无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ
研究与开发

树脂改性对脱硫离子液中氟氯离子脱除性能的影响研究

  • 王贵斌 ,
  • 张宏伟 ,
  • 刘丽娟 ,
  • 赵鹬 ,
  • 张栋强
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  • 1.兰州理工大学石油化工学院,甘肃 兰州 730050
    2.金川集团镍钴股份有限公司镍冶炼厂,甘肃 金昌 737100
王贵斌(1998— ),男,硕士研究生,研究方向为分离技术研究;E-mail:1603438498@qq.com
张栋强,教授,博士生导师,研究方向为膜分离技术和化工资源化利用技术研究;E-mail:zhangdq@lut.edu.cn

收稿日期: 2025-01-03

  网络出版日期: 2025-03-26

基金资助

甘肃省重点研发计划项目(23YFGA0051);甘肃省高等学校产业支撑计划项目(2024CYZC-17)

Study on effect of resin modification on removal performance of fluoride and chloride ions in desulfurization ionic liquid

  • WANG Guibin ,
  • ZHANG Hongwei ,
  • LIU Lijuan ,
  • ZHAO Yu ,
  • ZHANG Dongqiang
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  • 1. School of Petrochemical Engineering,Lanzhou University of Technology,Lanzhou 730050,China
    2. Nickel Smelting Plant,Jinchuan Group Nickel and Cobalt Company Limited,Jinchang 737100,China

Received date: 2025-01-03

  Online published: 2025-03-26

摘要

脱硫离子液中氟氯离子不断积累致其脱硫效率下降、离子液损耗和设备腐蚀加剧。因此,脱硫离子液中F-和Cl-的有效去除具有重要的研究意义。首先,优选717、D730、D301等6种阴离子交换树脂,考察其对脱硫离子液中F-和Cl-的脱除效果。结果表明,717树脂有着最佳的F-和Cl-脱除性能,其平衡吸附量分别为0.020 mg/g和3.506 mg/g。其次,对717树脂分别进行氯型、氢氧根型和硫酸根型改性,考察不同改性方法对单一F-、Cl-和SO42-脱除性能的影响。结果表明,氢氧根型树脂对单一的F-、Cl-和SO42-均具有最优的脱除性能,但其对SO42-的平衡吸附量远高于F-和Cl-;硫酸根型树脂对F-和Cl-的脱除效果略低于氢氧根型,但其对SO42-无吸附作用。在此基础上,探究不同改性717树脂对脱硫离子液中混合离子脱除性能的影响,发现硫酸根型树脂对F-和Cl-脱除效果最优。最后,通过FT-IR和XPS表征结果可知,硫酸根型树脂吸附F-和Cl-效果最优,主要因为氯型和氢氧根型树脂优先与SO42-发生离子交换,而硫酸根型树脂则是与F-和Cl-发生离子交换。

本文引用格式

王贵斌 , 张宏伟 , 刘丽娟 , 赵鹬 , 张栋强 . 树脂改性对脱硫离子液中氟氯离子脱除性能的影响研究[J]. 无机盐工业, 2026 , 58(1) : 18 -25 . DOI: 10.19964/j.issn.1006-4990.2025-0010

Abstract

The continuous accumulation of fluoride and chloride ions in the desulfurization ionic liquid leads to a decrease in desulfurization efficiency,increased ionic liquid loss,and exacerbated equipment corrosion.Therefore,the effective removal of F- and Cl- in desulfurization ionic liquid has significant research implications.Firstly,six anion exchange resins,such as 717,D730,and D301,were preferably selected to examine their effectiveness in removing F- and Cl- from the desulfurization ionic liquid.The results showed that the 717 resin had the best F- and Cl- removal performance with equilibrium adsorption capacities of 0.020 mg/g and 3.506 mg/g,respectively.Secondly,the 717 resin was modified with chlorine⁃,hydroxide⁃ and sulfate⁃type modifications to investigate the effects of different modifications on the single F-,Cl- and SO42- removal performance.The results showed that the hydroxide⁃type resin had the optimal removal performance for single F-,Cl- and SO42-,but its equilibrium adsorption capacity for SO42- was much higher than that for F- and Cl-.The sulfate⁃type resin was slightly less effective than the hydroxide⁃type for the removal of F- and Cl-,but had no adsorption effect on SO42-.On this basis,the effects of different modifications of 717 resin on the removal performance of mixed ions in desulfurization ionic liquid were investigated,and it was found that the sulfate⁃type resin had the best effect on the removal of F- and Cl-.Finally,the FT-IR and XPS characterization results showed that the sulfate⁃type resin adsorbed F- and Cl- optimally,mainly because the chlorine⁃type and hydroxide⁃type resins were preferentially ion⁃exchanged with SO42-,while the sulfate⁃type resin was ion⁃exchanged with F- and Cl-.

