铁氧化物在流化床温度和CO气氛下的形态迁移及其对NO催化还原

doi:10.16085/j.issn.1000-6613.2020-0175

化工进展 ›› 2020, Vol. 39 ›› Issue (11): 4474-4479.DOI: 10.16085/j.issn.1000-6613.2020-0175

铁氧化物在流化床温度和CO气氛下的形态迁移及其对NO催化还原

吕佳宇¹^,²(), 胡丽琳², 宋天星¹^,², 张扬², 张海²(), 马素霞¹, 吕俊复²

^1.太原理工大学电气与动力工程学院，山西太原 030024
^2.清华大学能源与动力工程系，热科学与动力工程教育部重点实验室，北京 100084

出版日期:2020-11-05 发布日期:2020-11-06
通讯作者: 张海
作者简介:吕佳宇（1993—），男，硕士研究生，研究方向为煤清洁燃烧技术。E-mail：3322859118@qq.com。
基金资助:
国家自然科学基金(U1710251);山西省科技重大专项项目(20181102001)

Occurrence transformation of iron oxides and their catalytic reduction of NO under fluidized bed temperature and CO

Jiayu LYU¹^,²(), Lilin HU², Tianxing SONG¹^,², Yang ZHANG², Hai ZHANG²(), Suxia MA¹, Junfu LYU²

^1.College of Electrical and Power Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Energy and Power Engineering, Tsinghua University, Beijing 100084, China

Online:2020-11-05 Published:2020-11-06
Contact: Hai ZHANG

摘要/Abstract

摘要：

利用小型固定床实验台实验研究了铁氧化物在典型流化床温度和CO还原性气氛下的形态迁移及其生成物对NO的催化还原作用，采用分级还原结合X射线衍射（XRD）表征分析，确定铁氧化物与CO和NO反应后生成物的价态及各种铁氧化物对NO的还原机制。结果表明，Fe₂O₃在实验条件下可依次被CO还原为Fe₃O₄、FeO和单质铁，反应过程中随着还原度的增加，还原速率逐级下降，从Fe₂O₃还原到Fe₃O₄的速率最高，FeO还原到Fe速率最低，在实验温度范围内，床温升高有利于提高Fe₂O₃到Fe₃O₄的还原速率和还原度。不同形态的铁氧化物对NO的催化还原特性不同，Fe₂O₃及其部分还原后生成的Fe₃O₄都不能直接与NO反应，Fe₂O₃对CO催化还原NO的效果很弱，而Fe₃O₄对CO还原NO的反应却有很强的催化作用，而进一步还原生成FeO与单质铁还可直接与NO反应。

关键词: 氧化铁, 还原, 形态迁移, 催化剂, 流化床

Abstract:

The occurrence transformation of iron oxides during their catalytic reduction of NO under typical fluidized bed temperatures and CO atmosphere was experimentally investigated in a fixed bed reactor using the staging reduction method. With the assistance of XRD characterization, the occurrences of the products of the reducing reactions and their catalytic NO reduction mechanisms were identified. The results revealed that Fe₂O₃ was reduced by CO to Fe₃O₄, FeO and Fe successively under the experimental conditions. With the increase of reduction degree, the reduction rate gradually decreased. The reduction rate of Fe₂O₃ to Fe₃O₄ was rapid, but that of FeO to Fe became very low. In the experimental temperature range, the increase of bed temperature was beneficial to the increase of the reduction rate and to the reduction degree of Fe₂O₃ to Fe₃O₄. Moreover, different oxides have their distinct NO reduction characteristics. Fe₂O₃ and the partially reduced Fe₃O₄ barely reacted with NO directly but Fe₃O₄ had strong catalytic effect for the NO reduction by CO which however was not the case for Fe₂O₃. The further reduced FeO and Fe can also react with NO directly.

Key words: iron oxides, reduction, occurrence transformation, catalyst, fluidized bed

中图分类号:

X701

吕佳宇, 胡丽琳, 宋天星, 张扬, 张海, 马素霞, 吕俊复. 铁氧化物在流化床温度和CO气氛下的形态迁移及其对NO催化还原[J]. 化工进展, 2020, 39(11): 4474-4479.

Jiayu LYU, Lilin HU, Tianxing SONG, Yang ZHANG, Hai ZHANG, Suxia MA, Junfu LYU. Occurrence transformation of iron oxides and their catalytic reduction of NO under fluidized bed temperature and CO[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4474-4479.

