Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响

引用本文: 郝志强, 于智慧, 李忠. Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响[J]. 无机化学学报, 2015, 31(8): 1571-1580. doi: 10.11862/CJIC.2015.186 shu

Citation: HAO Zhi-Qiang, YU Zhi-Hui, LI Zhong. Influence of Ni/Fe Molar Ratio on Surface Properties of Ni-Fe Catalysts and Hydrogenation Performance of Dinitrotoluene[J]. Chinese Journal of Inorganic Chemistry, 2015, 31(8): 1571-1580. doi: 10.11862/CJIC.2015.186 shu

Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响

郝志强 ^1, ,
于智慧 ^2, ,
李忠 ^{1,
,}

1.
1. 太原理工大学, 煤科学与技术教育部与山西省重点实验室, 太原 030024;
2.
2. 赛鼎工程有限公司, 太原 030024

通讯作者: 李忠,E-mail:lizhong@tyut.edu.cn

基金项目:
国家"973"计划(No.2012CB723105)资助项目。 (No.2012CB723105)

摘要: 采用Fe粉置换氯化镍溶液中的Ni²⁺制备了Ni-Fe催化剂,并应用于催化二硝基甲苯加氢合成甲苯二胺的反应中。运用XRD、低温氮吸附-脱附、H₂-TPD、XPS和TEM等技术手段对不同Ni/Fe物质的量的比(n_Ni/n_Fe)下催化剂进行了表征。结果表明,n_Ni/n_Fe对Ni-Fe催化剂表面性质影响显著。当n_Ni/n_Fe为1:4时,Fe抑制Ni氧化的作用达到最大,Ni-Fe催化剂化学氢吸附量和活性物种Ni的分散度分别达到了0.16 mmol·g^-1和23%,催化剂性能得到较大的提升。在优化的催化剂制备条件下,DNT(二硝基甲苯)的转化率和TDA(甲苯二胺)的选择性分别达到了~100%和99%。另外,对Ni-Zn漆原镍(Urushibara Ni)催化剂和Ni-Fe催化剂催化DNT加氢反应进程进行了研究,发现它们有相同的加氢中间产物,但反应不同阶段的催化速率存在差异。

关键词:

Ni-Fe催化剂;二硝基甲苯;甲苯二胺;催化加氢

English

Influence of Ni/Fe Molar Ratio on Surface Properties of Ni-Fe Catalysts and Hydrogenation Performance of Dinitrotoluene

1.
1. Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China;
2.
2. Sedin Engineering Company Limited, Taiyuan 030024, China

Corresponding author: 李忠,E-mail:lizhong@tyut.edu.cn

Received Date: 12 April 2015
Fund Project:
国家"973"计划(No.2012CB723105)资助项目。

Abstract: Ni-Fe catalysts were prepared via the replacement reaction of NiCl₂ by Fe and used for the selective hydrogenation of dinitrotoluene (DNT) in liquid phase. The influences of Ni/Fe molar ratio (n_Ni/n_Fe) on the surface properties and catalytic performance of Ni-Fe catalysts were investigated. The characterization results from XRD, Low temperature nitrogen adsorption -desorption, H₂-TPD, XPS and TEM show that n_Ni/n_Fe has a significant effect on the surface properties of Ni-Fe catalysts. When n_Ni/n_Fe is 1:4, the effect of Fe inhibition on the oxidation of nickel is more apparent, the chemical adsorption of hydrogen is 0.16 mmol·g^-1 and the dispersion of active species Ni achieves 23%. The performance of Ni-Fe catalysts is greatly improved. Under the optimized catalysts preparation conditions, the conversion of DNT (dinitrotoluene) and the selectivity of TDA (toluenediamine) could reach~100% and 99%, respectively. In addition, Ni-Zn Urushibara nickel catalysts and Ni-Fe catalysts have~the same catalytic hydrogenation~pathway but different catalytic reaction rate in a different reaction stages.

