Simulation and experimental study on modification of water and sulfur resistance by Mn-based denitration catalyst

WANG Jinyu; ZHU Huaizhi; AN Zewen; GONG Jian; WANG Cuiping

doi:10.11949/0438-1157.20190690

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Simulation and experimental study on modification of water and sulfur resistance by Mn-based denitration catalyst

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Simulation and experimental study on modification of water and sulfur resistance by Mn-based denitration catalyst
- CIESC Journal Vol. 70, Issue 12, Pages: 4635-4644(2019)
- 作者机构：
  
  青岛大学机电工程学院能源与动力工程系，山东青岛 266071
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20190690
  CLC： TQ 534.9
- Received：19 June 2019，
  
  Revised：2019-09-30，
  
  Online First：09 June 2020，
  
  Published：05 December 2019
- 稿件说明：
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王金玉, 朱怀志, 安泽文, 巩建, 王翠苹. Mn基脱硝催化剂抗水抗硫改性的模拟与实验研究[J]. 化工学报, 2019, 70(12): 4635-4644

WANG Jinyu, ZHU Huaizhi, AN Zewen, GONG Jian, WANG Cuiping. Simulation and experimental study on modification of water and sulfur resistance by Mn-based denitration catalyst[J]. CIESC Journal, 2019, 70(12): 4635-4644
王金玉, 朱怀志, 安泽文, 巩建, 王翠苹. Mn基脱硝催化剂抗水抗硫改性的模拟与实验研究[J]. 化工学报, 2019, 70(12): 4635-4644 DOI： 10.11949/0438-1157.20190690.

WANG Jinyu, ZHU Huaizhi, AN Zewen, GONG Jian, WANG Cuiping. Simulation and experimental study on modification of water and sulfur resistance by Mn-based denitration catalyst[J]. CIESC Journal, 2019, 70(12): 4635-4644 DOI： 10.11949/0438-1157.20190690.

摘要

为考察ZSM-5分子筛作载体和Ce掺杂对催化剂低温脱硝活性及抗水抗硫性的影响，通过分子动力学模拟和实验研究的手段研究了载体类型、掺杂Ce对催化剂性能的影响。分子动力学模拟发现，ZSM-5分子筛作载体较γ-Al

明显抑制H

O在其表面的吸附，在活性组分中添加Ce既抑制H

O在其表面的吸附，又减轻SO

对催化剂的毒化作用。实验研究发现，Mn-Fe-Ce/ZSM-5催化剂性能更优，Ce的添加对提高催化剂的低温脱硝活性和抗水抗硫性能具有明显的积极作用，ZSM-5分子筛作为载体也对提高催化剂抗水性能起到重要作用。通过SEM、XRD、BET、TG-DTG等表征手段和BaCl

鼓泡实验对Mn-Fe-Ce/ZSM-5催化剂抗硫性提高的原因分析发现，添加Ce使催化剂储氧释氧能力提高，将烟气中的SO

氧化为SO

并被烟气携带，避免了SO

与催化剂活性组分的反应，则催化剂表面的活性组分不被破坏，保证了催化剂的催化反应性能。

Abstract

To investigate the effect of ZSM-5 zeolite as carrier and Ce doping on the low temperature denitrification activity and water/sulfur resistance of the catalyst

the effects of carrier type and Ce doping on the performance of the catalyst were studied by molecular dynamics simulation and experimental research. Molecular dynamics simulations showed that ZSM-5 zeolite as a carrier significantly inhibited the adsorption of H

O on its surface compared with γ-Al

. Adding Ce to the active component not only inhibited the adsorption of H

O on its surface

but also mitigated the poisoning effect of SO

on the catalyst. The experimental study found that Mn-Fe-Ce/ZSM-5 has better denitration activity under low temperature and water/sulfur resistance. The addition of Ce has a positive effect on improving the low temperature activity and water/sulfur resistance of the catalyst. ZSM-5 zeolite as carriers also play an important role in improving the water resistance of the catalyst. The SEM

XRD

BET

TG-DTG and other characterization methods and BaCl

bubbling experiments were carried out to analyze the mechanisms for the improvement of sulfur resistance of Mn-Fe-Ce/ZSM-5 catalyst. It was found that the addition of Ce increased the oxygen storage and oxygen release capacity of the catalyst. Oxidation of SO

in the flue gas to SO

avoids the reaction of SO

with the active component

so that the active component on the surface of the catalyst is not destroyed

and the catalytic reaction performance of the catalyst is ensured.

