废弃SCR催化剂的循环再利用及表征分析研究

唐昊; 陆强; 杨江毅; 李慧; 李文艳; 杨勇平

废弃SCR催化剂的循环再利用及表征分析研究

华北电力大学生物质发电成套设备国家工程实验室, 北京 102206

基金项目:

国家重点基础研究发展规划 973 project

国家重点基础研究发展规划 2015CB251501

北京市科技新星 Z171100001117064

中央高校基本科研业务费 2016YQ05

中央高校基本科研业务费 2015ZZD02

详细信息

通讯作者:
LU Qiang, Tel:010-61772030, E-mail:qianglu@mail.ustc.edu.cn.

中图分类号: TQ032.4;X705
计量
- 文章访问数: 128
- HTML全文浏览量: 42
- PDF下载量: 14
- 被引次数: 0
出版历程
- 收稿日期: 2017-08-30
- 修回日期: 2017-12-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-02-10

Research on recycling and characterization analysis of the waste SCR catalyst

National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

Funds:

the Major State Basic Research Development Program of China 973 project

the Major State Basic Research Development Program of China 2015CB251501

Beijing Nova Program Z171100001117064

Fundamental Research Funds for the Central Universities 2016YQ05

Fundamental Research Funds for the Central Universities 2015ZZD02

摘要

摘要: 针对废弃SCR脱硝催化剂常规再利用处理后存在SO₂氧化率高的问题, 提出了一种新型的废弃催化剂再利用新工艺, 包括酸洗、还原酸浸和活性组分负载等步骤, 以有效控制再利用催化剂的SO₂氧化率。实验考察了经不同步骤处理后所得催化剂的组分、脱硝效率和SO₂氧化率的变化情况, 并对催化剂进行了深入的分析表征。结果表明, 新鲜催化剂、废弃催化剂、常规再利用催化剂、新型再利用催化剂的脱硝效率和SO₂氧化率分别为99.0%和0.43%、77.0%和0.46%、94.2%和0.80%、99.3%和0.48%, 采用本方法获得的再利用催化剂不仅脱硝效率完全恢复, 而且SO₂氧化率得到了很好的控制。通过对催化剂的分析表征发现, 采用常规再利用技术不能有效清除废弃催化剂表面的高聚态钒物种, 而本方法则可以有效清理这类高聚态钒物种, 并以高度分散的钒物种进行替代, 从而有效控制再利用催化剂的SO₂氧化率。
- 催化剂 /
- 废弃 /
- 再利用 /
- SO₂氧化
Abstract: In the light of a high SO₂ oxidation ratio of the recycled waste SCR catalyst during conventional recycling denitrification, a novel recycling technique, including acid washing, acid leaching under reduction condition and active components loading, was proposed to control the SO₂ oxidation ratio of the recycled catalyst.The experiments were performed to determine the components, denitrification efficiency and SO₂ oxidation ratio of the catalysts obtained in different recycling runs, and the catalysts used were characterized.The results indicate that the denitrification efficiency and SO₂ oxidation ratio of the fresh catalyst, waste catalyst, conventional recycled catalyst and novel recycled catalyst are 99.0% and 0.43%, 77.0% and 0.46%, 94.2% and 0.80%, 99.3% and 0.48%, respectively.Through novel recycling method, both denitrification efficiency and SO₂ oxidation ratio of the recycled catalyst are well recovered.The characterization results suggest that the highly polymerized vanadium species on the surface of the waste catalyst could not be removed by using conventional recycling method, but the novel recycling method is effective for removing these vanadium species and replacing them with highly dispersed vanadium species, resulting in a reduction of SO₂ oxidation ratio of the recycled catalyst.
- catalyst /
- waste /
- recycling /
- SO₂ oxidation

HTML全文

图 1 废弃SCR脱硝催化剂

Figure 1 Waste SCR denitrification catalyst

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图 2 催化剂性能评价系统示意图

Figure 2 Schematic of evaluation system for denitrification catalyst

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图 3 不同催化剂脱硝效率和SO₂氧化率

Figure 3 Denitrification efficiency(a) and SO₂ oxidation ratio(b) of different catalysts

