赤泥催化剂的制备及其对模拟烟气中微量氨的脱除性能

doi:10.11949/j.issn.0438-1157.20181051

化工学报 ›› 2019, Vol. 70 ›› Issue (3): 1056-1064.DOI: 10.11949/j.issn.0438-1157.20181051

赤泥催化剂的制备及其对模拟烟气中微量氨的脱除性能

王超¹(),李长明²,皇甫林²,李萍¹,杨运泉¹,高士秋²,余剑²(),许光文³

1. 湘潭大学化工学院，湖南湘潭 411105
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. 沈阳化工大学，辽宁沈阳 110142

收稿日期:2018-09-19 修回日期:2018-12-11 出版日期:2019-03-05 发布日期:2019-03-05
通讯作者: 余剑
作者简介:<named-content content-type="corresp-name">王超</named-content>（1993—），男，硕士研究生，<email>wang_chao999058@163.com</email>|余剑（1979—），男，博士，副研究员，<email>yujian@ipe.ac.cn</email>
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(MPCS-2017-A-06);多项复杂系统国家重点实验室自主研究课题(MPCS-2017-D-11)

Preparation of red mud-based catalyst and performance for trace ammonia in simulative tail gas

Chao WANG¹(),Changming LI²,Lin HUANGFU²,Ping LI¹,Yunquan YANG¹,Shiqiu GAO²,Jian YU²(),Guangwen XU³

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

Received:2018-09-19 Revised:2018-12-11 Online:2019-03-05 Published:2019-03-05
Contact: Jian YU

摘要/Abstract

摘要：

以赤泥固废为原料，采用酸解-碱沉淀法制备了赤泥粉体催化剂，并提出一种将催化剂直接喷入SNCR尾气中的除氨工艺，考察了催化剂加入点温度、空速、NH₃浓度及水蒸气对氨去除能力的影响。研究发现，该催化过程具有很高的活性和N₂的选择性，450℃以上NH₃的转化率可达100%，同时在400～500℃间，N₂的选择性高于80%，达到了很好的除氨效果；在500℃，空速为3×10⁶~6×10⁶ h^-1之间时，出口NH₃浓度均为0；此工艺对于逃逸NH₃浓度的适用性较强，入口[NH₃] = 50×10^-6~1000×10^-6 mol/L范围内均可完全脱除，且具有一定的抗水能力。通过一系列表征发现，该种方法制备的赤泥催化剂不仅消除了原始固废的强碱性，还提高了其表面酸性，具有较高的比表面积、孔容和丰富的表面微观结构，使NH₃的吸附及活化反应能力大大增加；该催化剂过程遵循iSCR机理，在400～500℃温度区间主要发生NH₃-SCO反应，低于400℃主要发生NH₃-SCR反应，粉体催化剂通过NH₃-SCR和NH₃-SCO协同反应达到了去除尾气中微量氨的目的。

关键词: 氨逃逸, 废物处理, 赤泥, 催化剂, 模拟, 内部催化氧化

Abstract:

A Fe-based powder catalyst was prepared from red mud (RM) solid waste with acid base neutralization method, which was used to eliminate the trace ammonia thought the proposed process of directly spraying the catalyst into SNCR tail gas. The effects of temperature, space velocity, NH₃ concentration and water vapor on ammonia removal capacity of the catalyst were investigated in details, and excellent removal efficiency could be achieved with 100% NH₃ conversion above 450℃ as well as > 80% selectivity of N₂ between 400—500℃. Especially, the trace ammonia in the tail gas can completely be cleared with 0 left between the space velocity of 3×10⁶—6×10⁶ h^-1 at 500℃. Meanwhile, the catalytic process is also effective for the removal of NH₃ with wide concentration of (40×10^-6~800×10^-6 mol/L) even in the presence of water. The multiple characterizations further revealed that the strong alkalinity of the original solid waste was removed together with the increase of surface acidity as well as large specific surface area and rich surface microstructure for the obtained red mud catalyst, which accounts for its significant increase of adsorption and activation of NH₃. Moreover, it was found the removal process of NH₃ follows the internal selective catalytic reduction (iSCR) mechanism, and the NH₃ was eliminated through both the NH₃-SCR and NH₃-SCO reactions, which mainly function below 400℃ and between 400-500℃, respectively.

Key words: ammonia slip, waste treatment, red med, catalyst, simulation, iSCR

中图分类号:

TQ 426.6

王超, 李长明, 皇甫林, 李萍, 杨运泉, 高士秋, 余剑, 许光文. 赤泥催化剂的制备及其对模拟烟气中微量氨的脱除性能[J]. 化工学报, 2019, 70(3): 1056-1064.

Chao WANG, Changming LI, Lin HUANGFU, Ping LI, Yunquan YANG, Shiqiu GAO, Jian YU, Guangwen XU. Preparation of red mud-based catalyst and performance for trace ammonia in simulative tail gas[J]. CIESC Journal, 2019, 70(3): 1056-1064.

图/表 8

图1 城市生活垃圾焚烧发电工艺示意图及氨逃逸脱除工艺管道布置

Fig.1 Schematic diagram of municipal solid waste incineration power generation process together with removal process of ammonia slip

图2 赤泥改性前后样品的XRD图谱（a）、热重分析（b）、N2吸附等温线（c）和孔径分布曲线（d）

Fig.2 XRD patterns (a), TG analysis (b), nitrogen adsorption isotherms (c) and pore size distributions（d）of RM and MRM

表1 赤泥改性前后样品的主要化学成分

Table 1 Main chemical composition of RM and MRM

样品	主要组成/%(mass)
样品	Na₂O	MgO	Al₂O₃	CaO	SO₃	Fe₂O₃	TiO₂	SiO₂	Others
RM	10.97	0.23	19.92	1.29	0.64	44.18	8.01	13.43	1.33
MRM	0.00	0.00	19.12	0.75	4.58	53.78	8.81	11.83	0.26

图3 赤泥改性前后的扫描电镜图

Fig.3 SEM images of RM and MRM

表2 赤泥改性前后的比表面积和孔体积

Table 2 Specific surface area and pore volumes of RM and MRM

样品

比表面积/(m²/g）

孔体积/

(cm³/g)

图4 赤泥改性前后样品的NH3-TPD谱图

Fig.4 NH3-TPD spectra of RM and MRM

图5 粉尘催化剂SCO性能的影响

Fig.5 Effect of space velocity，NH3 concentration and water on SCO activity over dust catalysts

图6 改性赤泥的NH3-SCO (a)、NH3-SCR (b)催化性能和产物组成

Fig.6 NH3-SCO (a) and NH3-SCR (b) performance and yield proportions of reaction products over MRM at different temperatures[reaction conditions: 1.5 g of catalyst, [NH3]=500×10-6 mol/L, [NO]=500×10-6 mol/L(only for SCR process), [O2]=5%(vol), balance gas: N2, total flow rate 1500 ml/min, GHSV=10000 h-1]

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赤泥催化剂的制备及其对模拟烟气中微量氨的脱除性能

Preparation of red mud-based catalyst and performance for trace ammonia in simulative tail gas

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