参考文献

1	HAYHURST A N, NINOMIYA Y. Kinetics of the conversion of NO to N₂ during the oxidation of iron particles by NO in a hot fluidised bed[J]. Chemical Engineering Science, 1998, 53(8): 1481-1489．
2	周浩生, 陆继东, 周琥, 等. 程序升温条件下铁及其氧化物在CO存在时对N₂O的还原机理[J]．环境科学学报, 2001, 2l(2): 167-171．
2	ZHOU Haosheng, LU Jidong, ZHOU Hu, et al. Reduction of N₂O in the presence of Fe and its oxides with CO at programmed temperature[J]．Acta Scientiae Circumstance, 2001, 2l(2): 167-171．
3	GRADON B, LASEK J. Investigations of the reduction of NO to N₂by reaction with Fe[J]. Fuel, 2010, 89: 3505-3509.
4	苏亚欣, 苏阿龙, 成豪. 金属铁直接催化还原NO的实验研究[J]. 煤炭学报, 2013, 38(S1): 206-210.
4	SU Yaxin, SU Along, CHENG Hao. Experimental study on direct catalytic reduction of NO by metallic iron[J]. Journal of China Coal Society, 2013, 38(S1): 206-210.
5	苏亚欣, 苏阿龙, 成豪. CO对铁丝网卷还原NO的影响实验研究[J]. 应用基础与工程科学学报, 2013, 21(4): 638-646.
5	SU Yaxin, SU Along, CHENG Hao. Experimental study on the effect of CO on the reduction of NO by wire netting[J]. Journal of Basic Science and Engineering, 2013, 21(4): 638-646.
6	BOHN C D, CLEETON J P, MüLLER C R, et al. The kinetics of the reduction of iron oxide by carbon monoxide mixed with carbon dioxide[J]. AIChE Journal, 2010, 56(4): 1026-1029.
7	苏亚欣, 苏阿龙, 任立铭. 铁基催化剂脱除NO气体的研究现状[J]. 化工进展, 2012(S1): 154-157.
7	SU Yaxin, SU Along, REN Liming. Review on state-of-art of NO reduction by iron-based catalyst[J]. Chemical Industry and Engineering Progress, 2012(S1): 154-157.
8	王学海, 方向晨, 刘忠生. Fe/γ-Al₂O₃催化剂上CO同时还原NO和SO₂研究[J]. 工业催化, 2012(10): 69-73.
8	WANG Xuehai, FANG Xiangchen, LIU Zhongsheng. Simultaneous catalytic reduction of NO and SO₂ with CO over Fe/γ-Al₂O₃ catalysts[J]. Industrial Catalysis, 2012(10): 69-73.
9	LI J, WANG S, ZHOU L, et al. NO reduction by CO over a Fe-based catalyst in FCC regenerator conditions[J]. Chemical Engineering Journal, 2014, 255: 126-133.
10	LI J, LUO G, CHU Y, et al. Experimental and modeling analysis of NO reduction by CO for a FCC regeneration process[J]. Chemical Engineering Journal, 2012, 184: 168-175.
11	FENNELL P S, DENNIS J S, HAYHURST A N. Latter stages of the reduction of NO to N₂on particles of Fe while simultaneously oxidizing Fe to it’s oxides[J]. Energy & Fuels, 2011, 25(4): 1510-1520.
12	JOZWIAK W K, KACZMAREK E, MANIECKI T P, et al. Reduction behavior of iron oxides in hydrogen and carbon monoxide atmospheres[J]. Applied Catalysis A: General, 2007, 326(1): 17-27.
13	赵沛, 郭培民, 张殿伟. 低温非平衡条件下氧化铁还原顺序研究[J]. 钢铁, 2006, 41(8): 12-15.
13	ZHAO Pei, GUO Peiming, ZHANG Dianwei. Study on reduction sequence of hematite at low-temperature non-equilibrium state[J]. Iron and Steel, 2006, 41(8): 12-15.
14	智强, 赵炜, 李辉. 模拟流态化CO还原Fe₂O₃微粉的试验研究[J]. 粉末冶金工业, 2014, 24(3): 11-16.
14	ZHI Qiang, ZHAO Wei, LI Hui. Experimental study on reduction of iron oxide micro-powder by CO in simulating fluidization state[J]. Powder Metallurgy Industry, 2014, 24(3): 11-16.
15	HOU B L, ZHANG H Y. Determination of the intrinsic kinetics of iron oxide reduced by carbon monoxide in an isothermal differential micro-packed bed[J]. Chinese Journal of Chemical Engineering, 2015(6): 974-980.
16	庞建明, 郭培民, 赵沛. 流化床中CO还原1~3mm铁矿粉研究[J]. 钢铁钒钛, 2016, 31(3): 15-19.
16	PANG Jianming, GUO Peimin, ZHAO Pei. Study on the reduction of 1~3mm iron ore powder by CO in fluidized bed[J].Iron Steel Vanadium Titanium, 2016, 31(3): 15-19.
17	李玉祥, 孙毅, 杨康, 等. 模拟流化床气基直接还原赤铁矿粉的试验研究[J]. 金属矿山, 2012, 41(1): 77-79.
17	LI Yuxiang, SUN Yi, YANG Kang, et al. Experimental study on simulating fluidized bed gas-based direct reduction of hematite powder[J]. Metal Mine, 2012, 41(1): 77-79.
18	徐春保, 吴胜利, 苍大强. 金属氧化物对CO还原NO反应的催化作用[J]. 环境科学, 1999, 20(1): 31-33.
18	XU Chunbao, WU Shengli, CANG Daqiang. The catalytic performance of several metallic oxides and complex metallic oxides on reaction of CO reducing NO[J]. Environmental Science, 1999, 20(1): 31-33.

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铁氧化物在流化床温度和CO气氛下的形态迁移及其对NO催化还原

Occurrence transformation of iron oxides and their catalytic reduction of NO under fluidized bed temperature and CO

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