低温烟气脱硝催化剂适用条件与动力学

doi:10.11949/j.issn.0438-1157.20181438

化工学报 ›› 2019, Vol. 70 ›› Issue (8): 2981-2990.DOI: 10.11949/j.issn.0438-1157.20181438

低温烟气脱硝催化剂适用条件与动力学

李萍^1,²(),李长明¹,段正康²,高士秋¹,许光文³,余剑¹()

1. 中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
2. 湘潭大学化工学院，湖南湘潭 411105
3. 沈阳化工大学，辽宁沈阳 110142

收稿日期:2018-12-04 修回日期:2019-03-01 出版日期:2019-08-05 发布日期:2019-08-05
通讯作者: 余剑
作者简介:李萍（1993—），女，硕士研究生，lppl1993@163.com
基金资助:
国家自然科学基金青年基金项目(21601192);中日政府间国际合作项目(2016YFE0128300);多项复杂系统国家重点实验室自主研究课题项目(MPCS-2017-A-06)

Application conditions and kinetics simulation over SCR catalyst for flue gas denitrification under low temperature

Ping LI^1,²(),Changming LI¹,Zhengkang DUAN²,Shiqiu GAO¹,Guangwen XU³,Jian YU¹()

1. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, China
3. Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2018-12-04 Revised:2019-03-01 Online:2019-08-05 Published:2019-08-05
Contact: Jian YU

摘要/Abstract

摘要：

随着国家对大气污染物排放要求的进一步提高，中低温脱硝催化剂也将迎来更大的市场和挑战。为进一步明确低温脱硝催化剂的应用特性，在不同温度、烟气流速、催化剂长度和水蒸气含量下对已产业化的蜂窝催化剂的脱硝活性进行了系统考察，获得该中低温脱硝催化剂的适用区间与动力学参数。实验表明，在温度高于160℃条件下，通过调变气速与催化剂长度可以实现理论氨氮比的脱硝率；且在考察水蒸气对脱硝活性的影响时，发现脱硝率随着水蒸气含量的增加而逐步降低，在低温条件下降低更加显著，最大降幅达30%；依据2 ~ 4 m/s气速下的脱硝率与停留时间的关系，拟合脱硝反应活化能为22.7 kJ/mol，属于典型的气体外表面扩散控制，可为低温脱硝催化剂选型提供重要参考；180000 m³/h烟气量的脱硝示范验证了该催化剂在180℃下脱硝率超过90%，显示了优良的工业应用和推广前景。

关键词: 选择性催化还原, 低温催化剂, 操作范围, 工业示范, 动力学参数

Abstract:

With the more stringent requirements of atmospheric pollutant emission standards, medium and low temperature catalyst would have larger market and greater challenge. In order to further clarify the application characteristics of the low temperature denitration catalyst, the denitration activity of the industrialized honeycomb catalyst was systematically investigated under different temperatures, flue gas flow rate, catalyst length and water vapor content. The applicable temperature range and kinetic parameters of the catalyst under low temperature window were also determined. These results showed that theoretical denitrification rate of NH₃/NO can be achieved above 160℃ by adjustments of gas velocity and length of honeycomb catalyst. Moreover, it was found that NO conversion gradually decreased with the increase of steam content, and the negative impact become more severely below 180℃ with less than 70% DeNO _x efficiency at 160℃ and 35% steam content in flue gas. According to the relationship between denitrification rate and residence time (at 2－4 m/s gas velocity), the reaction activation energy was calculated to be 22.7 kJ/mol, suggesting that the reaction is limited by the external diffusion. The industrial DeNO _x demonstration of flue gas with 180000 m³/h over this catalyst exhibits more than 90% DeNO _x efficiency at 180℃ and promising industrialization prospect.

Key words: SCR, low temperature catalyst, operating range, industrial application, kinetic parameters

中图分类号:

TQ 028.8

李萍, 李长明, 段正康, 高士秋, 许光文, 余剑. 低温烟气脱硝催化剂适用条件与动力学[J]. 化工学报, 2019, 70(8): 2981-2990.

Ping LI, Changming LI, Zhengkang DUAN, Shiqiu GAO, Guangwen XU, Jian YU. Application conditions and kinetics simulation over SCR catalyst for flue gas denitrification under low temperature[J]. CIESC Journal, 2019, 70(8): 2981-2990.

