HNO<sub>3</sub>改性促进活性炭低温脱硝机理的研究

郭倩倩; 景文; 侯亚芹; 刘勇进; 李风海; 黄张根

doi:10.19906/j.cnki.JFCT.2021027

HNO₃改性促进活性炭低温脱硝机理的研究

doi: 10.19906/j.cnki.JFCT.2021027

郭倩倩^{1, 2,},
景文^{2, 3},
侯亚芹²,
刘勇进²,
李风海¹,
黄张根^2, ,

1.
菏泽学院化学化工学院，山东菏泽 274015
2.
中国科学院山西煤炭化学研究所，煤转化国家重点实验室，山西太原 030001
3.
山东玉皇化工(集团)有限公司，山东菏泽 274500

基金项目: 科技部重点研发计划（2017YFC0210203），国家自然科学基金（21902173，21978314）和山西省重点研发计划（201703D11101804）的资助

详细信息

通讯作者:
Tel：+86 351 4043727, E-mail：zghuang@sxicc.ac.cn

中图分类号: X511
计量
- 文章访问数: 267
- HTML全文浏览量: 62
- PDF下载量: 36
- 被引次数: 0
出版历程
- 收稿日期: 2020-10-30
- 修回日期: 2020-11-29
- 网络出版日期: 2021-03-19
- 刊出日期: 2021-03-19

Effects of HNO₃ modification on the mechanism of low temperature NO reduction over activated carbon

1.
School of Chemistry and Chemical Engineering, Heze University, Heze 274015, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
Shandong Yuhuang Chemical (Group) Co., Ltd, Heze 274500, China

Funds: The project was supported by National Key Research and Development Program (2017YFC0210203), National Natural Science Foundation of China (21902173 and 21978314), and the Key Research and Development Program of Shanxi Province (201703D11101804).

摘要

摘要: 为了研究HNO₃改性对活性炭（AC）低温脱硝机理的影响，采用HNO₃在不同温度下对AC进行改性处理，改性前后样品在30−250 ℃进行脱硝活性测试，通过程序升温脱附（TPD）和瞬态响应实验对脱硝机理进行分析。结果表明，AC上NO转化率随反应温度升高逐渐降低再趋于稳定，反应物的吸附是速率控制步骤。含氧基团增加促进了NH₃的吸附，但这部分吸附态NH₃在30 ℃时几乎不参与反应，随反应温度升高不同程度活化，在30−90 ℃反应物的吸附是速率控制步骤，90 ℃后吸附态NH₃的活化是速率控制步骤。
- NO还原 /
- 活性炭 /
- SCR /
- 含氧基团 /
- HNO₃改性
Abstract: To study the effects of HNO₃ modification on NO reduction over activated carbon (AC) at low temperatures, the AC was modified using HNO₃ at different temperatures. The activity of the resulted activated carbons towards NO reduction with NH₃ was investigated in a temperature range of 30−250 ℃. The temperature programmed desorption (TPD) and transient response experiments were used to study the mechanism of NO reduction. The results reveal that the NO conversion decreased with temperature at the initial stage and then kept stable. The adsorption of reactants was the rate-determining step. The increase of oxygen groups on the catalyst surface enhanced NH₃ adsorption. The adsorbed NH₃ hardly reacted with NO at 30 ℃. With increasing temperature, the adsorbed NH₃ was gradually activated. In the temperature range of 30−90 ℃, the adsorption of reactants was rate-determining step of NO reduction. When the temperature was higher than 90 ℃, the reaction was dominated by the activation of adsorbed NH₃.
- NO reduction /
- activated carbon /
- SCR /
- oxygen groups /
- HNO₃ modification

