漆原镍催化剂用于苯酚催化加氢

石斌; 成文文; 孔庆洋

漆原镍催化剂用于苯酚催化加氢

1.
中国石油大学(华东) 重质油国家重点实验室, 山东青岛 266580;
2.
滨州职业学院轻纺化工学院, 山东滨州 256603

基金项目: 中央高校基本科研业务费专项资金(27R1104054A)资助项目

详细信息

通讯作者:
石斌,Tel:0532-86984615(O),E-mail:shibin71@upc.edu.cn.

中图分类号: O643.3;TE665.6⁺2
计量
- 文章访问数: 606
- HTML全文浏览量: 80
- PDF下载量: 864
- 被引次数: 0
出版历程
- 收稿日期: 2015-02-08
- 修回日期: 2015-06-02
- 刊出日期: 2015-10-31

Hydrogenation of phenol over Urushibara Ni catalysts reduced by zinc powder

1.
State Key Laboratory of Heavy Oil, China University of Petroleum (Huadong), Qingdao 266580;
2.
Department of Textile and Chemical Engineering, Binzhou Vocational College, Binzhou 256603, China

Funds: The project was supported by the Fundamental Research Funds for the Central Universities (27R1104054A).

摘要

摘要: 利用锌粉将NiCl₂液相还原制备漆原镍催化剂,考察了碱/酸活化方法、锌粉用量、还原温度、添加载体等条件下漆原镍催化苯酚加氢反应的性能。结果表明,锌粉还原的漆原镍催化剂可用NaOH或者乙酸活化处理,NaOH的效果优于乙酸。与不添加载体的催化剂相比,添加载体组分明显提高了金属镍的分散性和利用率。γ-Al₂O₃、CaCO₃、MgO均可作为漆原镍催化剂载体组分,而γ-Al₂O₃效果最好。还原剂锌粉用量、载体加入量过少或过多,都会造成催化剂活性降低,这与其影响金属镍的可接近性及分散性相关。无载体或加入载体的漆原镍催化剂均可在120~160 ℃催化苯酚加氢反应,主要产物为环己醇和环己酮,并以环己醇为主。
- 漆原镍 /
- 催化剂 /
- 苯酚 /
- 加氢 /
- 锌粉 /
- 还原 /
- 载体
Abstract: Urushibara nickel catalysts were prepared from aqueous NiCl₂ solution with zinc powder as a reducing agent and used in phenol hydrogenation. The effects of zinc powder amount, reduction temperature and pretreatment-activation method on the catalytic performance of Urushibara nickel in phenol hydrogenation was investigated. To inhibit the magnetic agglomeration of the pure nickel catalyst, γ-Al₂O₃, CaCO₃ and MgO were added as a support. The results indicated that the nickel catalysts obtained by zinc reduction can be pretreated and activated by NaOH or acetic acid solution, though the former is superior to the latter. The catalytic activity of Urushibara nickel is related to the amount of zinc used for the reduction. The nickel catalyst reduced at 100 ℃ with an n(Zn)/n(NiCl₂·6H₂O) ratio of 4.5 exhibits the highest hydrogenation activity. γ-Al₂O₃ as a support can promote the dispersion and sediment of the reduced nickel and alleviate the magnetic agglomeration. The Urushibara nickel catalysts are active for phenol hydrogenation at 120~160 ℃, with cyclohexanol and cyclohexanone as the main products; the conversion of phenol reaches 53%~66%, with the selectivity of 95.0%~96.0% to cyclohexanol.
- Urushibara nickel /
- catalytic /
- phenol /
- hydrogenation /
- zinc /
- reduction /
- support

HTML全文

参考文献(19)

高晋生. 煤的热解、炼焦和煤焦油加工[M]. 北京: 化学工业出版社, 2010, 259-357. (GAO Jin-sheng. The pyrolysis and coking of coal and coal-tar processing[M]. Beijing: Chemical Industry Press, 2010, 259-357.)

郭志武, 靳海波, 佟泽民. 环己酮、环己醇制备技术进展[J]. 化工进展, 2006, 25(8): 852-859. (GUO Zhi-wu, JIN Hai-bo, TONG Ze-min. Advances in techniques for production of cyclohexanone and cyclohexanol[J]. Chem Ind Eng Prog(China), 2006, 25(8): 852-859.)

TALUKDAR A K, BHATTACHARYYA K G, SIVASANKER S. Hydrogenation of phenol over supported platinum and palladium catalysts[J]. Appl Catal A: Gen, 1993, 96 (2): 229-239.

SRINIVAS S T, RAO P K. Synthesis, characterization and activity studies of carbon supported platinum alloy catalysts[J]. J Catal, 1998, 179(1): 1-17.

MAHATA N, VISHWANATHAN V. Influence of palladium precursors on structural properties and phenol hydrogenation characteristics of supported palladium catalysts[J]. J Catal, 2000, 196(2): 262-270.

