SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2025, Vol. 82 ›› Issue (6): 153-164.DOI: 10.1016/j.cjche.2025.02.016

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Separation and recovery of V/W/Na from waste SCR catalyst leaching solution using membrane electrolysis—Ion morphology pretreatment solvent extraction-stripping method

Bo Pan1, Muneeb Ul Hassan Naseer1,2, Hao Du2, Shaona Wang1, Yeqing Lyu1, Biao Liu1, Haixu Wang3, Lanjie Li3   

  1. 1. CAS Key Laboratory of Green Process and Engineering, National Engineering Research Center of Green Recycling for Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    2. University of Chinese Academy of Sciences, Beijing 100049, China;
    3. Institute of Materials Technology Research, HBIS Group Co, Ltd, Hebei 063000, China
  • Received:2024-12-04 Revised:2025-02-13 Accepted:2025-02-16 Online:2025-03-14 Published:2025-08-19
  • Contact: Biao Liu,E-mail:Biaoliu@ipe.ac.cn;Lanjie Li,E-mail:lilanjie@hbisco.com
  • Supported by:
    The authors gratefully acknowledge the support the National Natural Science Foundation of China (5210440), S&T Program of Hebei (23311501D), and Program of HBIS Group under HG2023222.

Separation and recovery of V/W/Na from waste SCR catalyst leaching solution using membrane electrolysis—Ion morphology pretreatment solvent extraction-stripping method

Bo Pan1, Muneeb Ul Hassan Naseer1,2, Hao Du2, Shaona Wang1, Yeqing Lyu1, Biao Liu1, Haixu Wang3, Lanjie Li3   

  1. 1. CAS Key Laboratory of Green Process and Engineering, National Engineering Research Center of Green Recycling for Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    2. University of Chinese Academy of Sciences, Beijing 100049, China;
    3. Institute of Materials Technology Research, HBIS Group Co, Ltd, Hebei 063000, China
  • 通讯作者: Biao Liu,E-mail:Biaoliu@ipe.ac.cn;Lanjie Li,E-mail:lilanjie@hbisco.com
  • 基金资助:
    The authors gratefully acknowledge the support the National Natural Science Foundation of China (5210440), S&T Program of Hebei (23311501D), and Program of HBIS Group under HG2023222.

Abstract: In this study, a cleaner method for separation and recovery of V/W/Na in waste selective catalytic reduction (SCR) catalyst alkaline leaching solution was proposed. The method involved membrane electrolysis followed by ion morphology pretreatment and solvent extraction. An acidic V(V)/W(VI) solution was obtained using the membrane electrolysis method without adding any other chemical reagents. In addition, Na was recovered in the form of NaOH by product, avoiding the generation of Na containing wastewater. The electrolysis parameters were investigated, the lowest power consumption of 3063 kW·h·t-1 NaOH was obtained at a current density of 125 A·m-2 and an initial NaOH concentration of 2 mol·L-1. After electrolysis, oxalic acid was added to the acidic V/W containing solution, converting V(V) negative ion to V(IV) positive ion. Since W(VI) ion state remained in negative form, the generation of heteropolyacid ions (WxVyOzn-) was prevented. It was found that under the condition of oxalic acid addition/theoretical consumption 1.2 and reaction temperature 75 °C, 100% V(V) was converted to V(IV). Using 10% N263 + 10% n-octanol+80% sulfonated kerosene as extractant, the highest W(VI)/V(IV) separation coefficient of 7559.76 was obtained at pH = 1.8, O:A ratio = 1:1 and extraction time 15 min. With 2 mol·L-1 NaOH as stripping reagent, the W stripping efficiency reached 98.50% at O:A ratio = 2:1 after 4-stages of stripping. The enrichment of V remained in the solution was realized using P204 as extractant and 20% (mass) H2SO4 as stripping reagent. The parameters of extraction/stripping process were investigated, using 10% P204 + 10% TBP+80% sulfonated kerosene as extractant, the V extraction efficiency reached 97.50% at O:A ratio = 1:2 after 4 stages of extraction. Using 20% H2SO4 as the stripping reagent, the V stripping efficiency was 98.30% at an O:A ratio of 4:1 after five stages of stripping. After the entire process, a high-purity VOSO4 and Na2WO4 product solutions were obtained with V/W recovery efficiency 95.84%/98.50%, separately. This study examined a more effective and cleaner method for separating V/W/Na in Na2WO4/NaVO3 solution, which may serve as a reference for the separation and recovery of V/W/Na in waste SCR catalysts.

Key words: Waste SCR catalyst alkaline leaching solution, Membrane electrolysis, Ion state regulation, Solvent extraction, Cleaner separation

摘要: In this study, a cleaner method for separation and recovery of V/W/Na in waste selective catalytic reduction (SCR) catalyst alkaline leaching solution was proposed. The method involved membrane electrolysis followed by ion morphology pretreatment and solvent extraction. An acidic V(V)/W(VI) solution was obtained using the membrane electrolysis method without adding any other chemical reagents. In addition, Na was recovered in the form of NaOH by product, avoiding the generation of Na containing wastewater. The electrolysis parameters were investigated, the lowest power consumption of 3063 kW·h·t-1 NaOH was obtained at a current density of 125 A·m-2 and an initial NaOH concentration of 2 mol·L-1. After electrolysis, oxalic acid was added to the acidic V/W containing solution, converting V(V) negative ion to V(IV) positive ion. Since W(VI) ion state remained in negative form, the generation of heteropolyacid ions (WxVyOzn-) was prevented. It was found that under the condition of oxalic acid addition/theoretical consumption 1.2 and reaction temperature 75 °C, 100% V(V) was converted to V(IV). Using 10% N263 + 10% n-octanol+80% sulfonated kerosene as extractant, the highest W(VI)/V(IV) separation coefficient of 7559.76 was obtained at pH = 1.8, O:A ratio = 1:1 and extraction time 15 min. With 2 mol·L-1 NaOH as stripping reagent, the W stripping efficiency reached 98.50% at O:A ratio = 2:1 after 4-stages of stripping. The enrichment of V remained in the solution was realized using P204 as extractant and 20% (mass) H2SO4 as stripping reagent. The parameters of extraction/stripping process were investigated, using 10% P204 + 10% TBP+80% sulfonated kerosene as extractant, the V extraction efficiency reached 97.50% at O:A ratio = 1:2 after 4 stages of extraction. Using 20% H2SO4 as the stripping reagent, the V stripping efficiency was 98.30% at an O:A ratio of 4:1 after five stages of stripping. After the entire process, a high-purity VOSO4 and Na2WO4 product solutions were obtained with V/W recovery efficiency 95.84%/98.50%, separately. This study examined a more effective and cleaner method for separating V/W/Na in Na2WO4/NaVO3 solution, which may serve as a reference for the separation and recovery of V/W/Na in waste SCR catalysts.

关键词: Waste SCR catalyst alkaline leaching solution, Membrane electrolysis, Ion state regulation, Solvent extraction, Cleaner separation