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第 6 期 庞子涛,等: FeCoY 催化剂的催化还原脱硫脱硝性能 ·1117·
竞争吸附,抑制了金属硫化物的产生,或者产生的 脱硝过程仅遵循 COS 中间产物机理,1% O 2 对催化
金属硫化物重新被氧化为金属氧化物 [19-20] ,不能发 剂同时脱硫脱硝均有毒害作用,其中氧气对 SO 2 的
生反应(8),不能产生高活性的 COS,导致后续反 毒害作用可逆,而对 NO 的毒害作用不可逆。
应无法发生。而 SO 2 除了遵循 COS 反应机理外,可
参考文献:
能还遵循 Redox 反应机理,氧气的加入,不会影响
[1] China Environmental Protection Industry Association Desulphurization
金属氧化物与 CO 的反应,或者在该温度下影响较 and Denitrification Committee (中国环境保护产业协会脱硫脱硝委
小,反应(3)可以发生,所以 SO 2 在 O 2 加入一定 员会). Development report on desulfurization and denitrification
industry in 2017[J]. China Environmental Protection Industry, 2018,
时间后还有部分活性。可以初步推断 CO 催化还原 (7): 10-24.
[2] Li Hongqi (李鸿琦), Zhang Xiaolin (章小林), Li Xiaoding (李小定).
NO 只遵循 COS 反应机理,而 SO 2 遵循 Redox 和 COS Research development of flue gas desulfuration and denitrifictation
反应机理,这也就解释了 O 2 加入后 NO 的转化率最 integration technology[J]. Power Technology and Environmental
Protection (电力科技与环保), 2014, 30(3): 14-15.
终为零,而 SO 2 存在一定的转化率。在 150 min 时, [3] Erdal Tan,Suat Ünal,Alişan Doğan,et al.New “wet type” electron
beam flue gas treatment pilot plant[J]. Radiation Physics and
撤去 O 2 后,SO 2 的转化率几乎恢复到最佳水平,而 Chemistry, 2016, 119: 109-115.
[4] Xie G, Liu Z, Zhu Z, et al. Simultaneous removal of SO 2, and NO x,
NO 的转化率甚至出现了负值,O 2 毒化了 NO 的活 from flue gas using a CuO/Al 2O 3, catalyst sorbent : I. Deactivation of
性位点,吸附的 NO 脱附出来,脱附完成后 NO 的 SCR activity by SO 2, at low temperatures[J]. Journal of Catalysis,
2004, 224(1): 36-41.
转化率接近于零,这与宋永吉 [19] 等的结果基本一致。 [5] Zhao Y, Han Y, Ma T, et al. Simultaneous desulfurization and
denitrification from flue gas by Ferrate( Ⅵ )[J]. Environmental
在该反应条件下,O 2 对 NO 的活性位点产生了不可 Science & Technology, 2011, 45(9): 4060.
恢复的毒害,失去了脱硝活性,而对 SO 2 的毒害作 [6] Hao R, Zhao Y, Yuan B, et al. Establishment of a novel advanced
oxidation process for economical and effective removal of SO 2 and
用可以恢复。 NO[J]. Journal of Hazardous Materials, 2016, 318: 224-232.
[7] Guo S, Lv L, Jia Z, et al. Simultaneous removal of SO 2 and NO x with
由此可见,该系列催化剂需要在无氧条件下才 ammonia combined with gas-phase oxidation of NO using ozone[J].
Chemical Industry & Chemical Engineering Quarterly, 2015, 21(2):
能发挥良好的催化性能。但是在实际烟气中,存在 305-310.
体积分数 3%~5%的 O 2 。要解决氧气对催化剂的影 [8] Shi Fenghua (史风华). Study on desulfurization and denitration with
CO over rare earth oxide loaded on active carbon[D]. Beijing:
响,可以从催化剂自身的性能进行改进,但是仍处 BeijingUniversity of Chemical Technology (北京化工大学), 2013.
[9] Pantazis C C, Petrakis D E, Pomonis P J. Simultaneous and/or
于理论研究阶段 [12,15-16] 。还可以从工艺角度进行改 separate SO 2/NO reduction by CO over high surface area Cu/Ce
[8]
进,史风华 针对 CO 催化还原脱硫脱氮反应设计 containing mesoporous silica[J].Applied Catalysis B: Environmental,
2007, 77(1/2): 66-72.