关键词

Keywords

references

Miroslav R . Reduction of nitrogen oxides in flue gases [J ] . Environmental Pollution , 1998 , 102 ( 1 ): 685 - 689 .

张楚莹 , 王书肖 , 邢佳 , 等 . 中国能源相关的氮氧化物排放现状与发展趋势分析 [J ] . 环境科学学报 , 2015 , 28 ( 12 ): 2470 - 2479 .

Zhang C Y , Wang S X , Xing J , et al . Current st atus and future projections of NO x emissions from energy related in dustries in China [J ] . Acta Scientiae Circumstantiae , 2015 , 28 ( 12 ): 2470 - 2479 .

Xue Y , Tian H , Yan J , et al . Temporal trends and spatial variation characteristics of primary air pollutants emissions from coal-fired industrial boilers in Beijing, China [J ] . Environmental Pollution , 2016 , 213 : 717 - 726 .

Chiu C H , Hsi , H C , Lin H P , et al . Effects of properties of manganese oxide-impregnated catalysts and flue gas condition on multipollutant control of HgO and NO [J ] . Journal of Hazardous Materials , 2015 , 291 : 1 - 8 .

Wang X , Li Y J , Shi J W , et al . Simultaneous SO 2 /NO removal performance of carbide slag pellets by bagasse templating in a bubbling fluidized bed reactor [J ] . Fuel Processing Technology , 2018 , 180 : 75 - 86 .

Liu Z , Woo S I . Recent advances in catalytic DeNO x science and technology [J ] . Catalysis Reviews , 2006 , 48 ( 1 ): 43 - 89 .

黄海凤 , 张峰 , 卢晗锋 , 等 . 制备方法对低温NH 3 -SCR脱硝催化剂MnO x /TiO 2 结构与性能的影响 [J ] . 化工学报 , 2010 , 61 ( 1 ): 80 - 85 .

Huang H F , Zhang F , Lu H F , et al . Effect of preparation methods on structures and performance of MnO x /TiO 2 catalyst for low-temperature NH 3 -SCR [J ] . CIESC Journal , 2010 , 61 ( 1 ): 80 - 85 .

Qi G , Yang R T . Performance and kinetics study for low-temperature SCR of NO with NH 3 over MnO x -CeO 2 catalyst [J ] . Journal of Catalysis , 2003 , 217 ( 2 ): 434 - 441 .

Muniz J , Marban G , Fuertes A B . Low temperature selective catalytic reduction of NO over modified activated carbon fibers [J ] . Applied Catalysis B: Environmental , 2000 , 27 : 27 - 36 .

Lei Z , Liu X , Jia M . Modeling of selective catalytic reduction (SCR) for NO removal using monolithic honeycomb catalys [J ] . Energy & Fuels , 2009 , 23 : 6146 - 6151 .

Shi J , Zhang Z H , Chen M X , et al . Promotion effect of tungsten and iron co-addition on the catalytic performance of MnO x /TiO 2 for NH 3 -SCR of NO x [J ] . Fuel , 2017 , 210 ( 15 ): 783 - 789 .

Nam K B , Kwon D W , Hong S C . DRIFT study on promotion effects of tungsten-modified Mn/Ce/Ti catalysts for the SCR reaction at low-temperature [J ] . Applied Catalysis A: General , 2017 , 542 : 55 - 62 .

廖永进 , 张亚平 , 余岳溪 , 等 . MnO x /WO 3 /TiO 2 低温选择性催化还原NO x 机理的原位红外研究 [J ] . 化工学报 , 2016 , 67 ( 12 ): 5031 - 5039 .

Liao Y J , Zhang Y P , Yu Y X , et al . In situ FT-IR studies on low temperature NH 3 -SCR mechanism of NO x over MnO x /WO 3 /Ti O 2 catalyst [J ] . CIESC Journal , 2016 , 67 ( 12 ): 5031 - 5039 .

Wu Z B , Jiang B Q , Liu Y , et al . Experimental study on a low-temperature SCR catalyst based on MnO x /TiO 2 prepared by sol-gel method [J ] . Journal of Hazardous Materials , 2007 , 145 : 488 - 94 .

Jiang S Y , Zhou R X . Ce doping effect on performance of the Fe/β catalyst for NO x , reduction by NH 3 [J ] . Fuel Processing Technology , 2015 , 133 : 220 - 226 .

Huang T J , Zhang Y P , Zhuang K , et al . Preparation of honeycombed holmium-modified Fe-Mn/TiO 2 catalyst and its performance in the low temperature selective catalytic reduction of NO x [J ] . Journal of Fuel Chemistry & Technology , 2018 , 46 ( 3 ): 319 - 327 .