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图 4 温度对新鲜和再利用催化剂脱硝效率和SO₂氧化率的影响

Figure 4 Effect of temperature on the denitrification efficiency and SO₂ oxidation ratio of fresh and recycling catalysts(space velocity 162000 h^-1, NH₃/NO= 1.0)

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图 5 催化剂的XRD谱图

Figure 5 XRD patterns of the catalysts

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图 6 催化剂的NH₃-TPD谱图

Figure 6 NH₃-TPD profiles of the catalysts

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图 7 催化剂的H₂-TPR谱图

Figure 7 H₂-TPR profiles of the catalysts

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图 8 催化剂的V 2p_3/2 XPS谱图

Figure 8 XPS spectra of V 2p_3/2 for the catalysts

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图 9 催化剂的O 1s XPS谱图

Figure 9 XPS spectra of O 1s for the catalysts

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图 10 催化剂的FT-IR谱图

Figure 10 FT-IR spectra of the catalysts

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表 1 催化剂中各组分的含量

Table 1 Content of each component in the catalysts

Catalyst	Content w/%
Catalyst	TiO₂	V₂O₅	WO₃	SiO₂	Al₂O₃	BaO	SO₃	K₂O	Na₂O	Fe₂O₃	CaO
1#	80.75	0.56	4.61	3.95	3.13	2.51	1.71	0.18	0.08	0.76	1.55
2#	84.54	0.52	4.60	3.75	2.97	2.42	0.86	0.02	-	0.04	0.16
3#	83.58	1.07	5.06	3.75	2.95	2.41	0.85	0.02	-	0.04	0.15
4#	85.63	0.12	4.56	3.68	2.88	2.23	0.86	-	-	-	-
5#	84.15	1.10	5.12	3.66	2.86	2.22	0.85	-	-	-	-
6#	93.77	1.09	5.08	-	-	-	0.06	-	-	-	-

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表 2 催化剂的比表面积和孔结构

Table 2 Surface areas and pore structures of the catalysts

Catalyst	Surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore diameter d/nm
1#	43.7	0.24	22.0
2#	53.4	0.26	19.8
3#	53.4	0.17	12.4
4#	61.2	0.21	13.6
5#	55.8	0.20	13.6
6#	79.4	0.37	18.6

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表 3 催化剂中V⁵⁺、V⁴⁺、O_α和O_β的相对含量

Table 3 Relative contents of V⁵⁺, V⁴⁺, O_α and O_β in the catalysts

Catalyst	Relative content/%
Catalyst	V⁵⁺/(V⁵⁺+V⁴⁺)	V⁴⁺/(V⁵⁺+V⁴⁺)	O_α/(O_α+O_β)	O_β/(O_α+O_β)
1#	13.31	86.69	15.05	84.95
2#	22.51	77.49	25.34	74.66
3#	57.28	42.72	40.25	59.75
4#	-	-	28.77	71.23
5#	64.84	35.16	42.54	57.46
6#	66.00	34.00	47.38	52.62

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参考文献(31)