Key words:

Ni-Fe catalyst;dinitrotoluene;toluenediamine;catalytic hydrogenation

1. [1] YAN Shao-Wei(闫少伟), FAN Hui(范辉), LIANG Chuan (梁川), et al. Chem. J. Chinese Universities(高等学校化学学报), 2012,33(9):2067-2073[1] YAN Shao-Wei(闫少伟), FAN Hui(范辉), LIANG Chuan (梁川), et al. Chem. J. Chinese Universities(高等学校化学学报), 2012,33(9):2067-2073
2. [2] YAN Shao-Wei(闫少伟), FAN Hui(范辉), LIANG Chuan (梁川), et al. Chinese J. Catal.(催化学报), 2012,33(8):1374-1382[2] YAN Shao-Wei(闫少伟), FAN Hui(范辉), LIANG Chuan (梁川), et al. Chinese J. Catal.(催化学报), 2012,33(8):1374-1382
3. [3] Surapas S, Wei A, Daniel E R. J. Catal., 2011,284:90-101[3] Surapas S, Wei A, Daniel E R. J. Catal., 2011,284:90-101
4. [4] Wang L, Li D L, Koike M, et al. Appl. Catal. A:Gen., 2011,392:248-255[4] Wang L, Li D L, Koike M, et al. Appl. Catal. A:Gen., 2011,392:248-255
5. [5] Lei N, Priscilla M de Souza, Fabio B N, et al. J. Mol. Catal. A:Chem., 2014,388-389:47-55[5] Lei N, Priscilla M de Souza, Fabio B N, et al. J. Mol. Catal. A:Chem., 2014,388-389:47-55
6. [6] Yan X H, Sun J Q, Wang Y W, et al. J. Mol. Catal. A:Chem., 2006,252(1/2):17-22[6] Yan X H, Sun J Q, Wang Y W, et al. J. Mol. Catal. A:Chem., 2006,252(1/2):17-22
7. [7] Fang M X, Tang W, Yu C J, et al. Fuel Process. Technol., 2015,129:236-244[7] Fang M X, Tang W, Yu C J, et al. Fuel Process. Technol., 2015,129:236-244
8. [8] Lin C H, Shih Y H, MacFarlane J. Chem. Eng. J., 2015,262:59-67[8] Lin C H, Shih Y H, MacFarlane J. Chem. Eng. J., 2015,262:59-67
9. [9] Alokd B, Rajeevc C, Chandrashekharv V R, et al. Environ. Sci. Technol., 2007,41:7437-7443[9] Alokd B, Rajeevc C, Chandrashekharv V R, et al. Environ. Sci. Technol., 2007,41:7437-7443
10. [10] Han Y, Li W, Zhang M H, et al. Chemosphere, 2008,72:53-58[10] Han Y, Li W, Zhang M H, et al. Chemosphere, 2008,72:53-58
11. [11] Oliveira V L, Morais C, Servat K, et al. Electrochim. Acta, 2014,117:255-262[11] Oliveira V L, Morais C, Servat K, et al. Electrochim. Acta, 2014,117:255-262
12. [12] Tian D Y, Liu Z H, Li D D, et al. Fuel, 2013,104:224-229[12] Tian D Y, Liu Z H, Li D D, et al. Fuel, 2013,104:224-229
13. [13] YU Zhi-Hui(于智慧), YAN Ze(闫泽), FAN Hui(范辉), et al. Chinese J. Inorg. Chem.(无机化学学报), 2014,30(6):1317-1324[13] YU Zhi-Hui(于智慧), YAN Ze(闫泽), FAN Hui(范辉), et al. Chinese J. Inorg. Chem.(无机化学学报), 2014,30(6):1317-1324
14. [14] YU Zhi-Hui(于智慧), YAN Ze(闫泽), FAN Hui(范辉), et al. Chem. J. Chinese Universities(高等学校化学学报), 2014,35(10):2227-2233[14] YU Zhi-Hui(于智慧), YAN Ze(闫泽), FAN Hui(范辉), et al. Chem. J. Chinese Universities(高等学校化学学报), 2014,35(10):2227-2233
15. [15] Fang Z Q, Qiu X H, Chen J H, et al. J. Hazard. Mater., 2011,185:958-969[15] Fang Z Q, Qiu X H, Chen J H, et al. J. Hazard. Mater., 2011,185:958-969
16. [16] Kustov A L, Frey A M, Larsen K E, et al. Appl. Catal. A:Gen., 2007,320:98-104[16] Kustov A L, Frey A M, Larsen K E, et al. Appl. Catal. A:Gen., 2007,320:98-104
