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

doi:10.11949/0438-1157.20200234

Abstract

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

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

CLC Number:

TQ 137.1

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.

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.

Figures/Tables 9

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

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

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

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)

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

Fig.6 XRD patterns of different catalysts

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

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

Fig.8 SEM images of different catalysts

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