  Adsorption characteristic  /  Decontamination effect
张炜, 杨婉秋, 陈晓晴, 李凯旋, 宋立乾, 徐露华, 邱子诚, 李思敏. 钒钛磁铁尾矿基质改良生物滞留设施的研究. 矿业研究与开发, 2025 , 45 (8) : 178 -185 .
Wei ZHANG, Wanqiu YANG, Xiaoqing CHEN, Kaixuan LI, Liqian SONG, Luhua XU, Zicheng QIU, Simin LI. Study on the Improvement of Bioretention Facilities by Vanadium-Titanium Magnetite Tailings Substrate[J]. Mining Research and Development, 2025 , 45 (8) : 178 -185 .
20世纪50年代,钒钛磁铁矿开发利用被纳入国家战略,但其尾矿长期堆存会对区域生态环境产生较大的风险,尾矿“三化”处置势在必行[1]。当前,尾矿处置途径主要包括二次选别、回填、建材原料和农业生产等[2-5],但因受经济、环境及市场等因素限制,仍未从根本上解决尾矿资源化利用的问题。因此,尾矿的合理处置受到学者的广泛关注。
为应对城市化发展引发的雨洪灾害[6]等问题,我国提出以低影响开发为理念的海绵城市建设[7],可实现雨水径流的量质调控。其中,生物滞留设施作为低影响开发雨水系统的典型海绵生态技术,在国内外应用广泛[8-9]。基质是生物滞留设施发挥功能的关键,而传统生物滞留设施基质组成较为单一,对N、P等污染物的去除不够稳定[10-11]。对此,常通过添加功能性材料强化生物滞留设施的雨水量质调控性能[12]。如简单处理后的建筑废砖[13]、钢渣-稻壳灰[14]和木屑-无烟煤-天然沸石[15-16]等材料对常规污染物及重金属具有较好去除效果,但在应用时需注意基质本身析出对环境产生的二次污染[17]。随着环境保护政策的逐步收紧,“一砂难求”现象愈演愈烈。钒钛磁铁尾矿含有SiO2、CaO、Fe2O3、MgO等金属氧化物[18],不仅能够作为土壤改良剂,也可以通过离子交换、氧化还原、络合沉淀等作用处理环境污染物[19],可代替工程砂用作改良生物滞留设施的基质,从而提高除污效果。
本文利用钒钛磁铁尾矿基质改良生物滞留设施,通过理化性质和污染物浸出特性分析评估钒钛磁铁尾矿基质用于改良生物滞留设施的可行性,探究钒钛磁铁尾矿基质的吸附特性,并考察改良生物滞留设施的除污效果,以期通过以“废”治“废”提升海绵设施运行效果,拓展钒钛磁铁尾矿处置途径。
生物滞留设施试验装置如图1所示,采用外径160 mm的UPVC管试制,高度为1 000 mm,从上到下依次为超高层(50 mm)、蓄水层(100 mm)、基质层(750 mm)和砾石层(100 mm)。蓄水层上沿设外径15 mm的溢流管,砾石层底部设外径15 mm的出流管。为防止装置内壁水流短流,预先进行打毛处理。
试验用尾矿取自河北省承德市某钒钛磁铁尾矿库,经自然晾晒,采用“四分法”混合均匀后随机取样。土壤取自华北地区典型表层种植土,将自然风干的土壤(<2 mm)及尾矿砂(<2 mm)按体积比1:2均匀混合制备成改良基质(以下简称“钒钛磁铁尾矿基质”)。
为掌握钒钛磁铁尾矿的理化特性,测定其粒度分配、化学成分、微观形貌,以及3种基质的含湿率、pH值、电导率和渗透速率。粒度组成采用筛分法测定;化学成分采用电感耦合等离子谱仪(ICP)测定;微观形貌采用扫描电镜(SEM)表征;含湿率采用重量法测定;pH采用pH计测定;电导率采用电导率仪测定;渗透速率采用环刀法测定。