图/表 11

图1 实验装置流程

Fig.1 Schematic diagram for evaluation of catalytic activity

图2 蜂窝体催化剂表征结果

Fig.2 Characterization results of honeycomb catalyst

表1 蜂窝催化剂脱硝效率

Table 1 NO conversions over honeycomb catalyst under different reaction conditions

催化剂长度/cm	气速/(m/s)	NO转化率/%
催化剂长度/cm	气速/(m/s)	120℃	160℃	200℃	240℃
20	1	7.5	45.9	71.3	85.4
	2	6.7	27.5	51.3	70
	3	2.8	18.9	39.4	50.3
	4	2.8	18.7	38.5	50.7
40	1	23.9	78	95.6	100
	2	20.4	59	83.8	99.7
	3	10.3	43.7	76.9	91.3
	4	3.5	35.4	69.8	86.5
60	1	56.1	99.9	100	100
	2	31.5	85.6	98.5	100
	3	12	55.6	84.8	96.8
	4	7.9	23.7	70	92.8
80	1	60	100	100	100
	2	45.1	96.9	100	100
	3	16.5	70	96.6	100
	4	9.2	48.1	90.3	100

图3 不同催化剂长度对应的脱硝率与气速的关系

Fig.3 NO conversion vs gas velocity under different catalyst length

图4 气速、温度、脱硝率三维图

Fig.4 Three-dimensional diagrams for gas velocity， temperature and NO conversion from Table 1

图5 水蒸气含量对脱硝活性的抑制效果及催化剂抗硫抗水稳定性测试

Fig.5 Inhibition of steam content on catalytic activity and stability test in presence of SO2 and H2O

