燃煤电厂废弃SCR催化剂回收二氧化钛的研究
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摘要
对废弃的选择性催化还原(SCR)烟气脱硝催化剂中有价金属进行回收,将其变废为宝意义重大。以某燃煤电厂废弃的SCR脱销催化剂为研究对象,采用钠化焙烧工艺从废弃的SCR催化剂中回收二氧化钛(TiO2)等有价金属。分别考察了碳酸钠投加量、稀硫酸投加量、浸出热水量、浸出时间、浸出温度、焙烧时间、焙烧温度对Ti O2回收率的影响。结果表明:钠化焙烧、熟料浸出和硫酸水洗过程对TiO2的提取均影响显著。在优化条件下,TiO2回收率达到92.15%,产物纯度可达96.28%。可行性分析表明,所研制的SCR催化剂回收方案经济效益较好。
It is of great significance to recover the valuable metals from the inactive SCR denitration catalyst waste and make them recycled. Taking the waste SCR catalyst from a thermal power plant as the study object, the titanium dioxides are recovered with sodiumzation-calcinating technology from the abandoned SCR catalysts. In addition, the effects of sodium carbonate and dilute sulphuric acid dosages, the leaching water volume, time and temperature, and the calcinating time and temperature on the recovery rate are studied.The results indicate that the processes of sodiumzation-calcinating, raw material extraction and sulphuric acid washing have great impacts on the titanium dioxide extraction. Under the optimal condition, the recovery rate reaches as much as 92.15% with the product purity of96.28%. The feasibility analysis shows that the developed SCR catalyst recovery program has good economic returns.
It is of great significance to recover the valuable metals from the inactive SCR denitration catalyst waste and make them recycled. Taking the waste SCR catalyst from a thermal power plant as the study object, the titanium dioxides are recovered with sodiumzation-calcinating technology from the abandoned SCR catalysts. In addition, the effects of sodium carbonate and dilute sulphuric acid dosages, the leaching water volume, time and temperature, and the calcinating time and temperature on the recovery rate are studied.The results indicate that the processes of sodiumzation-calcinating, raw material extraction and sulphuric acid washing have great impacts on the titanium dioxide extraction. Under the optimal condition, the recovery rate reaches as much as 92.15% with the product purity of96.28%. The feasibility analysis shows that the developed SCR catalyst recovery program has good economic returns.
引文
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[17]盘思伟,杨建波,陈冬林,等.SCR脱硝催化剂动态再生试验研究[J].中国电力,2014,47(8):150-153.PAN Siwei,YANG Jianbo,CHEN Donglin,et al.Experimental study on regeneration of SCR De-NOxcatalysts[J].Electric Power,2014,47(8):150-153.
[18]刘红辉,刘伟,黄锐,等.燃煤电厂SCR脱硝催化剂失活及其再生性能研究[J].中国电力,2014,47(4):139-143.LIU Honghui,LIU Wei,HUANG Rui,et al.Study on performance of deactivated and regenerated catalysts for coal-fired power plant SCR denitration[J].Electric Power,2014,47(4):139-143.
[19]李俊峰,张兵兵,李翼然.基于钛基SCR法废脱销催化剂的回收利用[J].广州化工,2014,42(24):130-132.LI Junfeng,ZHANG Bingbing,LI Yiran.Study on reclamation of deactivated De-NOxSCR catalyst based on V2O5-Ti O2[J].Guangzhou Chemical Industry,2014,42(24):130-132.
[20]GUPTA C K,KRISHNAMURTY N.Extractive metallurgy of vanadium[M].New York:Elsevier,1992:203.
[21]李新兵,谢兵,冉俊峰.高硅高钙低品位钒渣提取五氧化二钒的研究[J].稀有金属,2011,35(5):747-752.LI Xinbing,XIE Bing,RAN Junfeng.Extraction of vanadium pentoxide from low grade vanadium slag with high silicon and high calcium[J].Chinese Journal of Rare Metals,2011,35(5):747-752.
[22]LIETTI L,NOVA Isabella,RAMIS G,et al.Characterization and reactivity of V2O5-Mo O3/Ti O2De-NOxSCR catalysts[J].Journal of Catalysis,1999,187(2):419-435.
[23]季先进,王继元,曾崇余,等.焙烧温度对Ti O2成型载体性能的影响[J].工业催化,2008,12(16):30-33.JI Xianjin,WANG Jiyuan,ZENG Chongyu,et al.Effects of calcination temperature on properties of formed Ti O2support[J].Industrial Catalysis,2008,12(16):30-33.
