失活商业SCR催化剂在线维护技术
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摘要
商业SCR催化剂在工业运行过程中由于其复杂的工况条件存在容易中毒、失活的问题,故利用在线维护技术对其进行活性恢复具有巨大的商业发展前景。为了探究泡沫清洗技术对商业SCR失活催化剂进行在线维护方案的可行性,采用一系列表征手段对在线维护前、后的失活SCR脱硝催化剂进行了表征分析,包括SEM、EDS、XRD、BET和XPS等,并对在线维护最佳的溶液浓度参数进行了探究。研究发现:当稀硫酸浓度为0.4 mol·L~(-1),微孔渗透液质量分数为2%,活性添加剂质量分数为3%,在线维护效果最优;经过在线维护之后,催化剂团聚现象得到明显改善,碱金属中毒现象得到缓解,催化剂氧化性能和表面酸度增强,催化剂活性因而得到恢复,其最佳脱硝效率可达92%,具备良好的工业应用潜力。
Due to the complicated working conditions for commercial SCR catalysts applied in bio-fuel plants,they must meet the poisoning and deactivation problems during the process of industrial operation. Therefore,their activation recovery with viable online maintenance solutions will have a great commercial potential. In order to identify the feasibility of the foam cleaning technology on the on-line maintenance of deactivated commercial SCR catalysts, a series of techniques, including SEM, EDS, XRD, BET and XPS, were used to characterize the deactivated commercial SCR catalysts before and after on-line maintenance. The optimum concentration parameters of cleaning solution for on-line maintenance were also investigated. The results showed that the optimum on-line maintenance effect happened at the dilute sulfuric acid concentration of 0.4 mg·L~(-1),the mass concentration for microporous permeate of 2%, and the mass concentration for active additive of 3%.After on-line maintenance, the agglomeration and alkali poisoning of the catalysts were significantly alleviated.The surface acidic sites and oxidation property of catalyst were enhanced, which contributed to the activity recovery of deactivated catalyst. The optimum denitration efficiency reached up to 92%, which showed a good industrial application potential.
Due to the complicated working conditions for commercial SCR catalysts applied in bio-fuel plants,they must meet the poisoning and deactivation problems during the process of industrial operation. Therefore,their activation recovery with viable online maintenance solutions will have a great commercial potential. In order to identify the feasibility of the foam cleaning technology on the on-line maintenance of deactivated commercial SCR catalysts, a series of techniques, including SEM, EDS, XRD, BET and XPS, were used to characterize the deactivated commercial SCR catalysts before and after on-line maintenance. The optimum concentration parameters of cleaning solution for on-line maintenance were also investigated. The results showed that the optimum on-line maintenance effect happened at the dilute sulfuric acid concentration of 0.4 mg·L~(-1),the mass concentration for microporous permeate of 2%, and the mass concentration for active additive of 3%.After on-line maintenance, the agglomeration and alkali poisoning of the catalysts were significantly alleviated.The surface acidic sites and oxidation property of catalyst were enhanced, which contributed to the activity recovery of deactivated catalyst. The optimum denitration efficiency reached up to 92%, which showed a good industrial application potential.
引文
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[22]CHEN C,CAO Y,LIU S,et al.SCR catalyst doped with copper for synergistic removal of slip ammonia and elemental mercury[J].Fuel Processing Technology,2018,181:268-278.
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[2]LI X,LI Y,DENG S,et al.A Ce-Sn-Ox catalyst for the selective catalytic reduction of NOx with NH3[J].Catalysis Communications,2013,40:47-50.
[3]FAN D Q,WANG J,YU T,et al.Catalytic deactivation mechanism research over Cu/SAPO-34 catalysts for NH3-SCR(I):The impact of 950℃hydrothermal aging time[J].Chemical Engineering Science,2018,176:285-293.
[4]PENG Y,LI J,SI W,et al.Deactivation and regeneration of a commercial SCR catalyst:Comparison with alkali metals and arsenic[J].Applied Catalysis B:Environmental,2015,168:195-202.