HTML全文

下载: 全尺寸图片幻灯片

图 1 NO转化率随反应温度的变化

Figure 1 Variation of NO conversion with reaction temperature over AC

下载: 全尺寸图片幻灯片

图 2 AC (a)和ACN80 (b)不同温度下NO_x的脱附量

Figure 2 Amount of NO_x desorbed on AC (a) and ACN80 (b) at various temperatures

下载: 全尺寸图片幻灯片

图 3 AC和ACN80不同温度下NH₃的脱附量

Figure 3 Amount of NH₃ desorbed on AC and ACN80 at various temperatures

下载: 全尺寸图片幻灯片

图 4 ACN80在30 ℃不同反应条件下NH₃的脱附曲线

Figure 4 TPD profiles of NH₃ after co-adsorption of NH₃ and O₂ and NO reduction with NH₃ over ACN80 at 30 ℃

下载: 全尺寸图片幻灯片

图 5 30 ℃下NO (a)和NH₃ (b)瞬态响应实验

Figure 5 Results of transient response experiments of NO (a) and NH₃ (b) at 30 ℃

下载: 全尺寸图片幻灯片

图 6 150 ℃下NO (a)和NH₃ (b)瞬态响应实验

Figure 6 Results of transient response experiments of NO (a) and NH₃ (b) over AC and ACN80 at 150 ℃

下载: 全尺寸图片幻灯片

表 1 活性测试反应条件

Table 1 Reaction conditions for activity test

Unit Range

NO 1 5×10⁻⁴
NH₃ 1 5×10⁻⁴
O₂ 1 4%
N₂ balance
Total flow rate mL/min 400
Temperature ℃ 30−250

下载: 导出CSV

参考文献(28)

[1]	梁彦正, 王学涛, 张乾蔚, 罗绍峰, 周瑜枫. 双金属Ce-Mn/ZSM-5催化剂的制备及NH₃-SCR脱硝性能研究[J]. 燃料化学学报,2020,48(2):205−212. doi: 10.3969/j.issn.0253-2409.2020.02.010 LIANG Yan-zheng, WANG Xue-tao, ZHANG Qian-wei, LUO Shao-feng, ZHOU Yu-feng. Study on the preparation and catalytic performance of bimetallic Ce-Mn /ZSM-5 catalyst for selective catalytic reduction of nitric oxide by NH₃[J]. J Fuel Chem Technol,2020,48(2):205−212. doi: 10.3969/j.issn.0253-2409.2020.02.010
[2]	YULIANG W, KETING G, XIANGXIANG L, HUI L, SHAOCHEN G, DONGDONG R. Performance of Mn-Ce co-doped siderite catalysts in the selective catalytic reduction of NO_x by NH₃[J]. J Fuel Chem Technol,2019,47(12):1495−1502. doi: 10.1016/S1872-5813(19)30061-1
[3]	LI S, WANG X, TAN S, SHI Y, LI W. CrO₃ supported on sargassum-based activated carbon as low temperature catalysts for the selective catalytic reduction of NO with NH₃[J]. Fuel,2017,191:511−517. doi: 10.1016/j.fuel.2016.11.095
[4]	杨辉, 刘豪, 朱德力, 王泽安, 邱建荣, 曾汉才. 活性炭纤维联合脱硫脱硝的机理分析[J]. 中国电机工程学报,2015,35:2495−2503. YANG Hui, LIU Hao, ZHU De-li, WANG Ze-an, QIU Jian-rong, ZENG Han-cai. Mechanism of Combined Removal of SO₂ and NO Over Activated Carbon Fibers[J]. Proc CSEE,2015,35:2495−2503.
[5]	YAN W, LI S, FAN C, DENG S. Effect of surface carbon-oxygen complexes during NO reduction by coal char[J]. Fuel,2017,204:40−46. doi: 10.1016/j.fuel.2017.05.045
[6]	步学朋, 徐振刚, 李文华, 梁大明, 孙仲超, 李雪飞, 熊银伍, 吴涛, 李兰廷, 张科达. 中国活性焦烟气净化研究分析[J]. 煤质技术,2010,16(2):67−71. doi: 10.3969/j.issn.1007-7677.2010.01.027 BU Xue-peng, XU Zhen-gang, LI Wen-hua, LIANG Da-ming, SUN Zhong-chao, LI Xue-fei, XIONG Yin-wu, WU Tao, LI Lan-ting, ZHANG Ke-da. Study and analysis on flue gas purification of active coke in China[J]. Coal Qual Technol,2010,16(2):67−71. doi: 10.3969/j.issn.1007-7677.2010.01.027
[7]	YOU F, YU G, XING Z, LI J, XIE S, LI C, WANG G, REN H, WANG Y. Enhancement of NO catalytic oxidation on activated carbon at room temperature by nitric acid hydrothermal treatment[J]. Appl Surf Sci,2019,471:633−644. doi: 10.1016/j.apsusc.2018.12.066
[8]	JIANG L, LIU Q, RAN G, KONG M, REN S, YANG J, LI J. V₂O₅-modified Mn-Ce/AC catalyst with high SO₂ tolerance for low-temperature NH₃-SCR of NO[J]. Chem Eng J,2019,370:810−821. doi: 10.1016/j.cej.2019.03.225
[9]	LIN Y, LI Y, XU Z, XIONG J, ZHU T. Transformation of functional groups in the reduction of NO with NH₃ over nitrogen-enriched activated carbons[J]. Fuel,2018,223:312−323. doi: 10.1016/j.fuel.2018.01.092
[10]	ZHU L, HUANG B, WANG W, WEI Z, YE D. Low-temperature SCR of NO with NH₃ over CeO₂ supported on modified activated carbon fibers[J]. Catal Commun,2011,12(6):394−398. doi: 10.1016/j.catcom.2010.10.028
[11]	GUO Q, JING W, HOU Y, HUANG Z, MA G, HAN X, SUN D. On the nature of oxygen groups for NH₃-SCR of NO over carbon at low temperatures[J]. Chem Eng J,2015,270:41−49. doi: 10.1016/j.cej.2015.01.086
[12]	HUANG C C, LI H S, CHEN C H. Effect of surface acidic oxides of activated carbon on adsorption of ammonia[J]. J Hazard Mater,2008,159(2/3):523−527. doi: 10.1016/j.jhazmat.2008.02.051
[13]	LE LEUCH L M, BANDOSZ T J. The role of water and surface acidity on the reactive adsorption of ammonia on modified activated carbons[J]. Carbon,2007,45(3):568−578. doi: 10.1016/j.carbon.2006.10.016
[14]	ZHANG W J, RABIEI S, BAGREEV A, ZHUANG M S, RASOULI F. Study of NO adsorption on activated carbons[J]. Appl Catal B: Environ,2008,83(1/2):63−71. doi: 10.1016/j.apcatb.2008.02.003
[15]	ATKINSON J D, ZHANG Z, YAN Z, ROOD M J. Evolution and impact of acidic oxygen functional groups on activated carbon fiber cloth during NO oxidation[J]. Carbon,2013,54:444−453. doi: 10.1016/j.carbon.2012.11.060
[16]	LAZARO M, GALVEZ M, RUIZ C, JUAN R, MOLINER R. Vanadium loaded carbon-based catalysts for the reduction of nitric oxide[J]. Appl Catal B: Environ,2006,68(3/4):130−138. doi: 10.1016/j.apcatb.2006.07.025
[17]	ZHU Z, LIU Z, LIU S, NIU H, HU T, LIU T, XIE Y. NO reduction with NH₃ over an activated carbon-supported copper oxide catalysts at low temperatures[J]. Appl Catal B: Environ,2000,26:25−35. doi: 10.1016/S0926-3373(99)00144-7
[18]	ZHU Z, LIU Z, LIU S, NIU H. Adsorption and reduction of NO over activated coke at low temperatures[J]. Fuel,2000,79:651−658. doi: 10.1016/S0016-2361(99)00192-1
[19]	GÁLVEZ M E, LÁZARO M J, MOLINER R. Novel activated carbon-based catalyst for the selective catalytic reduction of nitrogen oxide[J]. Catal Today,2005,102−103:142−147. doi: 10.1016/j.cattod.2005.02.020
[20]	MOCHIDAA I, SHIRAHAMAA N, KAWANOA S, KORAIA Y, YASUTAKEB A, TANOURAC M, FUJIIC S, YOSHIKAWAD M. NO oxidation over activated carbon fiber (ACF). Part 1. Extended kinetics over a pitch based ACF of very large surface area[J]. Fuel,2000,79:1713−1723. doi: 10.1016/S0016-2361(00)00034-X
[21]	BUSCAA G, LIETTIB L, RAMISA G, BERTIC F. Chemical and mechanistic aspects of the selective catalytic reduction of NO_x by ammonia over oxide catalysts: A review[J]. Appl Catal B: Environ,1998,18:1−36. doi: 10.1016/S0926-3373(98)00040-X
[22]	吴孝敏, 倪凯文, 宇小龙, 赵宁. 暴露CeO₂不同晶面的VO_x-MnO_x/CeO₂催化剂低温NH₃-SCR脱硝的原位红外研究[J]. 燃料化学学报,2020,48:179−188. doi: 10.3969/j.issn.0253-2409.2020.02.007 WU Xiao-min, NI Kai-wen, YU Xiao-long, ZHAO Ning. In-situ DRIFTs study on different exposed facets of VO_x-MnO_x/CeO₂ catalysts for low-temperature NH₃-SCR[J]. J Fuel Chem Technol,2020,48:179−188. doi: 10.3969/j.issn.0253-2409.2020.02.007
[23]	LEI Z, HAN B, YANG K, CHEN B. Influence of H₂O on the low-temperature NH₃-SCR of NO over V₂O₅/AC catalyst: An experimental and modeling study[J]. Chem Eng J,2013,215−216:651−657. doi: 10.1016/j.cej.2012.11.011
[24]	FU M, LI C, LU P, QU L, ZHANG M, ZHOU Y, YU M, FANG Y. A review on selective catalytic reduction of NO_x by supported catalysts at 100-300 °C-catalysts, mechanism, kinetics[J]. Catal Sci Technol,2014,4(1):14−25. doi: 10.1039/C3CY00414G
[25]	CAO F, XIANG J, SU S, WANG P, SUN L, HU S, LEI S. The activity and characterization of MnO_x-CeO₂-ZrO₂/γ-Al₂O₃ catalysts for low temperature selective catalytic reduction of NO with NH₃[J]. Chem Eng J,2014,243:347−354. doi: 10.1016/j.cej.2014.01.034
[26]	TENG H, TU Y T, LAI Y C, LIN C C. Reduction of NO with NH₃ over carbon catalysts: The effects of treating carbon with H₂SO₄ and HNO₃[J]. Carbon,2001,39:575−582. doi: 10.1016/S0008-6223(00)00171-8
[27]	SUN D, LIU Q, LIU Z, GUI G, HUANG Z. Adsorption and oxidation of NH₃ over V₂O₅/AC surface[J]. Appl Catal B: Environ,2009,92:462−467. doi: 10.1016/j.apcatb.2009.09.005
[28]	张强, 刘璐, 于梦云, 周洲. 氧化铝载体硫酸化对锰铈催化剂SCR脱硝性能的影响[J]. 燃料化学学报,2019,47(9):1137−1145. doi: 10.3969/j.issn.0253-2409.2019.09.014 ZHANG Qiang, LIU Lu, YU Meng-yun, ZHOU Zhou. Effect of sulfuric acid modification of Al₂O₃ support on the SCR performance of MnCe/Al₂O₃ catalysts[J]. J Fuel Chem Technol,2019,47(9):1137−1145. doi: 10.3969/j.issn.0253-2409.2019.09.014