了脱硫脱硝除尘一体化工艺,在反应器进口设置耗 [10] PengYaguang (彭亚光). Preparation of Ce xTi (1x)O 2 composite oxides
and the research of desulfurization and denitrification performance
氧装置(既可以实现消耗氧气,也可以产生一定量 [D]. Central South University (中南大学), 2014.
[11] Li Peng (李鹏), Ren Xiaoguang (任晓光), Liu Yining (刘怡宁). et
的 CO 用于催化反应),并以煤炭为耗氧原料,进行 al. Desulfuization and denitrifition properties of CuO/ γ-Al 2O 3
了模拟实验,证明了在富氧条件下该技术的理论可 catalysts[J]. Industrial Catalysis (工业催化), 2014, 22(1): 72-75.
[12] Wang Ting (王婷). A study on simultaneous desulfurization and
能性。在实际工业生产中,结合实际烟气成分,从 denitrification by catalytic reduction method[D]. Beijing:
BeijingUniversity of Chemical Technology (北京化工大学), 2016.
工艺角度出发在催化剂反应器前端消除氧气,以达 [13] Huang Wei (黄伟), Sun Shengkai (孙盛凯), Li Yujie (李玉杰), et al.
Effects of nitric acid modification on the properties of activated
到催化剂的最佳催化性能。CO 催化还原法脱硫脱 carbon [J]. Biomass Chemical Engineering (生物质化学工程), 2006,
氮,能实现产物无害化,以废治废,具有良好的工 40(6): 17-21.
[14] Yang Chunyan (杨春雁), Zhang Xiwen (张喜文), Ling Fengxiang
业应用前景。 (凌凤香). Chemical adsorption instrument in the catalyst preparation
process application [J]. Liaoning Chemical Industry (辽宁化工),
2004, 33(11): 645-648.
3 结论 [15] Wen Bin (温斌). Simultaneous removal of the catalytic materials of
NO x, SO x, and CO in FCC flue gas and their action principles[D].
Beijing: Petroleum and Chemical Science Research Institute (石油化
(1)用 HNO 3 预处理过的 AC 能去除表面灰分 工科学研究院), 2000.
[16] Zhang Jinli ( 张锦丽 ). Experiments of desulfurization and
疏通孔道,显著降低催化剂的脱硝还原温度提高脱 denitrification andmechanism studies on desulfurization over
硫效率,其中,酸炭比为 2.5 时效果最好,10Fe2Y/ modifiediron series oxides[D]. Wuhan: Huazhong University of
Science and Technology (华中科技大学), 2014.
[17] Liu Zhaoqiong (刘赵穹), Ma Jun (马骏), Yang Xiyao (杨锡尧).
AC-2.5 催化剂脱硫转化率最高能达到 90.56%,T 90%
SnO 2-TiO 2 solid solution catalyst for simultaneous reduction of SO 2
约为 273 ℃。 and NO by CO Ⅲ. Catalyst active sites and reaction mechanism[J].
Chinese Journal of Catalysis (催化学报), 2004, 25(8): 624-632.
(2)通过 FeCoY/AC-X 催化同时脱硫脱硝正交 [18] Zhang Xiaoling (张晓玲). Study on simultaneous catalytic reduction
实验可以得出最优组合为 10Fe6Co3Y/AC-2.5,脱硫 of sulfur dioxide and nitric oxide on rare earth oxide[D]. Wuhan:
Huazhong University of Science and Technology (华中科技大学), 2007.
脱硝转化率均能达到 100%,T 90% 约为 218 ℃,其中, [19] Song Yongji (宋永吉), Wang Ting (王婷), Zhao Yu (赵玉), et al.
Desulfurization and denitrification performance of M-Y/AC catalysts
Fe 对催化剂的影响效果最显著,在 XRD 谱图中检 [J]. Journal of Fuel Chemistry and Technology (燃料化学学报),
测到了明显的 CoFe 2 O 4 尖晶石结构的特征衍射峰。 2016, 44(9): 1112-1118.
[20] Wang Xuehai (王学海), Fang Xiangchen (方向晨), Liu Zhongsheng
(3)在 10Fe6Co3Y/AC-2.5 抗氧化性实验中, (刘忠生). Simultaneous catalytic reduction of NO and SO 2 with CO
over Fe / γ-Al 2O 3 catalysts[J]. Industrial Catalysis (工业催化), 2012,
初步得出脱硫过程为 Redox-COS 协同作用机理,而 20(10): 63-67.