[1]	黄增斌, 李翠清, 王振, 徐胜美, 冯凌波, 王虹, 宋永吉, 张伟.不同分子筛负载锰铈催化剂的低温NH₃-SCR脱硝性能[J].燃料化学学报, 2016, 44(11):495-499. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18936.shtml HUANG Zeng-bin, LI Cui-qing, WANG Zhen, XU Sheng-mei, FENG Ling-bo, WANG Hong, SONG Yong-ji, ZHANG Wei. Performance of Mn-Ce catalysts supported on different zeolites in the NH₃-SCR of NO_x[J]. J Fuel Chem Technol, 2016, 44(11):495-499. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18936.shtml
[2]	商雪松, 陈进生, 赵金平, 张福旺, 徐亚, 徐琪. SCR脱硝催化剂失活及其原因研究[J].燃料化学学报, 2011, 39(6):465-470. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17761.shtml SHANG Xue-song, CHEN Jin-sheng, ZHAO Jin-ping, ZHANG Fu-wang, XU Ya, XU Qi. Discussion on the deactivation of SCR denitrification catalyst and its reasons[J]. J Fuel Chem Technol, 2011, 39(6):465-470. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17761.shtml
[3]	HUO Y T, CHANG Z D, LI W J, LIU S X, DONG B. Reuse and valorization of vanadium and tungsten from waste V₂O₅-WO₃/TiO₂ SCR catalyst[J]. Waste Biomass Valor, 2015, 6(2):159-165. doi: 10.1007/s12649-014-9335-2
[4]	ZHAO Z P, GUO M, ZHANG M. Extraction of molybdenum and vanadium from the spent diesel exhaust catalyst by ammonia leaching method[J]. J Hazard Mater, 2015, 286:402-409. doi: 10.1016/j.jhazmat.2014.12.063
[5]	陈晨, 陆强, 蔺卓玮, 李文艳, 董长青.燃煤电厂废弃SCR脱硝催化剂元素回收研究进展[J].化工进展, 2016, 35(10):3306-3312. http://www.hgjz.com.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=18273 CHEN Chen, LU Qiang, LIN Zhuo-wei, LI Wen-yan, DONG Chang-qing. Research progress of element recovery of waste De-NO_x SCR catalyst from coal-fired power plants[J]. Chem Ind Eng Prog, 2016, 35(10):3306-3312. http://www.hgjz.com.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=18273
[6]	LEE J B, LEE T W, SONG K C, LEE I Y. Method of regenerating honeycomb type SCR catalyst by air lift loop reactor: US, 2006/0094587A1[P]. 2006-05-04.
[7]	史伟伟. SCR脱硝催化剂再生浸渍及其SO₂氧化控制[D]. 广州: 华南理工大学, 2013. SHI Wei-wei. Impregnation regeneration and SO₂ oxidation control of the SCR denitrification catalysts[D]. Guangzhou: South China University of Technology, 2013.
[8]	刘建华. 平板式SCR脱硝催化剂再生及其SO₂氧化控制[D]. 广州: 华南理工大学, 2016. LIU Jian-hua. Regeneration and SO₂ oxidation control of plate-type SCR denitrification catalysts[D]. Guangzhou: South China University of Technology, 2016.
[9]	MENASHA J, DUNN-RANKIN D, MUZIO L, STALLINGS J. Ammonium bisulfate formation temperature in a bench-scale single-channel air preheater[J]. Fuel, 2011, 90(7):2445-2453. doi: 10.1016/j.fuel.2011.03.006
[10]	YAKHNIN V Z, MENZINGER M. Deactivation avalanches through the interaction of locally deactivated catalyst with traveling hot spots[J]. Stud Surf Sci Catal, 1999, 126:291-298. doi: 10.1016/S0167-2991(99)80478-9
[11]	DUNN J P, STENGER H G, WACHS I E. Oxidation of SO₂ over supported metal oxide catalysts[J]. J Catal, 1999, 181(2):233-243. doi: 10.1006/jcat.1998.2305