[5]SHANG X,HU G,CHI H,et al.Regeneration of full-scale commercial honeycomb monolith catalyst(V2O5-WO3/TiO2)used in coal-fired power plant[J].Journal of Industrial&Engineering Chemistry,2012,18:513-519.
[6]白伟,赵冬梅,肖雨亭.失活SCR脱硝催化剂化学清洗再生技术研究[J].中国电力,2015,48(4):6-10.
[7]樊恩亚,卫平波,眭国荣,等.锰铈脱硝催化剂的制备及其再生性能研究[J].环境科学与技术,2012,35(9):40-44.
[8]王玉雷,陈炳耀,李乐,等.环保气雾型水基泡沫清洗剂的研究[J].日用化学品科学,2010,33(11):19-23.
[9]YU Y,WANG J,CHEN J,et al.Regeneration of commercial selective catalyst reduction catalysts deactivated by Pb and other inorganic elements[J].Journal of Environmental Sciences,2016,47:100-108.
[10]黄力,陈志平,王虎,等.钒钛系SCR脱硝催化剂砷中毒研究进展[J].能源环境保护,2016,30(4):5-8.
[11]周春玲,朱趁安,章文荣,等.泡沫驱用起泡剂的筛选及性能评价[J].石油化工应用,2017,36(12):49-52.
[12]UDDIN M A,SHIMIZU K,ISHIBE K,et al.Characteristics of the low temperature SCR of NOx with NH3over TiO2[J].Journal of Molecular Catalysis A:Chemical,2009,309:178-183.
[13]BHARDWAJ R,CHEN X H,VIDIC R.Impact of fly ash composition on mercury speciation in simulated flue gas[J].Air Repair,2009,59:1331-1338.
[14]YOUN S,SONG I,LEE H,et al.Effect of pore structure of TiO2on the SO2poisoning over V2O5/TiO2catalysts for selective catalytic reduction of NOx with NH3[J].Catalysis Today,2017,303:19-24.
[15]CHANG H Z,SHI C N,LI M G,et al.The effect of cations(NH4+,Na+,K+,and Ca2+)on chemical deactivation of commercial SCR catalyst by bromides[J].Chinese Journal of Catalysis,2018,39:710-717.
[16]ZHENG Y,JENSEN A D,JOHNSSON J E.Deactivation of V2O5-WO3-TiO2SCR catalyst at a biomass-fired combined heat and power plant[J].Applied Catalysis B:Environmental,2005,60:253-264.
[17]ZONG L,DONG F,ZHANG G,et al.Highly efficient mesoporous V2O5/WO3-TiO2catalyst for selective catalytic reduction of NOx:Effect of the valence of V on the catalytic performance[J].Catalysis Surveys from Asia,2017,21:103-113.
[18]唐云,杨凤林,刘冰.γ-Al2O3负载Mn基催化剂低温催化臭氧氧化NO[J].环境工程学报,2018,12(9):2540-2547.
[19]CHEN W,LI Z,HU F,et al.In-situ DRIFTS investigation on the selective catalytic reduction of NO with NH3over the sintered ore catalyst[J].Applied Surface Science,2018,439:75-81.
[20]XIONG Z,WU C,HU Q,et al.Promotional effect of microwave hydrothermal treatment on the low-temperature NH3-SCR activity over iron-based catalyst[J].Chemical Engineering Journal,2012,286:459-466.
[21]QING M X,SU S,WANG L L,et al.Getting insight into the oxidation of SO2to SO3over V2O5-WO3/TiO2catalysts:Reaction mechanism and effects of NO and NH3[J].Chemical Engineering Journal,2019,361:1215-1224.
[22]CHEN C,CAO Y,LIU S,et al.SCR catalyst doped with copper for synergistic removal of slip ammonia and elemental mercury[J].Fuel Processing Technology,2018,181:268-278.
[23]ZHU M,LAI J K,TUMULURI U,et al.Nature of active sites and surface intermediates during SCR of NO with NH3by supported V2O5-WO3/TiO2catalysts[J].Journal of the American Chemical Society,2017,139:15624-15627.