17. [17] Adabavazeh Z, Karimzadeh F, Enayati M H. Adv. Powder Technol., 2012,23(3):284-289[17] Adabavazeh Z, Karimzadeh F, Enayati M H. Adv. Powder Technol., 2012,23(3):284-289
18. [18] Pandey D, Deo G. J. Mol. Catal. A:Chem., 2014,382:23-30[18] Pandey D, Deo G. J. Mol. Catal. A:Chem., 2014,382:23-30
19. [19] Zhang Z, Cissoko N, Wo J J, et al. J. Hazard. Mater., 2009,165(13):78-86[19] Zhang Z, Cissoko N, Wo J J, et al. J. Hazard. Mater., 2009,165(13):78-86
20. [20] Jacob I, Fisher M, Hadari Z, Herskowitz M, et al. J. Catal., 1986,101(1):28-34[20] Jacob I, Fisher M, Hadari Z, Herskowitz M, et al. J. Catal., 1986,101(1):28-34
21. [21] Benrabaa R, Lfberg A, Rubbens A, et al. Catal. Today, 2013,203:188-195[21] Benrabaa R, Lfberg A, Rubbens A, et al. Catal. Today, 2013,203:188-195
22. [22] Zhang W H, Quan X, Wang J X, et al. Chemosphere, 2006,65:58-64[22] Zhang W H, Quan X, Wang J X, et al. Chemosphere, 2006,65:58-64
23. [23] SHI Qiu-Jie(石秋杰), LEI Jing-Xin(雷经新), ZHANG Ning (张宁). Acta Phys.-Chim. Sin.(物理化学学报), 2007,23:98-102[23] SHI Qiu-Jie(石秋杰), LEI Jing-Xin(雷经新), ZHANG Ning (张宁). Acta Phys.-Chim. Sin.(物理化学学报), 2007,23:98-102
24. [24] Wu Z J, Zhang M H, Zhao Z F, et al. J. Catal., 2008,256:323-330[24] Wu Z J, Zhang M H, Zhao Z F, et al. J. Catal., 2008,256:323-330
25. [25] Han Y L, Yan W L. Water Res., 2014,66:149-159[25] Han Y L, Yan W L. Water Res., 2014,66:149-159
26. [26] Schrick B, Blough J L, Jones A D, et al. Chem. Mater., 2002,14(12):5140-5147[26] Schrick B, Blough J L, Jones A D, et al. Chem. Mater., 2002,14(12):5140-5147
27. [27] WANG Wei-Yan(王威燕), YANG Yun-Quan(杨运泉), LUO He-An(罗和安), et al. Chinese J. Catal.(催化学报), 2011,32(10):1645-1650[27] WANG Wei-Yan(王威燕), YANG Yun-Quan(杨运泉), LUO He-An(罗和安), et al. Chinese J. Catal.(催化学报), 2011,32(10):1645-1650
28. [28] Wei J J, Qian Y J, Liu W J, et al. J. Environ. Sci., 2014,26:1162-1170[28] Wei J J, Qian Y J, Liu W J, et al. J. Environ. Sci., 2014,26:1162-1170
29. [29] LIU Hao(刘皓), LI Ruo-Yu(李若愚), ZHANG Meng(张濛), et al. Chinese J. Catal. (催化学报), 2009,30(7):606-612[29] LIU Hao(刘皓), LI Ruo-Yu(李若愚), ZHANG Meng(张濛), et al. Chinese J. Catal. (催化学报), 2009,30(7):606-612

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 578
HTML全文浏览量: 100

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响

通讯作者: 李忠,E-mail:lizhong@tyut.edu.cn

English

Influence of Ni/Fe Molar Ratio on Surface Properties of Ni-Fe Catalysts and Hydrogenation Performance of Dinitrotoluene

Corresponding author: 李忠,E-mail:lizhong@tyut.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响

通讯作者: 李忠,E-mail:lizhong@tyut.edu.cn

English

Influence of Ni/Fe Molar Ratio on Surface Properties of Ni-Fe Catalysts and Hydrogenation Performance of Dinitrotoluene

Corresponding author: 李忠,E-mail:lizhong@tyut.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs