氢键有机框架纳滤膜净化磷酸中金属离子的研究

doi:10.19964/j.issn.1006-4990.2024-0662

Abstract

Abstract:

Wet-process phosphoric acid offers greater economic advantages over its thermal-process counterpart.However，it introduces substantial quantities of metal ions during production，which requires economical and environmentally sustainable removal strategies.Nanofiltration membranes，which efficiently separate ions and molecules with minimal environmental impact，have demonstrated considerable potential in the purification of phosphoric acid.However，the extremely low pH and high viscosity of crude phosphoric acid significantly hinder the applicability of conventional nanofiltration membranes，often leading to membrane degradation and reduced permeability.For this reason，a highly permeable，acid-resistant nanofiltration membrane（HOF-HDI） was synthesized for phosphoric acid purification by interfacial polymerization，employing C₃H₈N₆SO₄（HOF） as the aqueous-phase monomer and hexamethylene diisocyanate（HDI） as the organic-phase monomer.The successful fabrication of the membrane was confirmed through FT-IR and XPS.By optimizing the monomer concentration and thermal curing temperature，the optimal preparation conditions were established.The experimental results revealed that the HOF-HDI membrane achieved a permeation rate of 0.85 L/（h·m²·bar） in phosphoric acid solution（20% mass fraction in terms of P₂O₅）.The rejection rates for Al³⁺，Mg²⁺，and Fe³⁺ ions decreased in the following order：Al³⁺（51.00%），Mg²⁺ （47.99%），Fe³⁺（46.33%）.Static and dynamic acid resistance tests demonstrated the superior acid stability of the modified membrane.Investigating the influence of monomer type on membrane structure revealed that cavity-containing monomers enhance membrane permeability.Collectively，these findings underscored the great promise of the HOF-HDI nanofiltration membrane for effective phosphoric acid purification.

Key words: nanofiltration membrane, acid-resistant, high permeability, hydrogen-bonded organic framework, phosphoric acid

CLC Number:

TQ126.31

WANG Jiandong, GONG Jianping, CHEN Jianjun, LI Jun, LIU Daijun. Study on removing metal ions from phosphoric acid by hydrogen-bonded organic framework nanofiltration membrane[J]. Inorganic Chemicals Industry, 2025, 57(11): 23-30.

Figures/Tables 7

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

References 30

[1]	WANG Jiandong， JIANG Yuxing， TIAN Zhuangzhuang，et al.Highly permeable acid-stable poly（sulfonamide-urea） nanofiltration membrane for purifying phosphoric acid［J］.Separation and Purification Technology，2025，362：131662.
[2]	KHALESS K， CHANOURI H， AMAL S，et al.Wet process phosphoric acid purification using functionalized organic nanofiltration membrane［J］.Separations，2022，9（4）：100.
[3]	MERROUNE A， BRAHIM J AIT， ACHIOU B，et al.Closed-loop purification process of industrial phosphoric acid：Selective recovery of heavy metals and rare earth elements via solvent extracti- on［J］.Desalination，2024，580：117515.
[4]	GONG Xiaokang， HU Chao， JIN Yanru，et al.Preparation of refined phosphoric acid with recycling of raffinate acid by the extraction of metal impurities［J］.Journal of Cleaner Production，2024，434：140158.
[5]	GONG Jianping， HOU Shaochun， XU Tao，et al.Separation of phosphorus from mixed rare earth concentrate for enrichment of REEs［J］.Industrial & Engineering Chemistry Research，2022，61（51）：18854-18869.
[6]	田壮壮，陈建钧，金央，等.纳滤膜脱除磷酸中金属离子的实验研究［J］.无机盐工业，2023，55（12）：133-139，158.
	TIAN Zhuangzhuang， CHEN Jianjun， JIN Yang，et al.Experimental study on removing metal ions from phosphoric acid by nanofiltration membrane［J］.Inorganic Chemicals Industry，2023，55（12）：133-139，158.
[7]	GONZÁLEZ M P， NAVARRO R， SAUCEDO I，et al.Purificationof phosphoric acid solutions by reverse osmosis and nanofiltration［J］.Desalination，2002，147（1/2/3）：315-320.
[8]	DIALLO H， RABILLER-BAUDRY M， KHALESS K，et al.On the electrostatic interactions in the transfer mechanisms of iron during nanofiltration in high concentrated phosphoric acid［J］.Journal of Membrane Science，2013，427：37-47.
[9]	ZHANG Yanqiu， WANG Hao， GUO Jing，et al.Ice-confined synthesis of highly ionized 3D-quasilayered polyamide nanofiltration membranes［J］.Science，2023，382（6667）：202-206.
[10]	ZHAO Guoke， ZHANG Yang， LIU Yiqun.pH stable thin film composite poly（amine-urea） nanofiltration membranes with excellent rejection performance［J］.Separation and Purification Technology，2023，320：124108.
[11]	PARK H M， ISMAEL M， TAKABA H，et al.Acid-resistant thin-film composite nanofiltration membrane prepared from polyamide-polyurea and the behavior of density functional theory study［J］.Journal of Membrane Science，2022，645：120175.
[12]	LI Xiang， LIN Weibin， SHARMA V，et al.Polycage membranes for precise molecular separation and catalysis［J］.Nature Communications，2023，14：3112.
[13]	YU Biao， XING Jinlong， ZHANG Peng，et al.Hydrogen-bonded organic framework nanosheets with rich free oxygen atoms for NO₂ sensing［J］.Inorganic Chemistry，2025，64（3）：1258-1262.
[14]	LI Jinghong， YUAN Zhengyi， LIANG Ruicong，et al.Capturing alkanes from natural gas by using a hydrogen-bonded organic framework composed of tetracarboxylic acid［J］.Crystal Growth & Design，2025，25（3）：502-507.
[15]	巩传芳.基于氢键的有机框架材料的制备与性质研究［D］.青岛：中国石油大学（华东），2017.
	GONG Chuanfang.Synthesis and property investigations of hydrogen bonded organic frameworks［D］.Qingdao：China University of Petroleum（East China），2017.
[16]	JI Wenyan， DUAN Feng， SU Chunlei，et al.New insights into confined diffusion mechanisms of end-capping reagent regulated interfacial polymerization［J］.Journal of Membrane Science，2023，681：121754.
[17]	MI Zhiming， LIAO Lintao， MENG Lingjun，et al.Chelidonic acid-regulated synthesis of asymmetric polyamide nanofiltration membrane：Mechanisms and separation performance［J］.Separation and Purification Technology，2025，360：131031.
[18]	LIU Beibei， ZHANG Shuo， YAO Zheng，et al.Carbon nitride quantum dot-based thin-film nanocomposite membranes for efficient dye removal［J］.ACS Applied Nano Materials，2023，6（18）：16297-16308.
[19]	CHEN Guijing， LI Xifan， LI Xin，et al.Active-passive synergistic alleviation of membrane scaling from groundwater by grafting charged positive monomers on the surface of nanofiltration membranes［J］.Desalination，2025，599：118436.
[20]	CAO Yang， WAN Yinhua， CHEN Chulong，et al.Preparation of acid-resistant nanofiltration membrane with dually charged separation layer for enhanced salts removal［J］.Separation and Purification Technology，2022，292：120974.
[21]	CAO Yang， LUO Jianquan， CHEN Chulong，et al.Highly permeable acid-resistant nanofiltration membrane based on a novel sulfonamide aqueous monomer for efficient acidic wastewater treatment［J］.Chemical Engineering Journal，2021，425：131791.
[22]	LI Yu， ZHAO Guoke， PAN Guoyuan，et al.Thin-film composite nanofiltration membrane based on polysulfonamide for extremely acidic conditions［J］.Separation and Purification Technology，2025，356：129918.
[23]	LÓPEZ J， GIBERT O， CORTINA J L.Evaluation of an extreme acid-resistant sulphonamide based nanofiltration membrane for the valorisation of copper acidic effluents［J］.Chemical Engineering Journal，2021，405：127015.
[24]	ZHAO Guoke， SUN Jie， WAN Ying，et al.Scalable fabrication of poly（urea-thiourea） nanofiltration membrane elements for extreme pH conditions and efficient alkali recovery［J］.Separation and Purification Technology，2025，359：130563.
[25]	XIE Tengteng， CHEN Kuo， XIE Hongxue，et al.Highly negatively charged nanofiltration membrane prepared with a novel diamino-sulfonamide aqueous monomer for efficient removal of anionic dyes［J］.Applied Surface Science，2022，599：153914.
[26]	XU Shanshan， HE Rongrong， DONG Chenjun，et al.Acid stable layer-by-layer nanofiltration membranes for phosphoric acid purification［J］.Journal of Membrane Science，2022，644：120090.
[27]	ZHANG Yang， WAN Ying， LI Yu，et al.Thin-film composite nanofiltration membrane based on polyurea for extreme pH condition［J］.Journal of Membrane Science，2021，635：119472.
[28]	ZHANG Huiru， HE Qiming， LUO Jianquan，et al.Sharpening nanofiltration：Strategies for enhanced membrane selectivity［J］.ACS Applied Materials & Interfaces，2020，12（36）：39948-39966.
[29]	BARGEMAN Gerrald.Recent developments in the preparation of improved nanofiltration membranes for extreme pH conditions［J］.Separation and Purification Technology，2021，279：119725.
[30]	GARCÍA DOMÉNECH N， PURCELL-MILTON F， GUN KO Y K.Recent progress and future prospects in development of advanced materials for nanofiltration［J］.Materials Today Communications，2020，23：100888.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on removing metal ions from phosphoric acid by hydrogen-bonded organic framework nanofiltration membrane

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 7

References 30

Related Articles 15

Metrics

Comments

Recommended 0

[1]	HE Lin, YANG Guanghong, LI Jun. Study on process of reducing loss of eutectic phosphorus in phosphogypsum by dihydrate wet-process phosphoric acid system [J]. Inorganic Chemicals Industry, 2025, 57(9): 30-36.
[2]	WANG Bo, ZOU Yanming. Study on application of purifying wet-process phosphoric acid to produce battery-grade ammonium dihydrogen phosphate [J]. Inorganic Chemicals Industry, 2025, 57(8): 82-86.
[3]	YU Panpan, WU Zongjin, WU Lang, YANG Yi, LIN Qian, PAN Hongyan. Study on synergistic preparation of wood chip based carbon materials with phosphoric acid-sulfuric acid and their electrochemical properties [J]. Inorganic Chemicals Industry, 2025, 57(4): 79-88.
[4]	YANG Wenjuan, GONG Li, FU Yizhong, JIANG Wei, TU Zhongbing, XIE Mi, ZHU Guihua. Study on rapid deposition technology of wet process concentrated phosphoric acid [J]. Inorganic Chemicals Industry, 2025, 57(11): 59-64.
[5]	ZHANG Li, ZHANG Dan, PAN Hongyan, DONG Yonggang, LI Wenfei, QIN Hong. Study on preparation of low ash activated carbon by phosphoric acid method [J]. Inorganic Chemicals Industry, 2024, 56(2): 95-103.
[6]	HUANG Zhaojie, ZHAO Xiaoxu, WANG Haitao, CHANG Na, ZHANG Guoxin, XIE Yonglei, YIN Yanmei, LU Na, WANG Wei. Study on ultrafiltration+nanofiltration double membrane treatment of iron process iron phosphate production wastewater [J]. Inorganic Chemicals Industry, 2024, 56(11): 145-150.
[7]	JIN Shengshi, LIU Kaijie, LIU Qiuwen, ZHANG Yibo, YANG Xiangguang. Study on catalytic performance of phosphoric acid modified CeO₂ nanorod supported Pt catalyst for propane combustion [J]. Inorganic Chemicals Industry, 2024, 56(1): 141-148.
[8]	ZHANG Ying, LI Jun, JIN Yang, HUANG Meiying. Study on pyrolysis regeneration of activated carbon for Tributyl phosphate decolorization [J]. Inorganic Chemicals Industry, 2024, 56(1): 59-66.
[9]	LI Jiaqiang, LI Jun, JIN Yang, CHEN Ming. A gas chromatographic analysis method for acetic acid content in phosphoric acid and acetic acid mixed system [J]. Inorganic Chemicals Industry, 2023, 55(5): 115-120.
[10]	ZHOU Qinglie, WANG Baoqi, ZHANG Zhiye, ZHANG Yinghu, WANG Jian, YANG Lin. Development of new process of removing metal cations from wet-process phosphoric acid by extraction [J]. Inorganic Chemicals Industry, 2023, 55(3): 84-91.
[11]	TIAN Zhuangzhuang, CHEN Jianjun, JIN Yang, CHEN Ming, LI Jun, LIU Daijun. Experimental study on removing metal ions from phosphoric acid by nanofiltration membrane [J]. Inorganic Chemicals Industry, 2023, 55(12): 133-139.
[12]	HE Fuduo, YUAN Yifan, ZHOU Xiaohou, XU Lu, SUN Chongqing, WANG Xinlong, XU Dehua. Preparation of monoammonium phosphate containing amino acid from waste feathers by in situ acid hydrolysis of wet process of phosphoric acid [J]. Inorganic Chemicals Industry, 2023, 55(10): 100-105.
[13]	LIN Yuqing,ZHANG Yiren,QIU Yulong,ZHANG Jiayu,YU Jianguo. Progress and prospect of membrane technology in lithium extraction from salt lake brine [J]. Inorganic Chemicals Industry, 2023, 55(1): 33-45.
[14]	HE Lei,ZHU Ganyu,ZHENG Guangming,WU Wenfen,ZhANG Jianbo,LI Fang,LI Huiquan,CHEN Wen. Study on crystallization process and mechanism of phosphogypsum in wet process phosphoric acid system [J]. Inorganic Chemicals Industry, 2022, 54(7): 110-116.
[15]	FU Ziqi, ZHANG Cheng, SHENG Yong, JI Lijun. Study on preparation of phosphoric acid by leaching fluoride residue from wet-process phosphoric acid with organic solvents [J]. Inorganic Chemicals Industry, 2022, 54(7): 129-134.