钙基吸收剂硫氮协同脱除过程中表面产物层生长机制

doi:10.11949/j.issn.0438-1157.20141246

化工学报 ›› 2015, Vol. 66 ›› Issue (5): 1867-1873.DOI: 10.11949/j.issn.0438-1157.20141246

钙基吸收剂硫氮协同脱除过程中表面产物层生长机制

陈国庆¹, 高继慧², 高建民², 吴少华², 秦裕琨²

1 国电科学技术研究院, 江苏南京 210031;
2 哈尔滨工业大学能源科学与工程学院, 黑龙江哈尔滨 150001

收稿日期:2014-08-18 修回日期:2015-02-04 出版日期:2015-05-05 发布日期:2015-05-05
通讯作者: 陈国庆
基金资助:
国家自然科学基金项目(51176043);国家自然科学基金“煤炭联合基金”项目(51134015)。

Growth mechanism of product layer in SO₂ and NO_x simultaneous removal by calcium-based sorbent

CHEN Guoqing¹, GAO Jihui², GAO Jianmin², WU Shaohua², QIN Yukun²

1 Guodian Science and Technology Research Institute, Nanjing 210031, Jiangsu, China;
2 School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China

Received:2014-08-18 Revised:2015-02-04 Online:2015-05-05 Published:2015-05-05
Supported by:
supported by the National Natural Science Foundation of China (51176043) and the National Natural Science Foundation-Shenhua Group, “Coal Joint Fund” (51134015).

摘要/Abstract

摘要： 为了分析钙基吸收剂硫氮协同脱除过程中产物层的生长机制,采用氢氧化钙单晶体表面(0001)模拟吸收剂孔隙的孔壁及外表面,针对脱硫、脱硝及硫氮协同脱除过程中产物层的生长规律进行了分析,结合晶体生长理论及脱硫和脱硝过程中产物层生长的差异,提出了硫氮协同脱除过程中产物层生长的机制。研究结果表明,脱硫反应首先发生在单晶表面局部区域,并使该区域膨胀形成颗粒状凸起结构;之后,随着反应区域不断扩大,表面膨胀趋于一致,从而形成连续致密产物层。由于脱硝产物易溶于水,且在液膜中扩散,因此脱硝反应对单晶表面表现出刻蚀作用。硫氮协同脱除过程中,脱硝反应的刻蚀作用抑制了脱硫连续致密产物层的形成,同时,液膜中脱硝产物的出现也改变了脱硫产物的生长习性,因此反应后产物层为疏松结构。

关键词: 钙基吸收剂, 同时脱硫脱硝, 产物层生长, 燃煤污染

Abstract: In order to analyze the growth mechanism of product layer in SO₂ and NO_x removal by calcium-based sorbent, the single-crystal Ca(OH)₂(0001) surface was used to simulate the pore wall and external surface of the sorbent. The growth of product layer was analyzed under different reaction environments. The growth mechanism of product layer in SO₂ and NO_x simultaneous removal by calcium-based sorbent was proposed, combining crystal growth theory and discrepancy between SO₂ and NO_x single removal. SO₂ removal reaction firstly occurred in the local area of the single-crystal surface to result in expansion of surface and formation of convex structure. Subsequently, the reaction and expansion area gradually extended, which led to formation of the continuous dense product layer. Due to solubility and diffusion of NO₂ removal product in the water film, NO₂ reaction had an obvious etching effect on the sorbent surface. When SO₂ removal reaction coexisted with NO₂ removal reaction, the etching action of NO₂ removal reaction could inhibit formation of the continuous dense SO₂ removal product layer. Meanwhile, the presence of NO₂ removal product could change the growth habit of the SO₂ removal product. Therefore, the sorbent surface structure after simultaneously reacting with SO₂ and NO_x was loose.

Key words: calcium-based sorbent, SO₂ and NO_x removal, growth of product layer, coal fired pollutants

中图分类号:

TQ132.3⁺2

陈国庆, 高继慧, 高建民, 吴少华, 秦裕琨. 钙基吸收剂硫氮协同脱除过程中表面产物层生长机制[J]. 化工学报, 2015, 66(5): 1867-1873.

CHEN Guoqing, GAO Jihui, GAO Jianmin, WU Shaohua, QIN Yukun. Growth mechanism of product layer in SO₂ and NO_x simultaneous removal by calcium-based sorbent[J]. CIESC Journal, 2015, 66(5): 1867-1873.