参考文献

[1] CHENG Teng, ZHOU Xincheng, YANG Linjun,et al.Emission characteristics of soluble ions in fine particulates in limestone?gypsum wet flue gas desulfurization system[J].Energy & Fuels202034(3):3836-3842.
[2] NING Huanyuan, TANG Ruijian, LI Changming,et al.Recent advances in process and materials for dry desulfurization of industrial flue gas:An overview[J].Separation and Purification Technology2025353:128425.
[3] LI Xueke, HAN Jinru, LIU Yan,et al.Summary of research progress on industrial flue gas desulfurization technology[J].Separation and Purification Technology2022281:119849.
[4] LIU Shaojun, YU Xinning, LIN Guoxin,et al.Insights into the effect of adsorption?desorption cycles on SO2 removal over an activated carbon[J].Aerosol and Air Quality Research201919(2):411-421.
[5] 张冠华,李桂珍,陶正淼,等.有色金属冶炼厂环集烟气离子液脱硫技术实践[J].硫酸工业2024(6):53-56.
  ZHANG Guanhua, LI Guizhen, TAO Zhengmiao,et al.Practice of collected fugitive gas ionic liquid desulfurization technology in nonferrous metal smelting plants[J].Sulphuric Acid Industry2024(6):53-56.
[6] 林敏清,刘航.离子液脱硫技术在环集烟气处理中的应用[J].有色冶金节能201834(5):43-47.
  LIN Minqing, LIU Hang.Application of ionic liquid desulfurization technology in treatment of flue gas collecting[J].Energy Saving of Nonferrous Metallurgy201834(5):43-47.
[7] 孙海明.离子液脱硫技术在铜冶炼环集烟气处理中的应用[J].当代化工研究2018(1):35-36.
  SUN Haiming.Application of ionic liquid desulfurization technology in copper smelting ring flue gas treatment[J].Modern Chemical Research2018(1):35-36.
[8] GAN Yonghai, WANG Xiaomeng, ZHANG Li,et al.Coagulation removal of fluoride by zirconium tetrachloride:Performance evaluation and mechanism analysis[J].Chemosphere2019218:860- 868.
[9] ZHAO Minghu, WANG Shixing, ZHANG Libo.Removal of chlorine from zinc sulfate solution:A review[J].Environmental Science and Pollution Research202229(42):62839-62850.
[10] SHI Jiaqian, ZHOU Chuncai, XU Shihai,et al.Ultrasound?improved removal of chloride ions from coking circulating water by Friedel′s salt precipitation:Efficiency enhancement and mech?anisms[J].Process Safety and Environmental Protection2024189:47-60.
[11] RAGHAV S, NAIR M, KUMAR D.Tetragonal prism shaped Ni-Al bimetallic adsorbent for study of adsorptive removal of fluoride and role of ion?exchange[J].Applied Surface Science2019498:143785.
[12] ZHANG Pengyu, ZHOU Huan, XU Zhixiong,et al.Study on the adsorption mechanism of chloride ion in aqueous solution on Mg/Al-CLDH modified by high temperature calcination[J].Inorganic Chemistry Communications2023150:110403.
[13] 冯江涛,王睎,赵旭阳,等.改性聚吡咯材料去除水中氟离子的性能[J].化工进展202140(7):4036-4046.
  FENG Jiangtao, WANG Xi, ZHAO Xuyang,et al.Removal of fluoride from water by modified polypyrrole[J].Chemical Industry and Engineering Progress202140(7):4036-4046.
[14] LUO Zhengwei, WANG Dan, ZHU Dongmei,et al.Separation of fluoride and chloride ions from ammonia?based flue gas desulfurization slurry using a two?stage electrodialysis[J].Chemical Engineering Research and Design2019147:73-82.
[15] HERNáNDEZ J, RUIZ D.Removal of chloride ions from a copper leaching solution,using electrodialysis,to improve the uranium extraction through ion?exchange[J].Journal of Hazardous Materials2021420:126582.
[16] RODRíGUEZ-IGLESIAS J, ALCALá L, MEGIDO L,et al.Removal of fluoride from coke wastewater by aluminum doped chelating ion?exchange resins:A tertiary treatment[J].Environmental Science and Pollution Research202229(6):8705-8715.
[17] SINGH S, GERMAN M, CHAUDHARI S,et al.Fluoride removal from groundwater using Zirconium Impregnated Anion Exchange Resin[J].Journal of Environmental Management2020263:110415.
[18] ABU-ARABI M K, EMEISH S, HUDAIB B I.Chloride removal from Eshidiya phosphate mining wastewater[J].Desalination and Water Treatment201351(7/8/9):1634-1640.
[19] FARAHBOD F.Laboratory evaluation of operating conditions for chloride removal from diethanolamine using ion exchange resin and introduction of optimal parameters[J].Applied Water Science202212(9):229.
[20] LI Yiming, YANG Zhongzhu, YANG Kaihua,et al.Removal of chloride from water and wastewater:Removal mechanisms and recent trends[J].Science of the Total Environment2022821:153174.
[21] 孙凤娟,刘万超,闫琨,等.离子交换树脂法去除脱硫废水中氯离子的研究[J].无机盐工业201951(6):45-48.
  SUN Fengjuan, LIU Wanchao, YAN Kun,et al.Removal of chloride ion from desulfurization wastewater by ion?exchange resin[J].Inorganic Chemicals Industry201951(6):45-48.
[22] NASR A BEN, CHARCOSSET C, AMAR R BEN,et al.Fluoride removal from aqueous solution by Purolite A520E resin:Kinetic and thermodynamics study[J].Desalination and Water Treatment201554(6):1604-1611.
[23] LI Huosheng, CHEN Yongheng, LONG Jianyou,et al.Simultaneous removal of thallium and chloride from a highly saline industrial wastewater using modified anion exchange resins[J].Journal of Hazardous Materials2017333:179-185.
[24] MEENAKSHI S, VISWANATHAN N.Identification of selective ion?exchange resin for fluoride sorption[J].Journal of Colloid and Interface Science2007308(2):438-450.
[25] DAVARPANAH M, AHMADPOUR A, ROHANI BASTAMI T.Preparation and characterization of anion exchange resin decorated with magnetite nanoparticles for removal of p-toluic acid from aqueous solution[J].Journal of Magnetism and Magnetic Materials2015375:177-183.
[26] AMIRI A, SHANBEDI M, ESHGHI H,et al.Highly dispersed multiwalled carbon nanotubes decorated with Ag nanoparticles in water and experimental investigation of the thermophysical pro?perties[J].The Journal of Physical Chemistry C2012116(5):3369-3375.
[27] DAVARPANAH M, MAGHREBI M, HOSSEINIPOUR E.Microwave?induced high surface functionalization of multi?walled carbon nanotubes for long?term dispersion in water[J].Applied Phy? sics A2014115(1):167-175.
[28] KANG Jiali, LI Junfeng, MA Chengxiao,et al.Goethite/montmorillonite adsorption coupled with electrocoagulation for improving fluoride removal from aqueous solutions[J].RSC Advances202212(12):7475-7484.
[29] 由晗杨,张毅,李文英,等.氯型季胺特种树脂吸附地下水NO3 -的动力学和热力学[J].工业水处理202040(4):49- 54.
  YOU Hanyang, ZHANG Yi, LI Wenying,et al.Sorption kinetics and thermodynamics study of NO3 - in groundwater by chlorinated quaternary amine special resin[J].Industrial Water Treatment202040(4):49-54.
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