微米级管状氧化镁团簇体的合成及其吸附磷的性能

doi:10.19964/j.issn.1006-4990.2021-0760

摘要/Abstract

摘要：

利用自组装技术合成了微米级管状团簇体碱式碳酸镁（MTBMg），进一步热解得到管状团簇体氧化镁（MTMgO）。采用X射线衍射（XRD）、扫描电镜（SEM）和BET分析对MTMgO的结构、形貌进行了表征。结果表明，在水解温度为80 ℃、反应物浓度为0.6 mol/L条件下利用自组装技术构筑了MTBMg，热解后形成的MTMgO保留了前驱体MTBMg的相似结构，且具有丰富的微米尺寸氧化镁，为磷的吸附提供了活性位点。磷模拟废水吸附结果表明，在废水pH为3~11条件下MTMgO表现出优异的吸附磷的性能，其吸附过程满足Langmuir等温吸附模型；当废水pH=10时MTMgO对磷的理论吸附量最大，为2 120.12 mg/g。动力学分析结果表明，对于MTMgO吸附磷的过程准一级和准二级动力学方程拟合度均较高，是化学吸附与物理吸附并存的过程，随着MTMgO加入量增加由化学吸附为主导向物理吸附为主导转变。当废水中磷的质量浓度为800 mg/L时，吸附剂对磷的去除率仍达到96.47%。

关键词: 氧化镁, 碱式碳酸镁, 磷, 等温吸附, 自组装

Abstract:

Micron?tubular?basic magnesium carbonate clusters（MTBMg） was synthesized by self?assembly technology，and micron?tubular?magnesium oxide clusters（MTMgO） was obtained by further pyrolysis.The composition and morphology of MTMgO were characterized by X-ray diffraction（XRD），scanning electron microscopy（SEM） and BET analysis.The results showed that the MTBMg was synthesized at hydrolysis temperature of 80 ℃ and reaction concentration of 0.6 mol/L，the MTMgO retained the similar structure of precursors and had abundant micro?sized MgO particles，which provided active sites for phosphate adsorption.The adsorption results of phosphorus simulated wastewater showed that the MTMgO exhibited excellent phosphate adsorption performance at wastewater pH of 3~11 and the isothermal adsorption was fitted with the Langmuir model.The maximum adsorption capacity of MTMgO was 2 120.12 mg/g at pH of 10.The kinetic results showed that the phosphate adsorption by MTMgO fitted both pseudo first order kinetics primary and pseudo second order kinetics models，indicating that the adsorption of phosphate could be described by both chemisorption and physical adsorption mechanism.With the increase dosage of MTMgO，the adsorption process shifted from chemisorption?dominated to physisorption?dominated.When the mass concentration of phosphorus in wastewater was 800 mg/L，the phosphate removal rate by adsorbent was 96.47%.

Key words: MgO, basic magnesium carbonate, phosphate, isothermal adsorption, self-assembly

中图分类号:

梁海,原天龙,王婉婷,杨云洪,梁文洁,王晓民,邓信忠. 微米级管状氧化镁团簇体的合成及其吸附磷的性能[J]. 无机盐工业, 2022, 54(9): 77-84.

LIANG Hai,YUAN Tianlong,WANG Wanting,YANG Yunhong,LIANG Wenjie,WANG Xiaomin,DENG Xinzhong. Synthesis of micron?tubular?magnesium oxide clusters and its adsorption performance for phosphate[J]. Inorganic Chemicals Industry, 2022, 54(9): 77-84.

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参考文献 26

[1]	SHAKOOR M B， YE Zhilong， CHEN Shaohua.Engineered biochars for recovering phosphate and ammonium from wastewater:A review[J].Science of the Total Environment，2021，779.Doi:10.1016/j.scitotenv.2021. doi: 10.1016/j.scitotenv.2021.
[2]	FANG Liping， WU Baile， CHAN J K M， et al.Lanthanum oxide nanorods for enhanced phosphate removal from sewage:A response surface methodology study[J].Chemosphere，2018，192:209-216.
[3]	MORELLIB， HAWKINST R，NIBLICKB，et al.Critical review of eutrophication models for life cycle assessment[J].Environmental Sci ence & Technology，2018，52（17）:9562-9578.
[4]	WEI Ting， LI Qiangang， WANG Hongjie， et al.Advanced phosphate and nitrogen removal in water by La-Mg composite[J].Environmental Research，2021，193.Doi:10.1016/j.envres.2020.110529. doi: 10.1016/j.envres.2020.110529.
[5]	ZHU Danchen， YANG Haiping， CHEN Xu， et al.Temperature⁃dependent magnesium citrate modified formation of MgO nanoparticles biochar composites with efficient phosphate removal[J].Che⁃ mosphere，2021，274.Doi:10.1016/j.chemosphere.2021.129904. doi: 10.1016/j.chemosphere.2021.129904.
[6]	ZHAO Chenxi， WANG Bing， THENG B K G， et al.Formation and mechanisms of nano⁃metal oxide⁃biochar composites for pollutants removal:A review[J].Science of the Total Environment，2021，767. Doi:10.1016/j.scitotenv.2021.145305. doi: 10.1016/j.scitotenv.2021.145305.
[7]	GHAEDI A M， VAFAEI A.Applications of artificial neural networks for adsorption removal of dyes from aqueous solution:A review[J].Advances in Colloid and Interface Science，2017，245:20-39.
[8]	GHAEDI A M， PANAHIMEHR M， NEJAD A R S， et al.Factorial experimental design for the optimization of highly selective adsorption removal of lead and copper ions using metal organic framework MOF-2（Cd）[J].Journal of Molecular Liquids，2018，272:15-26.
[9]	LUO Haoyu， WANG Yijie， WEN Xiaoqing， et al.Key roles of the crystal structures of MgO-biochar nanocomposites for enhancing phosphate adsorption[J].Science of the Total Environment，2021，766. Doi:10.1016/j.scitotenv.2020.142618. doi: 10.1016/j.scitotenv.2020.142618.
[10]	GUO Wanli， NAZIM H， LIANG Zongsuo， et al.Magnesium deficiency in plants:An urgent problem[J].The Crop Journal，2016，4（2）:83-91.
[11]	YE Tiantian， MIN Xiangyu， LI Xinju， et al.Improved holding and releasing capacities of coal gangue toward phosphate through alkali⁃activation[J].Chemosphere，2022，287.Doi:10.1016/j.chemosphere.2021.32382. doi: 10.1016/j.chemosphere.2021.32382.
[12]	XI Huan， JIANG Haoli， ZHAO Dan， et al.Highly selective adsorption of phosphate from high⁃salinity water environment using MgO-loaded and sodium alginate⁃immobilized bentonite beads[J].Journal of Cleaner Production，2021，313.Doi:10.1016/j.jclepro. 2021.127773. doi: 10.1016/j.jclepro. 2021.127773.
[13]	XIA Yan， DONG Kangyu， XIANG Xiangmei， et al.Phosphorus hyperaccumulation in nano-MgO using a circular recovery process based on multiple phase transitions from periclase to bruci⁃te[J].Science of the Total Environment，2020，727.Doi:10.1016/j.scitotenv.2020.138510. doi: 10.1016/j.scitotenv.2020.138510.
[14]	杨斌，苏琪，杨高玲，等.喷雾干燥法制备氧化镁材料及其吸附性能[J].化工学报，2018，69（7）:3068-3075.
	YANG Bin， SU Qi， YANG Gaoling， et al.Preparation and adsorption properties of magnesium oxide via spray drying[J].CIESC Journal，2018，69（7）:3068-3075.
[15]	YU Zhichao， XU Chonghe， YUAN Kangkang， et al.Template-free synthesis of MgO mesoporous nanofibers with superior adsorption for fluoride and Congo red[J].Ceramics International，2018，44（8）:9454-9462.
[16]	郑力.氧化镁/果胶复合除磷剂的制备及其除磷机理研究[D].武汉:华中科技大学，2017.
	ZHENG Li.Identification of the mechanism for phosphates removal by using A modified phosphate absorbent prepared from MgO and pectin[D].Wuhan:Huazhong University of Science and Technology，2017.
[17]	葛立发.纳米氧化镁复合材料的制备与性能研究[D].武汉:华中科技大学，2019.
	GE Lifa.Investigation on preparation of magnesium oxide nanocompositesand their properties[D].Wuhan:Huazhong University of Science and Technology，2019.
[18]	WANG Tao， XU Youfeng， SU Qiying， et al.Hierarchical porous nanosheet⁃assembled MgO microrods with high adsorption capacity[J].Materials Letters，2014，116:332-336.
[19]	JIN Zhen， JIA Yong， ZHANG Kaisheng， et al.Effective removal of fluoride by porous MgO nanoplates and its adsorption mechanism[J].Journal of Alloys and Compounds，2016，675:292-300.
[20]	张雅君.小分子自组装形成纳米管的机理研究[D].苏州:苏州大学，2017.
	ZHANG Yajun.Formation mechanism of nanotubes via self⁃assembly of a small molecule[D].Suzhou:Soochow University，2017.
[21]	覃利琴，杨黄根，陈德，等.辅助溶剂热法合成纳米晶自组装CaWO₄:Tb³⁺微球及其发光性能[J].无机盐工业，2021，53（1）:36-39，43.
	QIN Liqin， YANG Huanggen， CHEN De， et al.Assistanted solvothermal synthesis of nanocrystalline self⁃assembled CaWO₄:Tb³⁺ microspheres and luminescence properties[J].Inorganic Chemicals Industry，2021，53（1）:36-39，43.
[22]	LIU Xiaoning， FU Junyan， TANG Yiwei， et al.Mg-coordinated self-assembly of MgO-doped ordered mesoporous carbons for selective recovery of phosphorus from aqueous solutions[J].Chemical Engineering Journal，2021，406.Doi:10.1016/j.cej.2020.126748. doi: 10.1016/j.cej.2020.126748.
[23]	常军，贾福康，胡成山，等.电解锰渣基沸石对锰离子的吸附性能研究[J].无机盐工业，2019，51（9）:61-66.
	CHANG Jun， JIA Fukang， HU Chengshan， et al.Adsorption of manganese ion by zeolite synthesized from electrolytic manganese residue[J].Inorganic Chemicals Industry，2019，51（9）:61-66.
[24]	LIU Jiwei， JIANG Jianguo， AIHEMAITI A， et al.Removal of phosphate from aqueous solution using MgO-modified magnetic biochar derived from anaerobic digestion residue[J].Journal of Environmental Management，2019，250.Doi:10.1016/j.jenvman.2019.109438. doi: 10.1016/j.jenvman.2019.109438.
[25]	XIA Peng， WANG Xuejing， WANG Xin， et al.Struvite crystallization combined adsorption of phosphate and ammonium from aqueous solutions by mesoporous MgO loaded diatomite[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects，2016，506:220-227.
[26]	李友凤，敖克厚，樊磊磊，等.氧化铈-二氧化硅介孔材料制备及对铜离子的吸附性能[J].无机盐工业，2020，52（12）:34-39.
	LI Youfeng， AO Kehou， FAN Leilei， et al.Preparation of CeO₂-SiO₂ mesoporous material and its adsorption property for copper ions[J].Inorganic Chemicals Industry，2020，52（12）:34-39.