[12]	ORSENIGO C, LIETTI L, TRONCONI E, FORZATTI P, BREGANI. Dynamic investigation of the role of the surface sulfates in NO_x reduction and SO₂ oxidation over DeNO_x-SCR catalysts[J]. Ind Eng Chem Res, 1998, 165(37):2350-2359. https://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=P1000F7T.TXT
[13]	LIU X S, WU X D, XU T F, WENG D, SI Z C, RAN R. Effects of silica additive on the NH₃-SCR activity and thermal stability of a V₂O₅/WO₃-TiO₂ catalyst[J]. Chin J Catal, 2016, 37(8):1340-1346. doi: 10.1016/S1872-2067(15)61109-3
[14]	徐浩, 延卫, 游莉.不同酸处理对钛基体性能的影响[J].稀有金属材料与工程, 2011, 40(9):1550-1554. XU Hao, YAN Wei, YOU Li. Effects of various acids treatment on the properties of titanium substrate[J]. Rare Met Mater Eng, 2011, 40(9):1550-1554.
[15]	刘俊, 王亮亮, 费兆阳, 陈献, 汤吉海, 崔咪芬, 乔旭.非晶态CeO₂@TiO₂催化剂的结构、性质及其选择催化还原脱硝性能[J].燃料化学学报, 2016, 44(8):954-960. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18880.shtml LIU Jun, WANG Liang-liang, FEI Zhao-yang, CHEN Xian, TANG Ji-hai, CUI Mi-fen, QIAO Xu. Structure and properties of amorphous CeO₂@TiO₂ catalyst and its performance in the selective catalytic reduction of NO with NH₃[J]. J Fuel Chem Technol, 2016, 44(8):954-960. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18880.shtml
[16]	FANG C, ZHANG D S, CAI S X, ZHANG L, HUANG L, LI H R, MAITARAD P, SHI L Y, GAO R H, ZHANG J P. Low-temperature selective catalytic reduction of NO with NH₃ over nanoflaky MnO_x on carbon nanotubes in situ prepared via a chemical bath deposition route[J]. Nanoscale, 2013, 05(19):9199-9207. doi: 10.1039/c3nr02631k
[17]	RAMIS G, BUSCA G, LORENZELLL V. Spectroscopic characterization of magnesium vanadate catalysts. Part 2. FTIR study of the surface properties of pure and mixed-phase powders[J]. J Chem Soc Faraday Trans, 1994, 90(9):1293-1299. doi: 10.1039/FT9949001293
[18]	LIU X, LI J H, LI X, PENG Y, WANG H, JIANG X M, WANG L W. NH₃ selective catalytic reduction of NO:A large surface TiO₂ support and its promotion of V₂O₅ dispersion on the prepared catalyst[J]. Chin J Catal, 2016, 37(6):878-887. doi: 10.1016/S1872-2067(15)61041-5
[19]	PENG Y, LI J H, SI W Z, LUO J M, WANG Y, JIE F, LI X, CRITTENDEN J, HAO J M. Deactivation and regeneration of a commercial SCR catalyst:Comparison with alkali metals and arsenic[J]. Appl Catal B:Environ, 2015, 168-169:195-202. doi: 10.1016/j.apcatb.2014.12.005
[20]	LI Q C, CHEN S F, LIU Z Y, LIU Q Y. Combined effect of KCl and SO₂ on the selective catalytic reduction of NO by NH₃ over V₂O₅/TiO₂ catalyst[J]. Appl Catal B:Environ, 2015, 164:475-482. doi: 10.1016/j.apcatb.2014.09.036
[21]	DONG G J, ZHANG Y F, ZHAO Y, BAI Y. Effect of the pH value of precursor solution on the catalytic performance of V₂O₅-WO₃/TiO₂ in the low temperature NH₃-SCR of NO_x[J]. J Fuel Chem Technol, 2014, 42(12):1455-1463. doi: 10.1016/S1872-5813(15)60003-2