Chen X , Wang P , Fang P , et al . Tuning the property of Mn-Ce composite oxides by titanate nanotubes to improve the activity selectivity and SO 2 /H 2 O tolerance in middle temperature NH 3 -SCR reaction [J ] . Fuel Processing Technology , 2017 , 167 : 221 - 228 .

Jiang B Q , Wu Z B , Liu Y , et al . DRIFT Study of the SO 2 effect on low-temperature SCR reaction over Fe-Mn/TiO 2 [J ] . Journal of Physical Chemistry C , 2010 , 114 ( 11 ): 4961 - 4965 .

Shen B X , Liu T . Deactivation of MnO x -CeO x /ACF catalysts for low temperature NH 3 -SCR in the presence of SO 2 [J ] . Acta Physico-Chimica Sinica , 2010 , 26 ( 11 ): 3009 - 3016 .

Phil H H , Reddy M P , Kumar P A , et al . SO 2 resistant antimony promoted V 2 O 5 /TiO 2 catalyst for NH 3 -SCR of NO x at low temperatures [J ] . Applied Catalysis B: Environmental , 2008 , 78 ( 3 ): 301 - 308 .

Li Y , Han X , et al . Role of CTAB in the improved H 2 O resistance for selective catalytic reduction of NO with NH 3 over iron titanium catalyst [J ] . Chemical Engineering Journal , 2018 , 347 ( 1 ): 313 - 321 .

Park T S , Jeong S K , Hong S H , et al . Selective catalytic reduction of nitrogen oxides with NH 3 over natural manganese ore at low temperature [J ] . Ind. Eng. Chem. Res ., 2001 , 40 ( 21 ): 4491 - 4495 .

刘亭 . 锰铈基低温选择性催化还原(SCR)脱硝催化剂的研究 [D ] . 天津 : 南开大学 , 2011 .

Liu T . Study on manganese sulfhydryl group low temperature selective catalytic reduction (SCR) denitration catalyst [D ] . Tianjin : Nankai University , 2011 .

Kijlstra W S , Biervliet M , Poels E K , et al . Deactivation by SO 2 of MnO x /Al 2 O 3 catalysts used for the selective catalytic reduction of NO with NH 3 at low temperatures [J ] . Applied Catalysis B: Environmental , 1998 , 16 ( 4 ): 327 - 337 .

孙克勤 , 钟秦 , 黄丽娜 . SCR钒基催化剂吸附氨和水的密度泛函研究 [J ] . 环境化学 , 2008 , 27 ( 1 ): 33 - 38 .

Sun K Q , Zhong Q , Huang L N . DFT Study of ammonia and water adsorption on vanadia-based catalysts catalysts for SCR reaction [J ] . Environmental Chemistry , 2008 , 27 ( 1 ): 33 - 38 .

程浩 . 铈掺杂对铜基氧载体释氧性能以及CO化学链燃烧影响的研究 [D ] . 武汉 : 华中科技大学 , 2016 .

Cheng H . Study of the influence of Ce-doping on the oxygen releasing properties of copper based oxygen carrier and CO chemical looping combustion [D ] . Wuhan : Huazhong University of Science and Technology , 2016 .

王雪冲 . 碱土金属对Ce基催化剂SCR烟气脱硝性能的影响研究 [D ] . 北京 : 中国石油大学 , 2016 .

Wang X C . The effect of alkaline earth metals on Ce based catalyst for selective catalytic reduction of NO [D ] . Beijing : China University of Petroleum , 2016 .

Reddy B M , Lakshmanan P , Khan A , et al . Structural characterization of CeO 2 -ZrO 2 /TiO 2 and V 2 O 5 /CeO 2 -ZrO 2 /TiO 2 mixed oxide catalysts by XRD, Raman spectroscopy, HREM, and other techniques [J ] . Journal of Physical Chemistry B , 2005 , 109 ( 5 ): 1781 .

Luo M , Chen J , Chen L , et al . Struc ture and redox properties of Ce x Ti 1- x O 2 solid solution [J ] . Chem. Mater ., 2001 , 13 ( 1 ): 197 - 202 .

Chen L , Weng D , Wang J , et al . Low-temperature activity and mechanism of WO 3 -modified CeO 2 -TiO 2 catalyst under NH 3 -NO/NO 2 SCR conditions [J ] . Chinese Journal of Catalysis , 2018 , 39 ( 11 ): 1804 - 1813 .

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