朱俊华, 丁洁莲, 曾崇余. 载体对Pd催化剂苯酚加氢制备环己酮性能的影响[J]. 催化学报, 2007, 28(5): 441-445. (ZHU Jun-hua, DING Jie-lian, ZENG Chong-yu. Effect of supports on catalytic performance of palladium catalysts for hydrogenation of phenol to cyclohexanone[J]. Chin J Catal, 2007, 28(5): 441-445.)

LU F, LIU J. Synthesis of chain-like Ru nanoparticle arrays and its catalytic activity for hydrogenation of phenol in aqueous media[J]. Mater Chem Phys, 2008, 108(2/3): 369-374.

王鸿静, 项益智, 徐铁勇, 周汉君, 马磊, 李小年. Ba修饰的Pd/Al₂O₃对苯酚液相原位加氢制环己酮反应的催化性能[J]. 催化学报, 2009, 30(9): 933-938. (WANG Hong-jing, XIANG Yi-zhi, XU Tie-yong, ZHOU Han-jun, MA Lei, LI Xiao-nian. Catalytic performance of Ba-Modified Pd/Al₂O₃ for liquid phase in situ hydrogenati on of phenol to cyclohexanone[J]. Chin J Catal, 2009, 30(9): 933-938.)

项益智, 卢春山, 张群峰, 马磊, 巫晓琼, 李小年. Raney Ni催化剂上苯酚液相原位加氢表观动力学[J]. 化工学报, 2008, 59(8): 2007-2013. (XIANG Yi-zhi, LU Chun-shan, ZHANG Qun-feng, MA Lei, WU Xiao-qiong, LI Xiao-nian. Apparent kinetics of in-situ hydrogenation of phenol in liquid phase over Raney Ni catalyst[J]. J Chem Ind Eng, 2008, 59(8): 2007-2013.)

HU S, XUE M, CHEN H, SHEN J. The effect of surface acidic and basic properties on the hydrogenation of aromatic rings over the supported nickel catalysts[J]. Chem Eng J, 2010, 162(1): 371-379.

LIU H, JIANG T, HAN B, LIANG S, ZHOU Y. Selective phenol hydrogenation to cyclohexanone over a dual supported Pd-Lewis acid catalyst[J]. Science, 2009, 326(5957): 1250-1252.

姬生菲, 申延明, 刘东斌, 徐世博. Pd/CNTs苯酚气相加氢制环己酮催化剂[J]. 沈阳化工大学学报, 2012, 26(1): 26-30. (JI Sheng-fei, SHEN Yan-ming, LIU Dong-bin, XU Shi-bo. Gas-phase hydrogenation of phenol to cyclohexanone over Pd/CNTs catalyst[J]. J Shenyang Univ Chem Technol, 2012, 26(1): 26-30.)

URUSHIBARA Y. A new method of catalytic hydrogenation[J]. Bull Chem Soc Japan, 1952, 25(4): 280-280.

KLEIN J C, HERCULES D M. Surface characterization of model Urushibara catalysts[J]. J Catal, 1983, 82(2): 424-441.

YAN Z, LIN L, LIU S. Synthesis of γ-Valerolactone by hydrogenation of biomass-derived levulinic acid over Ru/C catalyst[J]. Energy Fuels, 2009, 23(8): 3853-3858.

陈晓冬, 叶志文. 漆原镍催化加氢制备间甲苯胺[J]. 精细石油化工, 2007, 24(4): 18-21. (CHEN Xiao-dong, YE Zhi-wen. Catalytic performance of urushibara nickel catalyst for m-toluidine synthesis[J]. Spec Petrochem, 2007, 24(4): 18-21.)

HORIKOSHI S, TSUZUKI J, SAKAI F, KAJITANI M, SERPONE N. Microwave effect on the surface composition of the Urushibara Ni hydrogenation catalyst and improved reduction of acetophenone[J]. Chem Comun, 2008, 37: 4501-4503.

刘皓, 李若愚, 张濛, 李伟, 张明慧, 陶克毅. 漆原镍催化剂用于硝基化合物催化加氢[J]. 催化学报, 2009, 30(7): 606-612. (LIU Hao, LI Ruo-yu, ZHANG Meng, LI Wei, ZHANG Ming-hui, TAO Ke-yi. Hydrogenation of nitro compounds catalyzed by urushibara nickel catalysts hydrogenation of nitro compounds catalyzed by urushibara nickel catalysts[J]. Chin J Catal, 2009, 30(7): 606-612.)

陈金芳, 贾涛, 黄筱玲. 4-甲基-2-硝基苯胺常压液相漆原镍催化加氢制备4-甲基邻苯二胺[J]. 应用化学, 2000, 17(6): 672-674. (CHEN Jin-fang, JIA Tao, HUANG Xiao-ling. Preparation of toluene-3, 4-diamine from 2-Nitro-4-aminotoluene catalyzed by urushibara-Ni[J]. Chin J Appl Chem, 2000, 17(6): 672-674.)

施引文献

资源附件(0)

访问统计