图6 相同停留时间下气速对脱硝率的影响

Fig.6 NO conversion vs gas velocity at the same residence time

图7 不同温度对应的脱硝率随停留时间的变化关系

Fig.7 NO conversion vs residence time under different temperatures

图8 速率常数拟合

Fig.8 Fitting of rate constant linear

图9 lnK-1/T线性回归图

Fig.9 Linear fitting for lnK-1/T on Arrhenius equation

图10 脱硝示范工艺流程

Fig.10 Process flow of industrial demonstration

参考文献 30

1	李穹, 吴玉新, 杨海瑞, 等 . SNCR脱硝特性的模拟及优化[J]. 化工学报, 2013, 64(5): 1789-1796.
	Li Q , Wu Y X , Yang H R , et al . Simulation and optimization of SNCR process[J]. CIESC Journal, 2013, 64(5): 1789-1796.
2	Lai J K , Wachs I E . A perspective on the selective catalytic reduction (SCR) of NO with NH₃ by supported V₂O₅-WO₃/TiO₂ catalysts[J]. ACS Catalysis, 2018, 8(3): 6537-6551.
3	顾卫荣, 周明吉, 马薇 . 燃煤烟气脱硝技术的研究进展[J]. 化工进展, 2012, 31(9): 2084-2092.
	Gu W R , Zhou M J , Ma W . Technology statue and analysis on coal-fired flue gas denitrification[J]. Chemical Industry and Engineering Progress, 2012, 31(9): 2084-2092.
4	苗强 . 脱硝技术的现状及展望[J]. 洁净煤技术, 2017, 23(2): 12-19.
	Miao Q . Progress and prospects of denitration technology[J]. Clean Coal Technology, 2017, 23(2):12-19.
5	顾庆华, 胡秀丽 . SCR脱硝反应区域运行温度影响因素研究[J]. 洁净煤技术, 2015, 21(2):77-80.
	Gu Q H , Hu X L . Influencing factors of operating temperature of denitration SCR reactor[J]. Clean Coal Technology, 2015, 21(2):77-80.
6	Tao X X , Xu N , Xie M H , et al . Progress of the technique of coal microwave desulfurization[J]. International Journal of Coal Science & Technology, 2014, 1(1): 113-128.
7	谢慧, 周跃, 张奎, 等 . 玻璃窑炉应用SCR烟气脱硝技术的中试研究[J]. 玻璃, 2013, 3:35-39.
	Xie H , Zhou Y , Zhang K , et al . SCR de-nitrification pilot-plant test of flue gas from glass furnace[J]. Glass, 2013, 3:35-39.
8	Udayan S , Naushita S , Siba S M . Environmental life cycle assessment of Indian coal-fired power plants[J]. International Journal of Coal Science & Technology, 2016, 3(2): 215-225.
9	陈杭君, 赵华, 丁经纬 . 火电厂烟气脱硝技术介绍[J]. 热力发电, 2005, 2: 15-18.
	Chen H J , Zhao H , Ding J W . Introduction of flue gas denitration technology of thermal power plant[J]. Thermal Power Generation, 2005, 2: 15-18.
10	郦建国, 朱法华, 孙雪丽 . 中国火电大气污染防治现状及挑战[J]. 中国电力, 2018, 51(6): 2-10.
	Li J G , Zhu F H , Sun X L . Current status and challenges of atmospheric pollution prevention and control of thermal power plants in China[J]. Electric Power, 2018, 51(6): 2-10.
11	张慧玲 . 焦炉烟气脱硝技术的分析与探讨[J]. 山西焦煤科技, 2016, 8: 7179-7182.
	Zhang H L . Analysis and discussion of coke oven flue gas denitration technology[J]. Shanxi Coking Coal Science & Technology, 2016, 8: 7179-7182.
12	尹涛, 张家平, 叶明强, 等 . 炼焦炉应用SCR烟气脱硝的中试研究[J]. 环境工程学报, 2016, 10(3): 151-153.
	Yin T , Zhang J P , Ye M Q , et al . SCR de-nitrification pilot-plant test of flue gas from coking furnace[J]. Chinese Journal of Environmental Engineering, 2016, 10(3): 151-153.
13	刘亭, 王廷春, 吴瑞青, 等 . 低温NH₃-SCR脱硝催化剂研究进展[J]. 安全与环境学报, 2012, 19(6): 42-44.
	Liu T , Wang T C , Wu R Q , et al . Research advance review for low-temperature NH₃-SCR catalysts[J]. Journal of Safety and Environment, 2012, 19(6): 42-44.
14	苗永旗, 庄柯, 袁立明 . 低温SCR脱硝催化剂研究进展[J]. 电力科技与环保, 2013, 29(1): 13-15.
	Miao Y Q , Zhuang K , Yuan L M . Research process of low-temperature SCR catalysts[J]. Electric Power Environmental Protection, 2013, 29(1): 13-15.
15	Svachula J , Ferlazzo N , Forzatti P , et al . Selective reduction of nitrogen oxides (NO _x ) by ammonia over honeycomb selective catalytic reduction catalysts[J]. Industrial & Engineering Chemistry Research, 1993, 32(6): 1053-1060.
16	Zuercher S , Hackel M , Schaub G . Kinetics of selective catalytic NO _x reduction in a novel gas-particle filter reactor (catalytic filter element and sponge insert) [J]. Industrial & Engineering Chemistry Research, 2008, 47(5): 1435-1442.
17	肖翠微, 李婷 . 低温SCR锰系脱硝催化剂的研究进展[J]. 洁净煤技术, 2016, 22(1): 95-100.
	Xiao C W , Li T . Research progress of low-temperature SCR denitrification manganese-based catalysts[J]. Clean Coal Technology, 2016, 22(1): 95-100.
18	杨永利, 徐东耀, 晁春艳, 等 . 负载型Mn基低温NH₃-SCR脱硝催化剂研究综述[J]. 化工进展, 2016, 35(4): 1094-1100.
	Yang Y L , Xu D Y , Chao C Y , et al . Research advance review on supported Mn-based catalysts at low-temperature selective catalytic reduction of NO _x with NH₃ [J]. Chemical Industry and Engineering Progress, 2016, 35(4): 1094-1100.
19	郑玉婴, 汪谢 . Mn基低温SCR脱硝催化剂的研究进展[J]. 功能材料, 2014, 45(11): 11008-11012.
	Zheng Y Y , Wang X . Research progress on Mn-based catalysts for low-temperature selective catalytic reduction of NO _x [J]. Journal of Functional Materials, 2014, 45(11): 11008-11012.
20	梅笛, 谢峻林, 方德, 等 . SCR脱硝催化剂的碱及碱土金属中毒研究进展[J]. 硅酸盐通报, 2014, 33(6): 1398-1402.
	Mei D , Xie J L , Fang D , et al . Research progress on alkali and alkaline earth metal poison of SCR catalyst[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(6): 1398-1402
21	沈伯雄, 刘亭, 杨婷婷, 等 . 低温SCR脱硝催化剂过渡金属氧化物改性及硫中毒失活机制研究[J]. 环境科学, 2009, 30(8): 2204-2209.
	Shen B X , Liu T , Yang T T , et al . Deactivation by SO₂ of transition metal oxides modified low-temperature SCR catalyst for NO _x reduction with NH₃ [J]. Environmental Science, 2009, 30(8): 2204-2209.
22	Tsuji K , Shiraishi I . Combined desulfurization, denitrification and reduction of air toxics using activated coke (Ⅰ): Activity of activated coke[J]. Fuel, 1997, 76(6): 555-560.
23	李长明, 许启成, 郭凤, 等 . 低温焦化烟气脱硝催化剂制备与中试验证研究[J]. 洁净煤技术, 2017, 23(4): 63-70.
	Li C M , Xu Q C , Guo F , et al . Production and pilot-scale test of honeycomb DeNO _x catalyst for low temperature flue gas from coking plant[J]. Clean Coal Technology, 2017, 23(4): 63-70.
24	Gao Y , Luan T , Lu T , et al . Performance of V₂O₅-WO₃-MoO₃/TiO₂ catalyst for selective catalytic reduction of NO _x by NH₃ [J]. Chinese Journal of Chemical Engineering, 2013, 21(1): 1-7.
25	Li C M , Yu J , He Y , et al . The industrial feasibility of low temperature DeNO _x in the presence of SO _x : a project case in a medium coking plant[J]. RSC Advances, 2018, 8(33): 18260-18265.
26	Zhang Y S , Li C M , Wang C , et al . Pilot-scale test of a V₂O₅-WO₃/TiO₂-coated type of honeycomb DeNO _x catalyst and its deactivation mechanism[J]. Industrial & Engineering Chemistry Research, 2019, 58(2): 828-835.
27	Schütt M , Gallinger M , Moos R . Particulate filter substrates with SCR-functionality manufactured by Co-extrusion of ceramic substrate and SCR active material[J]. Top. Catal. , 2016, 60: 1-5.
28	Xiong S , Xiao X , Liao Y , et al . Global kinetic study of NO reduction by NH₃ over V₂O₅-WO₃/TiO₂: relationship between the SCR performance and the key factors[J]. Ind. Eng. Chem. Res. , 2015, 54: 11011-11023.
29	Koebel M , Elsener M . Selective catalytic reduction of NO over commercial DeNO _x catalysts: experimental determination of kinetic and thermodynamic parameters[J]. Chemical Engineering Science, 1998, 53(6): 657-669.
30	Busca G , Liett L , Ramis G , et al . Chemical and mechanistic aspects of the selective catalytic reduction of NO _x by ammonia over oxide catalysts: a review[J]. Applied Catalysis B: Environmental, 1998, 18(2): 1-36.