c（Mg²⁺）/ （mol·L^-1）	Langmuir模型			Freundlich模型
c（Mg²⁺）/ （mol·L^-1）	q/ （mg·g^-1）	K_L/ （L·mg^-1）	R²	n	K_F/ （mg^1-ⁿ ·L ⁿ ·g^-1）	R²
0.4	1 441.83	0.15	0.97	4.15	408.80	0.91
0.5	1 616.10	0.17	0.96	4.30	506.00	0.86
0.6	1 810.85	0.14	0.96	5.10	649.00	0.81
0.7	1 539.83	0.21	0.97	3.96	489.95	0.90
0.8	1 303.28	0.26	0.95	5.34	481.90	0.85

水解温度/℃	Langmuir模型			Freundlich模型
水解温度/℃	q/ （mg·g^-1）	K_L/ （L·mg^-1）	R²	n	K_F/ （mg^1-ⁿ ·L ⁿ ·g^-1）	R²
50	1 503.6	0.12	0.96	3.62	393.03	0.86
60	1 609.9	0.10	0.99	3.30	367.16	0.92
70	1 661.4	0.10	0.99	5.97	678.40	0.86
80	1 810.8	0.14	0.97	5.12	649.02	0.81
90	1 656.3	0.10	0.96	3.51	408.95	0.85

pH	Langmuir模型			Freundlich模型
pH	q/ （mg·g^-1）	K_L/ （L·mg^-1）	R²	K_F/ （mg^1-ⁿ ·L ⁿ ·g^-1）	n	R²
3	1 615.52	0.19	0.94	474.76	3.93	0.86
5	1 810.85	0.14	0.96	649.02	5.12	0.81
7	1 922.37	0.08	0.98	396.91	3.22	0.93
9	2 034.37	0.07	0.99	363.07	3.08	0.96
10	2 120.12	0.11	0.95	539.95	3.96	0.85
11	1 975.92	0.10	0.97	463.01	3.56	0.92

吸附剂加入量/（g·L^-1）	准一级方程			准二级方程
吸附剂加入量/（g·L^-1）	q/ （mg·g^-1）	K₁/ min^-1	R²	q/ （mg·g^-1）	K₂/ （g·mg^-1·min^-1）	R²
0.25	1 541.90	0.035	0.981	1 735.56	2.77×10^-6	0.982
1.00	375.15	0.050	0.978	425.10	1.56×10^-4	0.993
2.00	193.28	0.100	0.996	214.99	6.21×10^-4	0.980

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