工程科学学报，第41卷，第5期：600-609.2019年5月 Chinese Journal of Engineering,Vol.41,No.5:600-609,May 2019 D0L:10.13374/j.issn2095-9389.2019.05.006;htp:/journals..ustb.edu.cm 从腐泥土型红土镍矿制备共掺杂MgFe,O4物相转化 规律及催化性能 韩星，间治开，陈婷，张梅，郭敏⑧ 北京科技大学冶金与生态工程学院，北京100083 ☒通信作者，E-mail:guomin(@usth.cdu.cm 摘要采用酸浸-水热-煅烧法从腐泥土型红土镍矿中制备磁性多金属共掺杂型MgFe,0,异相类芬顿(Fenton)催化剂.利 用X射线衍射(XRD)、傅立叶红外光谱(FTIR)、扫描电子显微镜(SEM)和比表面积及孔径分布测定(BET-BH)等手段，考察 了煅烧温度对所制备产物结构、形貌和比表面积及孔径分布的影响，并研究了所制备产物作为异相Fenton催化剂降解罗丹明 B(RhB)溶液的催化活性.结果表明，水热合成产物为层状双（多）金属氢氧化物和尖晶石型MgFe,0,复合物.通过300℃的 燬烧，层状双（多）金属氢氧化物就能分解并生成MgF04;随着煅烧温度的提高，产物结晶度增加、粒径尺寸变大，形貌逐渐 生长为近球型颗粒且分散度渐渐提高，同时介孔数量减少、比表面积减小.经过500℃煅烧的试样H-C500显示出优异的催化 降解活性.在体系反应温度为45℃、pH值为6.44、催化剂用量为0.625g·L且H,02体积分数为1.0%的条件下，经过 300mi,10mg·L的罗丹明B溶液降解率可达到97.8%，同时总有机碳(T0C)去除率达到77.8%.重复使用3次后，催化剂 仍能保持较高活性，降解率和T0C去除率减少量分别少于3.0%和5.0%. 关键词腐泥土型红土镍矿：酸浸；水热；煅烧；共掺杂MgFe,O,;异相类Fenton催化剂 分类号TF803.21:TB34 Phase transformation and catalytic performance of metal-doped MgFe,O prepared from saprolite laterite HAN Xing,YAN Zhi-kai,CHEN Ting,ZHANG Mei,GUO Min School of Metallurgical and Ecological Engineering,University of Science and Technology Beijing,Beijing 100083,China XCorresponding author,E-mail:guomin@ustb.edu.cn ABSTRACT Heterogeneous Fenton-like method has attracted considerable attention because of its potential effectiveness in minerali- zation of organic contaminants in a wide range of reaction medium pH.Spinel ferrites MFe2O(M=Fe,Zn,Cu,Ni,Mn,Co)as het- erogeneous Fenton-like catalysts have been studied extensively due to their good catalytic activity,prominent physical and chemical stability,and excellent magnetic properties,which allow their easy separation from the reaction medium by magnetic field for further circular utilization.Considering the group of ferrites,limited research focused on the utilization of MgFeO as heterogeneous Fenton catalytic agent,whereas most of the catalysts are synthesized by pure chemical reagents.In this study,magnetic multi-metal co-doped MgFe,O heterogeneous Fenton-like catalyst was synthesized from saprolite laterite by acid leaching-hydrothermal calcination method. The effect of calcination temperature on the phase,morphology,specific surface area,and pore size distribution of samples were char- acterized by X-ray diffraction,scanning electron microscopy,Fourier-transform infrared,Brunauer-Emmett-Teller/Barrett-Joyner- Halenda analysis.The catalytic activity of the as-prepared products as heterogeneous Fenton catalysts for the degradation of Rhodamine 收稿日期：2018-04-28 基金项目：国家重点基础研究发展计划资助项目(2014CB643401):国家自然科学基金资助项目(51672025)；山西低附加值煤基资源高值利 用协同创新中心资助项目工程科学学报,第 41 卷,第 5 期:600鄄鄄609,2019 年 5 月 Chinese Journal of Engineering, Vol. 41, No. 5: 600鄄鄄609, May 2019 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2019. 