[1]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[2]	李泽严, 樊星, 李坚. 非热等离子体强化TiO₂催化尿素分解副产物水解性能的研究[J]. 化工学报, 2021, 72(9): 4698-4707.
[3]	邱爽, 肖永厚, 刘建辉, 贺高红. 一步法制备高活性NH₃-SCR催化剂Cu-SAPO-34：Si含量的影响[J]. 化工学报, 2021, 72(5): 2578-2585.
[4]	史玉婷, 皇甫林, 李长明, 王月, 高士秋, 伞晓广, 韩振南, 余剑. V₂O₅-MoO₃/TiO₂催化滤袋的制备及中试应用[J]. 化工学报, 2021, 72(11): 5598-5606.
[5]	刘涛, 张书廷. Ba、Co共掺MnO_x复合氧化物低温选择性催化还原NO研究[J]. 化工学报, 2020, 71(7): 3106-3113.
[6]	王晨,陈泽翔,王建强,沈美庆,王军. 基于NH₃-SCR反应铜基小孔分子筛催化剂Na中毒对比研究[J]. 化工学报, 2020, 71(12): 5551-5560.
[7]	张霄玲,鲍佳宁,李运甲,皇甫林,李文松,高士秋,许光文,李长明,余剑. 工业MnO_x颗粒催化剂的制备及其低温脱硝应用研究[J]. 化工学报, 2020, 71(11): 5169-5177.
[8]	汤常金,孙敬方,董林. 超低温（< 150℃）SCR脱硝技术研究进展[J]. 化工学报, 2020, 71(11): 4873-4884.
[9]	陈潇雪, 宋敏, 孟凡跃, 卫月星. Fe _x MnCe₁-AC低温SCR催化剂SO₂中毒机理研究[J]. 化工学报, 2019, 70(8): 3000-3010.
[10]	张涛, 刘琪英, 张彩红, 张琦, 马隆龙. Ni/La₂O₂CO₃催化剂对山梨醇氢解产物的选择性调控[J]. 化工学报, 2017, 68(6): 2359-2367.
[11]	王君, 刘天璐, 黄群星, 池涌, 马增益. 储运含油污泥慢速热解特性分析[J]. 化工学报, 2017, 68(3): 1138-1145.
[12]	戚春萍, 武文粉, 王晨晔, 李会泉. 燃煤电厂废旧SCR脱硝催化剂中TiO₂载体的回收与再利用[J]. 化工学报, 2017, 68(11): 4239-4248.
[13]	石建伟, 吴威, 杨荟楠, 苏明旭, 蔡小舒. 基于激光光谱法的尿素水溶液液膜多参数测量[J]. 化工学报, 2017, 68(1): 79-86.
[14]	刘建华, 杨晓博, 张琛, 吴凡, 李忠, 夏启斌. Fe₂O₃对V₂O₅-WO₃/TiO₂催化剂表面性质及其性能的影响[J]. 化工学报, 2016, 67(4): 1287-1293.
[15]	李倩, 谷华春, 辛颖, 李壮壮, 张昭良. V₂O₅-WO₃/TiO₂脱硝催化剂机械强度和孔隙率的响应曲面模型[J]. 化工学报, 2015, 66(9): 3496-3503.

低温烟气脱硝催化剂适用条件与动力学

Application conditions and kinetics simulation over SCR catalyst for flue gas denitrification under low temperature

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价