Wang Shuting;Wu Mina;Yang Zixuan;Bi Tingtao;Zhang Wenjie;

• 1:Yunnan Academy of Ecological Environment Sciences
• 2:Kunming Metallurgical Research Institute Co.
• 3: Ltd.
• 4:National Key Laboratory of New Technology for Strengthened Metallurgy of Nonferrous Metals

Abstract：

Among the numerous technologies for degrading NO_x,selective catalytic reduction(SCR) technology has been widely adopted due to its high NO_x removal efficiency and minimal byproducts.The key component of SCR technology is the catalyst responsible for the degradation effect,typically a vanadium-titanium(V-Ti) based catalyst.After 2～3 years of operation,the activity of these catalysts' declines,and they may even become deactivated.As the consumption of fossil fuels like coal continues to increase,the demand for SCR catalysts also rises steadily.It is projected that the demand for SCR catalysts will exceed 120,000 metric tons by 2025,while the cumulative amount of decommissioned SCR catalysts requiring treatment will surpass 800,000 metric tons.Decommissioned SCR catalysts contain significant amounts of valuable metals such as vanadium(V),tungsten(W),molybdenum(Mo),and titanium(Ti),but are also contaminated with hazardous components like arsenic and sulfur compounds-Consequently,they are classified as hazardous waste in the National Catalogue of Hazardous Wastes and prohibited from traditional landfill disposal.Therefore,the development of green and comprehensive recycling processes for decommissioned SCR catalysts is urgently needed.This approach not only provides an important source of strategic metals,enabling their reuse,but also prevents the environmental threats posed by this waste,holding significant importance for achieving both economic and social benefits.Completely deactivated SCR catalysts typically contain 80%～90% TiO_2,5%～10% WO_3,and 0.5%～1% V_2O_5.Currently,the recovery of valuable metals from SCR catalyst's primarily employs hydrometallurgical(wet) and pyrometallurgical(smelting) processes.In hydrometallurgical leaching,acids or alkalis are used to dissolve the metal compounds in the decommissioned catalyst,causing the metals to enter the leachate in ionic form.Metals like V,W,and Ti are then selectively separated and recovered from this leachate.When inorganic acids(HCl,HNO_3,H_2SO_4) are used as leaching agents,dissolution studies have shown the leaching efficiency follows the order:HCl>H_2SO_4>HNO_3.However,using HCl as the leaching agent carries significant drawbacks:it readily generates toxic chlorine gas(Cl_2),has high volatility,and exhibits strong corrosivity.Consequently,H_2SO_4 is more commonly used as the leaching agent in industrial applications.Compared to inorganic acids,organic acids exhibit weaker acidity,imposing lower corrosion resistance requirements on reaction equipment.Furthermore,organic acids can form complexes with metal ions,enhancing the dissolution of valuable metals in the organic acid solution.Alkaline leaching(using NaOH,KOH,NH,OH,Na_2CO_3,etc.)of decommissioned SCR catalysts offers milder reaction conditions.This method selectively dissolves W and V while retaining Ti in the residue phase,thereby reducing the complexity of subsequent separation and purification steps.In the preparation of SCR catalysts,V and W are basically loaded on the surface of nanoscale TiO_2.During fine grinding and leaching,V and W still agglomerate with TiO_2,affecting the leaching effect.Even in enhanced pressure leaching,the leaching rate of V and W is basically about 90%,and part of them is difficult to leach.In order to improve the leaching effect of V and W,the alkali roasting process is proposed,which has the advantage of high recovery rate.However,it also has the disadvantages of high roasting temperature,the need for acidic solution to recover metals such as V and W in the follow-up,increasing the treatment cost,and easily producing a large amount of acidic waste liquid,which has an impact on the environment.In addition,new processes such as microwave-assisted process,chlorination method,and electrolysis method can also effectively recover valuable metals from waste SCR catalysts.The external microwave action in the roasting environment can generate instant high temperature and high pressure,accelerate the high-speed collision between solid particles,produce micro-jet action on the particle surface,realize the stripping of V and W,and at the same time enhance the mass transfer efficiency and improve the subsequent leaching rate.However,the related technology still has shortcomings,and there is still a certain gap from industrial production.The chlorination method mainly utilizes the boiling point differences among chlorides of V,W,Ti,Si,Al,etc.,in waste SCR catalysts to selectively recover VOCl_3 from the molten state,followed by vanadium precipitation with NH_4Cl to produce high-purity vanadium products.However,the chlorination method also has high energy consumption,easily generates toxic Cl_2,causes environmental impacts,and has great operational difficulties.The electrolysis method realizes directional enrichment of metals by leveraging the differences in redox properties of different metals.Electrolysis of the molten electrolyte enables the enrichment of Ti.With the continuous in-depth research,the follow-up development of waste SCR catalysts should focus on the research and development of new treatment technologies,the combination of different processes,the exploration of high-value utilization ways of waste SCR catalysts,and the optimization and improvement of existing processes,so as to reduce energy consumption and improve application benefits.At present,the recovery of valuable metals from waste SCR catalysts is a research hotspot,and a large number of exploratory tests have injected momentum into the development of this field.

Key Words： selective catalytic reduction catalysts;acid leaching;alkaline leaching;recovery;comprehensive utilization

Abstract:

Keywords:

Foundation: 云南省基础研究计划项目（202501AU070040）资助

Authors: Wang Shuting;Wu Mina;Yang Zixuan;Bi Tingtao;Zhang Wenjie;

DOI: 10.13373/j.cnki.cjrm.XY25060004

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