[22]	杨剑, 林凡, 陈奎, 孔明, 赵冬, 孟飞.含铈钒基SCR催化剂脱硝性能及SO₂失活机理研究[J].燃料化学学报, 2016, 44(11):1394-1400. doi: 10.3969/j.issn.0253-2409.2016.11.017 YANG Jian, LIN Fan, CHEN Kui, KONG Ming, ZHAO Dong, MENG Fei. Activity and SO₂ deactivation mechanism of vanadium series catalyst containing cerium[J]. J Fuel Chem Technol, 2016, 44(11):1394-1400. doi: 10.3969/j.issn.0253-2409.2016.11.017
[23]	沈伯雄, 卢凤菊, 高兰君, 岳时吉.中温商业SCR催化剂碱和碱土中毒特性研究[J].燃料化学学报, 2011, 44(4):500-506. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18820.shtml SHEN Bo-xiong, LU Feng-ju, GAO Lan-jun, YUE Shi-ji. Study on alkali and alkaline earths poisoning characteristics for a commercial SCR catalyst[J]. J Fuel Chem Technol, 2011, 44(4):500-506. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18820.shtml
[24]	LIU J, LI X Y, ZHAO Q D, KE J, XIAO H N, LV X J, LIU S M, TADÉ M, WANG S B. Mechanistic investigation of the enhanced NH₃-SCR on cobalt-decorated Ce-Ti mixed oxide:In situ, FT-IR analysis for structure-activity correlation[J]. Appl Catal B:Environ, 2017, 200:297-308. doi: 10.1016/j.apcatb.2016.07.020
[25]	沈伯雄, 熊丽仙, 刘亭, 王静, 田晓娟.纳米负载型V₂O₅-WO₃/TiO₂催化剂碱中毒及再生研究[J].燃料化学学报, 2010, 38(1):85-90. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17543.shtml SHEN Bo-xiong, XIONG Li-xian, LIU Ting, WANG Jing, TIAN Xiao-juan. Alkali deactivation and regeneration of nano V₂O₅-WO₃/TiO₂ catalysts[J]. J Fuel Chem Technol, 2010, 38(1):85-90. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17543.shtml
[26]	ZHAO H, BENNICI S, SHEN J, AUROUX A. The influence of the preparation method on the structural, acidic and redox properties of V₂O₅-TiO₂/SO₄^2- catalysts[J]. Appl Catal A:Gen, 2009, 356(2):121-128. doi: 10.1016/j.apcata.2008.12.037
[27]	EL-MAAZAWI M, FINKEN A N, NAIR A B, GRASSIAN V H. Adsorption and photocatalytic oxidation of acetone on TiO₂:An in situ transmission FT-IR study[J]. J Catal, 2000, 191(1):138-146. doi: 10.1006/jcat.1999.2794
[28]	姜烨, 高翔, 杜学森, 毛剑宏, 骆仲泱, 岑可法. PbO对V₂O₅/TiO₂催化剂NH₃选择性催化还原NO的影响[J].工程热物理学报, 2009, 30(11):1973-1976. doi: 10.3321/j.issn:0253-231X.2009.11.048 JIANG Ye, GAO Xiang, DU Xue-sen, MAO Jian-hong, LUO Zhong-yang, CEN Ke-fa. The effect of PbO on a V₂O₅/TiO₂ catalyst for selective catalytic reduction on NO with NH₃[J]. J Eng Thermophys, 2009, 30(11):1973-1976. doi: 10.3321/j.issn:0253-231X.2009.11.048
[29]	CHEN J P, YANG R T. Selective catalytic reduction of NO with NH₃ on SO₄^2-/TiO₂ superacid catalyst[J]. J Catal, 1993, 139(1):277-288. doi: 10.1006/jcat.1993.1023
[30]	SHANG X S, HU G R, HE C, ZHAO J P, ZHANG F W, XU Y, ZHANG Y F, LI J R, CHEN J S. Regeneration of full-scale commercial honeycomb monolith catalyst (V₂O₅-WO₃/TiO₂) used in coal-fired power plant[J]. J Ind and Eng Chem, 2012, 18(1):513-519. doi: 10.1016/j.jiec.2011.11.070
[31]	孔明, 刘清才, 赵东, 任山, 孟飞. NaCI与Hg⁰对V₂O₅-WO₃/TiO₂ SCR脱硝催化剂的协同作用研究[J].燃料化学学报, 2015, 43(12):1504-1509. doi: 10.3969/j.issn.0253-2409.2015.12.015 KONG Ming, LIU Qing-cai, ZHAO Dong, REN Shan, MENG Fei. Synergy of NaCl and Hg⁰ on V₂O₅-WO₃/TiO₂ SCR catalysts[J]. J Fuel Chem Technol, 2015, 43(12):1504-1509. doi: 10.3969/j.issn.0253-2409.2015.12.015