[24]段冉.高纯五氧化二钒的制备及偏钒酸铵结晶机理的研究[D].长沙:中南大学,2011:56-58.
[25]LASSNER E,SCHUBERT W D.Tungsten:properties chemistry,technology of element,alloys and chemical compounds[M].New York:Kluwer Academic Publishing/Plinum Publishers,1999:195.
[26]罗琳,藤田丰久,治进藤.从废弃的钨金属制品中回收钨和钒[J].矿冶,2002,11(1):50-54.LUO Lin,TOYOHISA Fujita,OSAMU Shindo.Recovery of tungsten and vanadium from the tungstate scrap[J].Mining and Metallurgy,2002,11(1):50-54.
[27]曾瑞,郝永利.废弃SCR催化剂回收利用项目建设格局的分析[J].中国环保产业,2014(9):41-46.ZENG Rui,HAO Yongli.Analysis on project construction pattern of abandoned SCR catalyzer recovery and utilization[J].China Ecvironmental Protection Industry,2014(9):41-46.
[28]BUSCA G,LIETTI L,RAMIS G,et al.Chemical and mechanistic aspects of the selective catalytic reduction of NOxby ammonia over oxide catalysts:A review[J].Applied Catalysis B:Environment,1998,18(1):1-36.
[2]火电厂大气排放标准:GB 13223—2011[S].
[3]陈其颢,朱林.SCR失效催化剂及其处置与再利用技术[J].电力科技与环保,2012,28(3):27-28.CHEN Qihao,ZHU lin.Disposal and recycling technologies of disabled SCR catalysts[J].Electric Power Technology and Environmental Protection,2012,28(3):27-28.
[4]MADIA G,KOEBEL M,ELSENNER M,et al.The effect of an oxidation precatalyst on the NOxreduction by ammonia SCR[J].Industrial&Engineering Chemistry Research,2002,41(15):3512-3517.
[5]WACHS I E,DEO G,WECKHUYSEN B M,et al.Selective catalytic reduction of NO with NH3over supported vanadia catalysts[J].Journal of Catalysis,1996,161(1):211-221.
[6]AMIRIDIS M D,SOLAR J P.Selective catalytic reduction of nitric oxide by ammonia over V2O5/Ti O2,V2O5/Ti O2/Si O2,and V2O5-WO3/Ti O2catalysts:Effect of vanadia content on the activation energy[J].Industrial and Engineering Chemistry Research,1996,35(3):978-981.
[7]曾瑞.有关我国SCR废催化剂回收产业的思考[J].中国环保产业,2013(4):55-61.ZENG Rui.Thinking about our SCR catalyst waste recycling industry[J].China Environmental Protection Industry,2013(4):55-61.
[8]刘慷,张强.火电厂脱NOx用SCR催化剂种类及工程应用[J].电力环境保护,2009,25(4):9-12.LIU Kang,ZHANG Qiang.Species and applicationg of SCR catalyst for flue gas denitrification in coal-fired power plant[J].Electric Power Environmental Protection,2009,25(4):9-12.
[9]MORADI F,BRANDIN J,SOHRABI M.Deactivation of oxidation and SCR catalysts usein flue gas cleaning by exposure to aerosols of high and low melting point salts,potassium salts and zinczinc chloride[J].Applied Catalysis B:Environmental,10/2003,46(1):65.
[10]云端,邓斯理.V2O5-WO3/Ti O2系SCR催化剂的钾中毒及再生方法[J].环境科学研究,2009,22(6):730-735.YUN Duan,DENG Sili.Potassium deactivation and regeneration method of V2O5-WO3/Ti O2SCR catalyst[J].Research of Environmental Sciences,2009,22(6):730-735.
[11]沈伯雄,熊丽仙,刘亭.纳米负载型V2O5-WO3/Ti O2催化剂碱中毒及再生研究[J].燃料化学学报,2010,38(1):85-90.SHEN Boxiong,XIONG Lixian,LIU Ting.Alkali deactivation and regeneration of nano V2O5-WO3/Ti O2catalysts[J].Journal of Fuel Chemistry and Technology,2010,38(1):85-90.
[12]KAMATA H,TAKAHASHI K,ODENBRAND CUI.The role of K2O in the selective reduction of NO with NH3over a V2O5(WO3)/Ti O2commercial selective catalytic reduction catalyst[J].Journal of Molecular Catalysis A:Chemical,1999,139(2/3):189-198.
[13]曹长武,宋丽莎,罗竹杰.火力发电厂化学监督技术[M].北京:中国电力出版社,2008:2-4.