污染物浸出量和浸出特性是评估基质改良可行性的先决条件[20]。将自然风干的尾矿样品置于烘箱内,在105 ℃温度下烘干至恒重,存于干燥器内备用。采用逐步稀释法将氢氧化钠、硝酸和去离子水配制为pH=7的浸提剂,探究其对尾矿浸出特性的影响。重金属浸出浓度测试方法:称取100 g过2 mm筛的尾矿样品,与1 000 mL浸提剂混合(固液比为1:10),在(25±2)℃条件下,以150 r/min的频率连续振荡10 d,每隔24 h,取20 mL浸出溶液,用硝酸酸化至pH<2,并通过载有0.45 μm滤膜的过滤装置过滤,将过滤后的样品置于冰箱保存待测。采用电感耦合等离子体质谱法[21](ICP-MS)测定重金属离子(Hg、Cd、As、Se、Cr、Mn、Cu和Zn)的浓度。
为探究钒钛磁铁尾矿对污染物的吸附性能,选用TP、NH3和作为目标污染物进行吸附试验。
称取干燥种植土、钒钛磁铁尾矿基质和砂土基质各3 g, 加入150 mL浓度均为5 mg/L的KH2PO4、NH4Cl和KNO3混合溶液于250 mL锥形瓶中,设置3组平行样。将锥形瓶放入恒温振荡器以(25±2) ℃、150 r/min的条件连续振荡24 h, 再以5 000 r/min转速离心5 min, 取上层清液过0.45 μm滤膜。采用1.3节中介绍的检测方法测定滤液污染物的浓度。
称取钒钛磁铁尾矿基质3 g,置于分别装有250 mL含KH2PO4(10 mg/L)、NH4Cl(10 mg/L)和KNO3(10 mg/L)的溶液中,放入恒温振荡器以(25±2) ℃、150 r/min连续振荡0.5 h、1 h、2 h、4 h、6 h、8 h、12 h、24 h,每组试验取3次平行样,计算污染物吸附量。
在25 ℃条件下,在一系列250 mL锥形瓶中分别放入3 g钒钛磁铁尾矿基质,然后分别加入 0.5, 1,2, 3,5, 10, 15, 20, 40 mg/L的KH2PO4,以及 0.5, 5,8, 10, 15, 20, 40, 80 mg/L的NH4Cl和KNO3溶液,放入恒温振荡器中,以150 r/min的转速振荡24 h,每组试验取 3 次平行样。
由于降雨随机性强,生物滞留设施采用人工配水模拟降雨径流进行试验,自来水储存在150 L水桶内,将配制好的药剂投加水桶并充分搅拌混匀。原水中径流污染物TP、NH3、的浓度分别为1 mg/L、10 mg/L、5 mg/L[22],采用KH2PO4、NH4Cl、KNO3配置溶液。
为模拟钒钛磁铁尾矿基质生物滞留设施的运行效果,进行了人工模拟降雨动态试验。将基质装填在生物滞留设施柱内,用自来水以20 L/d的速率持续进水两周,压实基质并冲刷基质表面残余杂质。待出水水质稳定后,开始模拟人工降雨,每个试验周期为3 d,第一天进水,落干期为2 d,进水时间30 min。出水60 min后于出水口取样分析,检测水中TP、NH3和浓度,每组试验重复2次。
每次试验结果取3个平行样的平均值进行分析,水质各项指标检测按照《水及废水监测分析方法》执行。
准一级动力学方程、准二级动力学方程[23]和粒子内扩散模型分别见式(1)、式(2)和式(3)。
式中:qe为平衡吸附量,mg/g;qt为t时刻吸附量,mg/g;K1为准一级吸附速率常数;K2为准二级吸附速率常数;Kt为颗粒内扩散速率常数;c为常数。
常见等温吸附模型有Langmuir模型和Freundlich模型[24],公式见式(4)和式(5)。
式中:qmax为最大吸附量,mg/g;C为溶液平衡浓度,mg/L;KL为Langmuir模型的常数因子;KF为Freundlich模型常数因子;1/n为吸附强度与表面异质性的相关常数。
钒钛磁铁尾矿的粒度分布如图2所示。由图2可知,粒度分布集中在0.35 mm以上,粒度较大,0.35 mm以上的颗粒含量为85.10%。在生物滞留设施中添加钒钛磁铁尾矿,不仅可以提高砂粒含量、降低成本,对调控水量、净化水质也极为重要[25]。钒钛磁铁尾矿的矿物成分如图3所示,由图3可知,钒钛磁铁尾矿主要成分为SiO2、CaO、Fe2O3、MgO和Al2O3,占比为95.68%。已有研究证实金属氧化物能提高对氮、磷的吸附效果[26],因此,钒钛磁铁尾矿可提高水质净化的效果。对钒钛磁铁尾矿进行SEM扫描分析,结果如图4所示。由图4可以看出,其表面结构粗糙,存在大量吸附位点,可提升对污染物的吸附能力。
种植土、钒钛磁铁尾矿和钒钛磁铁尾矿基质主要理化性质测定结果见表1。钒钛磁铁尾矿基质可以改善土壤结构,增强土壤渗透性、持水性和保水性,利于植物生长[27],在pH为8.29~8.45的弱碱性环境下,钒钛磁铁尾矿基质对雨水径流中污染物有较好的去除效果[28-29]。
钒钛磁铁尾矿的重金属浸出是限制其作为基质改良剂的关键因素,通过浸出试验,测定钒钛磁铁尾矿中重金属(Hg、Cd、As、Se、Cr、Mn、Cu和Zn)的最高浸出量和浸出速度。试验中,Hg、Cd、As和Se均未检出,故本文仅讨论Cr、Mn、Cu和Zn的浸出特性,以评估钒钛磁铁尾矿用作改良剂的可行性。
钒钛磁铁尾矿重金属浸出浓度结果如图5所示。在pH为7时,钒钛磁铁尾矿与浸提剂不同接触时间后,重金属Cu、Cr、Mn和Zn浸出浓度与浸出时间成正相关,不同重金属的浸出特性有所区别。Cu和Cr的浸出浓度呈现先上升后下降的变化趋势,且在前4天的溶解释放速率较高,此时溶液pH为碱性,重金属离子与OH-结合生成氢氧化物沉淀,随后浓度呈现下降趋势。Zn和Mn在前6天处于快速释放阶段,6~10 d处于缓慢释放阶段,且在浸出时间为7 d时,重金属浸出浓度基本达到平衡。这是因为初始阶段重金属浸出浓度较低,基质中可溶性重金属快速溶于溶液,随着时间延长,可溶性重金属不断减少,溶出速率变缓,浸出液重金属浓度逐渐增加,表明钒钛磁铁尾矿的重金属浸出行为主要受液相扩散的影响。
钒钛磁铁尾矿基质对TP、NH3和的吸附动力学模型拟合曲线如图6所示,基于准一级动力学方程、准二级动力学方程和颗粒内扩散模型,对TP、NH3和吸附特性进行拟合分析,拟合参数见表2。从图6可以看出,钒钛磁铁尾矿基质对TP、NH3和的吸附量均随着时间的延长而增加。对污染物的吸附表现出前期吸附速度快,后期缓慢的特点。在初始阶段,溶液中氮磷浓度较高,钒钛磁铁尾矿基质表面存在大量空余吸附点位和可交换离子,加快其与污染物的接触效率,吸附速度快;随着钒钛磁铁尾矿基质表面电性中和及空余吸附点位逐渐减少,吸附量的增长开始变得缓慢,最终趋于平衡,这与蒋艳红等[30]的研究结果一致。
对比表3中三种动力学方程的决定系数R2可知,钒钛磁铁尾矿基质对TP和NH3吸附的准二级动力学方程的R2分别为0.992和0.995,说明准二级动力学方程对TP和NH3吸附过程的描述更为符合,这与张芙蓉等[31]的研究结论相同,吸附过程主要以化学吸附为主,由液膜扩散和颗粒的内扩散共同控制,同时还可能包括外部液膜扩散、表面吸附和颗粒内扩散等作用[32]。而的吸附过程满足准一级动力学方程,以物理吸附为主。此外,准一级动力学拟合钒钛磁铁尾矿基质对TP、NH3和的平衡吸附量分别为45.94, 81.38, 29.66 mg/kg;准二级动力学拟合钒钛磁铁尾矿基质对TP、NH3和的平衡吸附量分别为52.94, 95.40, 40.25 mg/kg。
不同浓度下钒钛磁铁尾矿基质经过24 h振荡吸附后,将TP、NH3和的吸附结果绘制成等温吸附曲线,如图7所示。由图7可知,随着溶液平衡浓度的增加,尾矿基质对TP、NH3和的吸附量不断增大,随后逐渐减缓。这是因为在低浓度条件下,钒钛磁铁尾矿基质的吸附位点相对较多,可用于TP、NH3和的吸附,随着浓度升高,吸附位点相对减少,吸附速率变缓,并逐渐趋于平稳[33-34]。
Langmuir等温吸附模型被认为是均一理想单分子层的化学吸附,Freundlich模型则被认为是非均一多分子层物理吸附[35]。等温吸附模型拟合参数见表3,从表3可以看出,Langmuir模型(R2≥0.900)和Freundlich模型(R2≥0.982)均能较好地拟合钒钛磁铁尾矿基质对TP、NH3和的吸附特征,说明其对TP、NH3和的吸附过程由化学吸附和物理吸附协同作用。Langmuir公式中,最大理论吸附值qmax分别为242 mg/kg、509 mg/kg和292 mg/kg。在Freundlich公式中,KF和n均为与吸附能力和吸附量有关的参数,KF越大,吸附能力越强。当0.1<1/n<1时,更容易发生吸附,1/n分别为0.654, 0.115和0.724,表明TP、NH3和易于吸附在钒钛磁铁尾矿基质的表面。
通过动态试验,考察钒钛磁铁尾矿基质对各污染物的去除效果,如图8所示。由图8可知,在种植土、砂土基质和钒钛磁铁尾矿基质吸附拦截作用下,TP、NH3和的去除率分别为94.7%~98.0%、85.5%~91.4%和63.2%~88.1%,种植土的吸附效果最优,而后依次为钒钛磁铁尾矿基质和砂土基质。钒钛磁铁尾矿基质的TP、NH3和出水平均浓度分别为 0.028 mg/L、0.85 mg/L、1.474 mg/L,分别满足《地表水环境质量标准》(GB 3838—2002)中Ⅱ类、Ⅳ类和Ⅴ类水体标准。相较于种植土,砂土基质和钒钛磁铁尾矿基质的吸附率虽有所下降,但渗透速率优于种植土[36]。这表明可以利用钒钛磁铁尾矿代替工程砂,既可以改善设施渗透性能,也可以达到去除污染物的效果。
(1)钒钛磁铁尾矿的主要矿物成分为SiO2、CaO、Fe2O3、MgO和Al2O3,粒度集中在0.3 mm以上,微观形貌呈现丰富的喉道和孔隙,可提供大量吸附位点;钒钛磁铁尾矿渗透速率为279 mm/h,符合生物滞留设施的设计要求。
(2)钒钛磁铁尾矿浸出释放的主要重金属为Cu、Cr、Mn和Zn,且重金属毒性浸出浓度低于限值标准。
(3)钒钛磁铁尾矿基质对TP和NH3的吸附过程符合准二级动力学方程,更符合准一阶方程,TP和NH3的吸附在8 h达到平衡,二者的吸附均由液膜扩散和颗粒内扩散多步骤共同控制。Freundlich等温吸附模型能更好地描述钒钛磁铁尾矿基质对TP、NH3和的吸附过程,且以多分子层吸附为主。
(4)钒钛磁铁尾矿基质对TP和NH3的去除率为97.2%、91.4%,而对的去除率为70.5%,去除效果优于砂土基质,出水平均浓度均满足《地表水环境质量标准》(GB3838—2002)中Ⅱ类、Ⅳ类和Ⅴ类水质标准。
  • 国家重点研发计划项目(2021YFC1910601)
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2025年第45卷第8期
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  • 接收时间:2024-09-25
  • 首发时间:2026-10-28
  • 出版时间:2025-08-25
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  • 收稿日期:2024-09-25
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国家重点研发计划项目(2021YFC1910601)
作者信息
    1.河北工程大学 河北省水污染控制与水生态修复技术创新中心,河北 邯郸市 056038
    2.河北工程大学 污水处理及资源化利用河北省工程研究中心,河北 邯郸市 056038
    3.河北工程大学 邯郸市水利用技术重点实验室,河北 邯郸市 056038

通讯作者:

李思敏(1968—),男,陕西咸阳人,教授,博士研究生导师,主要从事雨水利用及资源化方面的研究。E-mail:
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
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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