05. 006; http: / / journals. ustb. edu. cn 从腐泥土型红土镍矿制备共掺杂 MgFe2 O4 物相转化 规律及催化性能 韩 星, 闫治开, 陈 婷, 张 梅, 郭 敏苣 北京科技大学冶金与生态工程学院, 北京 100083 苣通信作者, E鄄mail: guomin@ ustb. edu. cn 摘 要 采用酸浸鄄鄄水热鄄鄄煅烧法从腐泥土型红土镍矿中制备磁性多金属共掺杂型 MgFe2O4 异相类芬顿(Fenton)催化剂. 利 用 X 射线衍射(XRD)、傅立叶红外光谱(FTIR)、扫描电子显微镜(SEM)和比表面积及孔径分布测定(BET鄄鄄BJH)等手段,考察 了煅烧温度对所制备产物结构、形貌和比表面积及孔径分布的影响,并研究了所制备产物作为异相 Fenton 催化剂降解罗丹明 B(RhB)溶液的催化活性. 结果表明,水热合成产物为层状双(多)金属氢氧化物和尖晶石型 MgFe2O4 复合物. 通过 300 益 的 煅烧,层状双(多)金属氢氧化物就能分解并生成 MgFe2O4 ;随着煅烧温度的提高,产物结晶度增加、粒径尺寸变大,形貌逐渐 生长为近球型颗粒且分散度渐渐提高,同时介孔数量减少、比表面积减小. 经过 500 益煅烧的试样 H鄄C500 显示出优异的催化 降解活性. 在体系反应温度为 45 益 、pH 值为 6郾 44、催化剂用量为 0郾 625 g·L - 1 且 H2O2 体积分数为 1郾 0% 的条件下,经过 300 min,10 mg·L - 1的罗丹明 B 溶液降解率可达到 97郾 8% ,同时总有机碳(TOC)去除率达到 77郾 8% . 重复使用 3 次后,催化剂 仍能保持较高活性,降解率和 TOC 去除率减少量分别少于 3郾 0% 和 5郾 0% . 关键词 腐泥土型红土镍矿; 酸浸; 水热; 煅烧; 共掺杂 MgFe2O4 ; 异相类 Fenton 催化剂 分类号 TF803郾 21; TB34 收稿日期: 2018鄄鄄04鄄鄄28 基金项目: 国家重点基础研究发展计划资助项目(2014CB643401); 国家自然科学基金资助项目(51672025); 山西低附加值煤基资源高值利 用协同创新中心资助项目 Phase transformation and catalytic performance of metal鄄doped MgFe2O4 prepared from saprolite laterite HAN Xing, YAN Zhi鄄kai, CHEN Ting, ZHANG Mei, GUO Min 苣 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China 苣Corresponding author, E鄄mail: guomin@ ustb. edu. cn ABSTRACT Heterogeneous Fenton鄄like method has attracted considerable attention because of its potential effectiveness in minerali鄄 zation of organic contaminants in a wide range of reaction medium pH. Spinel ferrites MFe2O4 (M = Fe, Zn, Cu, Ni, Mn, Co) as het鄄 erogeneous Fenton鄄like catalysts have been studied extensively due to their good catalytic activity, prominent physical and chemical stability, and excellent magnetic properties, which allow their easy separation from the reaction medium by magnetic field for further circular utilization. Considering the group of ferrites, limited research focused on the utilization of MgFe2O4 as heterogeneous Fenton catalytic agent, whereas most of the catalysts are synthesized by pure chemical reagents. In this study, magnetic multi鄄metal co鄄doped MgFe2O4 heterogeneous Fenton鄄like catalyst was synthesized from saprolite laterite by acid leaching鄄鄄hydrothermal calcination method. The effect of calcination temperature on the phase, morphology, specific surface area, and pore size distribution of samples were char鄄 acterized by X鄄ray diffraction, scanning electron microscopy, Fourier鄄transform infrared, Brunauer鄄鄄 Emmett鄄鄄 Teller/ Barrett鄄鄄 Joyner鄄鄄 Halenda analysis. The catalytic activity of the as鄄prepared products as heterogeneous Fenton catalysts for the degradation of Rhodamine