[14]李德波,廖永进,陆继东,等.燃煤电站SCR催化剂更换周期及策略优化数学模型[J].中国电力,2013,46(12):118-121.LI Debo,LIAO Yongjin,LU Jidong,et al.Study on mathematical models for optimization of SCR catalyst replacement cycle and strategy[J].Electric Power,2013,46(12):118-121.
[15]沈伯雄,施建伟,杨婷婷.选择性催化还原脱氮催化剂的再生及其应用评述[J].化工进展,2008,27(1):64-67.SHEN Boxiong,SHI Jianwei,YANG Tingting.Regeneration technologies of SCR catalysts and their application[J].Chemical Industry and Engineering Progress,2008,27(1):64-67.
[16]王平,林海波,姚友工,等.SCR催化剂再生技术在燃煤电厂的应用[J].中国电力,2015,48(4):40-43.WANG Ping,LIN Haibo,YAO Yougong,et al.Application of SCR catalyst regeneration technology in coal-fired power plants[J].Electric Power,2015,48(4):40-43.
[17]盘思伟,杨建波,陈冬林,等.SCR脱硝催化剂动态再生试验研究[J].中国电力,2014,47(8):150-153.PAN Siwei,YANG Jianbo,CHEN Donglin,et al.Experimental study on regeneration of SCR De-NOxcatalysts[J].Electric Power,2014,47(8):150-153.
[18]刘红辉,刘伟,黄锐,等.燃煤电厂SCR脱硝催化剂失活及其再生性能研究[J].中国电力,2014,47(4):139-143.LIU Honghui,LIU Wei,HUANG Rui,et al.Study on performance of deactivated and regenerated catalysts for coal-fired power plant SCR denitration[J].Electric Power,2014,47(4):139-143.
[19]李俊峰,张兵兵,李翼然.基于钛基SCR法废脱销催化剂的回收利用[J].广州化工,2014,42(24):130-132.LI Junfeng,ZHANG Bingbing,LI Yiran.Study on reclamation of deactivated De-NOxSCR catalyst based on V2O5-Ti O2[J].Guangzhou Chemical Industry,2014,42(24):130-132.
[20]GUPTA C K,KRISHNAMURTY N.Extractive metallurgy of vanadium[M].New York:Elsevier,1992:203.
[21]李新兵,谢兵,冉俊峰.高硅高钙低品位钒渣提取五氧化二钒的研究[J].稀有金属,2011,35(5):747-752.LI Xinbing,XIE Bing,RAN Junfeng.Extraction of vanadium pentoxide from low grade vanadium slag with high silicon and high calcium[J].Chinese Journal of Rare Metals,2011,35(5):747-752.
[22]LIETTI L,NOVA Isabella,RAMIS G,et al.Characterization and reactivity of V2O5-Mo O3/Ti O2De-NOxSCR catalysts[J].Journal of Catalysis,1999,187(2):419-435.
[23]季先进,王继元,曾崇余,等.焙烧温度对Ti O2成型载体性能的影响[J].工业催化,2008,12(16):30-33.JI Xianjin,WANG Jiyuan,ZENG Chongyu,et al.Effects of calcination temperature on properties of formed Ti O2support[J].Industrial Catalysis,2008,12(16):30-33.
[24]段冉.高纯五氧化二钒的制备及偏钒酸铵结晶机理的研究[D].长沙:中南大学,2011:56-58.
[25]LASSNER E,SCHUBERT W D.Tungsten:properties chemistry,technology of element,alloys and chemical compounds[M].New York:Kluwer Academic Publishing/Plinum Publishers,1999:195.
[26]罗琳,藤田丰久,治进藤.从废弃的钨金属制品中回收钨和钒[J].矿冶,2002,11(1):50-54.LUO Lin,TOYOHISA Fujita,OSAMU Shindo.Recovery of tungsten and vanadium from the tungstate scrap[J].Mining and Metallurgy,2002,11(1):50-54.
[27]曾瑞,郝永利.废弃SCR催化剂回收利用项目建设格局的分析[J].中国环保产业,2014(9):41-46.ZENG Rui,HAO Yongli.Analysis on project construction pattern of abandoned SCR catalyzer recovery and utilization[J].China Ecvironmental Protection Industry,2014(9):41-46.
[28]BUSCA G,LIETTI L,RAMIS G,et al.Chemical and mechanistic aspects of the selective catalytic reduction of NOxby ammonia over oxide catalysts:A review[J].Applied Catalysis B:Environment,1998,18(1):1-36.