参考文献 22

[1]	Zhang H, Tong H L, Wang S J, et al. Simultaneous removal of SO2 and NO from flue gas with calcium-based sorbent at low temperature [J]. Ind. Eng. Chem. Res., 2006, 45 (18): 6099-6103
[2]	Zhao Yi (赵毅), Ma Shuangchen (马双忱), Huang Jianjun (黄建军), et al. Testing study on simultaneous removal SO2 and NOx by flue gas circulatting fluidized bed [J]. Proceeding of the CSEE (中国电机工程学报), 2005,25 (2): 120-124
[3]	Chen Guoqing (陈国庆), Gao Jihui (高继慧), Wang Shuai (王帅), et al. Mechanism of influence of flue gas component and Ca(OH)2 on the oxidation of NO over KMnO4 [J]. CIESC Journal (化工学报), 2009, 60 (9): 2314-2320
[4]	Wu Zuliang (吴祖良), Gao Xiang (高翔), Luo Zhongyang (骆仲泱), et al. Reactive characteristics and mechanism of the SO2 and NOx simultaneous removal process using a radical shower electro-catalytic oxidation system [J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2006, 20 (6): 925-931
[5]	Dogu T. The importance of pore structure in the kinetics of gas solid noncatalytic reactions [J]. Chem.Eng.J., 1981, 21: 213-222
[6]	Chen Guoqing (陈国庆), Gao Jihui (高继慧), Yin Yijun (尹伊郡), et al. Evolution of pore structure of Ca-based sorbent in simultaneous removal of SO2 and NOx [J]. Proceedings of the CSEE (中国电机工程学报), 2011, 31 (20): 60-66
[7]	Gao Xiang (高翔), Luo Zhongyang (骆仲泱), Chen Yafei (陈亚非), et al. Modeling the reactivity of aqueous Ca (OH)2 particle [J]. Acta Scientiae Circumstantiae (环境科学学报), 1999, 19: 351-356
[8]	Liu C F,Shih S M, Lin R B. Kinetics of the reaction of Ca (OH)2/fly ash sorbent with SO2 at low temperature [J]. Chem. Eng. Sci., 2002, 57: 93-104
[9]	Getler J L, Shelton H L, Furlong D A. Modeling the spray absorptionprocess for SO2 removal [J]. Control Technology News, 1979, 29: 1270-1273
[10]	Karatepe N, Erdogan N, Mericboyü A E, et al. Preparation of diatomite/Ca(OH)2 sorbents and modeling their sulphation reaction [J].Chem. Eng. Sci., 2004, 59: 3883-3889
[11]	Bausach M, Pera-Titus M, Fite C, et al. Kinetic modeling of the reaction between hydrated lime and SO2 at low temperature [J]. AIChE Journal, 2005, 51: 1455-1466
[12]	Wang Shichang (王世昌), Yao Qiang (姚强), Xu Xuchang (徐旭常), et al. Comparison of kinetic reaction rate and diffusion rate during dry FGD reaction with CaO particles [J]. Journal of Engineering Thermophysics (工程热物理学报), 2006, 27 (2): 219-222
[13]	Duo W L, Laursen K, Lim J, et al. Crystallization and fracture: formation of product layers in sulfation of calcined limestone [J].Powder Technol., 2000, 111: 154-167
[14]	Tang Xiaoyi, Li Zhenshan, Fang Fan, et al. AFM investigation of the morphology of CaSO4 product layer formed during direct sulfation on polished single-crystal CaCO3 surfaces at high CO2 concentrations [J]. Proceedings of the Combustion Institute, 2011, 33: 2683-2689
[15]	Gao Jihui, Chen Guoqing, Liu Jiaxun, et al. Simultaneous removal of SO2 and NOx by calcium hydroxide at low temperature: evolution of the absorbent surface structure [J]. Energy & Fuels, 2010, 24: 5454-5463
[16]	Lee K T, Mohameda A R, Bhatia S, Chu K H. Removal of sulfur dioxide by fly ash/CaO/CaSO4 sorbents [J]. Chem. Eng. J., 2005, 114: 171-177
[17]	Li Y R, Yang L Z, You C F, Qi H Y. Sulfation diffusion model for SO2 capture on the T-T sorbent at moderate temperatures [J]. Korean J. Chem. Eng., 2009, 26: 1155-1159
[18]	Liu C F, Shih S M. Effects of flue gas components on the reaction of Ca(OH)2 with SO2 [J]. Ind. Eng. Chem. Res., 2006, 45: 8765-8769
[19]	Bausach M, Pera-Titus M, Fite C. Water-induced rearrangement of Ca (OH)2 (0001) surfaces reacted with SO2 [J]. AIChE Journal, 2006, 52: 2876-2886
[20]	Chen Guoqing, Gao Jihui, Gao Jianmin, et al. Simulataneous removal of SO2 and NOx by calcium hydroxide at low temperature: effect of SO2 absorption on NO2 removal [J]. Ind.Eng.Chem.Res., 2010, 49 (3): 12140-12147
[21]	Gao Jihui (高继慧), Chen Guoqing (陈国庆), Fu Xiaolin (付晓林), et al. Effect of SO2 on NO removal by calcium hydroxide [J]. CIESC Journal (化工学报). 2010, 61 (11): 2836-2842
[22]	Wang Ping (王萍), Li Guochang (李国昌). Crystallography Tutorial (结晶学教程) [M]. Beijing: National Defense Industry Press, 2006: 20-30

钙基吸收剂硫氮协同脱除过程中表面产物层生长机制

Growth mechanism of product layer in SO₂ and NO_x simultaneous removal by calcium-based sorbent

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钙基吸收剂硫氮协同脱除过程中表面产物层生长机制

Growth mechanism of product layer in SO2 and NOx simultaneous removal by calcium-based sorbent

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Growth mechanism of product layer in SO₂ and NO_x simultaneous removal by calcium-based sorbent