工业MnOx颗粒催化剂的制备及其低温脱硝应用研究

doi:10.11949/0438-1157.20200234

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 5169-5177.DOI: 10.11949/0438-1157.20200234

• 催化、动力学与反应器 • 上一篇下一篇

工业MnO_x颗粒催化剂的制备及其低温脱硝应用研究

张霄玲^1,²(),鲍佳宁⁵,李运甲^1,²,皇甫林^1,²,李文松³,高士秋²,许光文⁴,李长明²,余剑²()

^1.中国科学院大学化学与化工学院，北京 100049
^2.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
^3.湘潭大学化工学院，湖南湘潭 411105
^4.沈阳化工大学，辽宁沈阳 110142
^5.约翰斯?霍普金斯大学环境健康与工程系，美国马里兰州巴尔的摩市 21287

收稿日期:2020-03-05 修回日期:2020-05-17 出版日期:2020-11-05 发布日期:2020-11-05
通讯作者: 余剑
作者简介:张霄玲（1995—），女，硕士研究生，1880175531@163.com
基金资助:
国家自然科学基金青年基金项目(21601192);多相实验室开放课题(MPCS-2019-0-03)

Preparation and industrial application of MnO_x particle catalyst for low temperature denitration

Xiaoling ZHANG^1,²(),Jianing BAO⁵,Yunjia LI^1,²,Lin HUANGFU^1,²,Wensong LI³,Shiqiu GAO²,Guangwen XU⁴,Changming LI²,Jian YU²()

^1.School of Chemistry and Chemical Engineering, University of Chinese Academy of Science, Beijing 100049, China
^2.State Key Laboratory of Multi-phase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.School of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, China
^4.Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^5.School of Environmental Health and Engineering, University of Johns Hopkins，Baltimore 21287, Maryland, USA

Received:2020-03-05 Revised:2020-05-17 Online:2020-11-05 Published:2020-11-05
Contact: Jian YU

摘要/Abstract

摘要：

以工业硫酸锰为前体，通过沉淀、洗涤、挤出、煅烧步骤批量制备了高活性颗粒状低温MnO_x脱硝催化剂（?5 mm×30 mm）。针对天然气冷热电三联供高含水低含硫烟气开展应用示范，研究催化剂在不同工况下的脱硝性能与长周期活性稳定性，结果表明：在入口NO_x浓度850~1000 mg/m3、床层温度145~175℃、空速4405 h^-1工况条件下，脱硝率达到87.88%～97.47%，连续运行1180 h后脱硝效率有约3%的微弱衰减。对长周期运行后催化剂进行取样，进行XRD、BET、SEM表征及活性测试结果表明：该催化剂在该高湿烟气长时间运行中发生了一定程度的晶型转变，颗粒烧结、尺寸变大以及比表面积降低，导致其脱硝活性降低。该研究结果将为高活性锰基催化剂的制备及其低温脱硝工业应用提供参考和借鉴。

关键词: 锰氧化物, 低温脱硝, 选择性催化还原, 失活, 工业应用

Abstract:

Powder nano-manganese oxide (MnO_x) material with excellent low-temperature denitration activity was prepared by precipitation-calcination method with manganese sulfate as precursor. The industrial catalyst of ?5 mm×30 mm granular MnO_xwas successfully produced by continuous extrusion molding technology. The produced industrial catalyst was applied in the denitration purification of low-temperature flue gas from cold, hot & electric triple supply(CCHP) system on the conditions of 5000 m³/h gas flow, 850—1000 mg/m³ inlet NO_x and the temperature from 145 to175℃. The NO conversion can achieve to 87.88%—97.47% under the GHSV of 4405 h^-1, and 3% decline of denitration efficiency was observed after use for 1180 hours. The laboratory test also confirmed the reduced activity for the used sample. Moreover, XRD, BET and SEM results showed the crystal transition, increased particle size and decreased surface area for the used MnO_x sample, which accounted for the observed decline of denitration efficiency after long term use on the industrial conditions. The results of this study will provide references for the preparation of highly active manganese-based catalysts and their industrial application in low-temperature denitrification.

Key words: manganese oxide, low-temperature denitration, SCR, deactivation, industrial application

中图分类号:

TQ 137.1

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.

Xiaoling ZHANG,Jianing BAO,Yunjia LI,Lin HUANGFU,Wensong LI,Shiqiu GAO,Guangwen XU,Changming LI,Jian YU. Preparation and industrial application of MnO_x particle catalyst for low temperature denitration[J]. CIESC Journal, 2020, 71(11): 5169-5177.

图/表 9

图1 冷热电三联供系统烟气脱硝装置照片（a）与工艺流程图（b）

Fig.1 The picture of denitration device from CCHP (a) and the corresponding process flow diagram (b)

图2 新鲜催化剂MnOx-350的XRD谱图（a），TG曲线（b）、N2等温吸脱附曲线（c）及孔径分布图（d）

Fig.2 XRD pattern (a), TG curve(b), N2 adsorption-desorption isotherms (c) and pore size distribution by N2 adsorption branch (d) of fresh granular MnOx-350 catalyst

图3 不同温度与空速下催化剂MnOx-350的脱硝性能（H2O:10%(体积)）

Fig.3 The catalytic performance of MnOx-350 catalyst under different reaction temperature and space velocity in simulated flue gas contained 10%(vol.) water vapor

图4 催化剂在CCHP低硫高湿烟气中脱硝应用性能：165~175℃(a)、155~165℃(b)、145~155℃(c)温区的脱硝活性以及运行1180 h后的脱硝活性（d）

Fig.4 The activity test of MnOx catalyst for the flue gas from CCHP system： NO conversion at different temperature range of 165—175℃(a), 155—165℃(b), 145—155℃(c) and after operation for 1180 h (d)

图5 不同催化剂高空速脱硝活性测试结果

Fig.5 SCR activities at a high GHSV for different catalysts

图6 催化剂XRD晶型表征谱图

Fig.6 XRD patterns of different catalysts

图7 催化剂的N2等温吸脱附曲线(a)及孔径分布图(b)

Fig.7 N2 adsorption-desorption isotherms (a) and pore size distribution (b) of different catalysts

表1 催化剂比表面、孔容及孔径数据

Table 1 Specific surface, pore volume and pore size of different catalysts

Sample	S_BET/ (m²/g)	Pore volume/(cm³/g)	Pore size/nm
MnO_x - 350	108.5	0.3663	8.381
MnO_x -350 - 1180	63.35	0.2963	10.64
MnO_x - 350 -hy	56.29	0.2420	10.99
MnO_x - 500	32.16	0.2507	31.73

图8 催化剂SEM形貌表征

Fig.8 SEM images of different catalysts

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工业MnO_x颗粒催化剂的制备及其低温脱硝应用研究

Preparation and industrial application of MnO_x particle catalyst for low temperature denitration

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工业MnOx颗粒催化剂的制备及其低温脱硝应用研究

Preparation and industrial application of MnOx particle catalyst for low temperature denitration

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工业MnO_x颗粒催化剂的制备及其低温脱硝应用研究

Preparation and industrial application of MnO_x particle catalyst for low temperature denitration