华南理工大学学报(自然科学版) ›› 2007, Vol. 35 ›› Issue (10): 124-130.

• 创刊五十周年纪念专辑 • 上一篇    下一篇

精细化学品的绿色氧化合成

纪红兵 钱宇 李忠 王乐夫   

  1. 华南理工大学 化工与能源学院,广东 广州 510640
  • 收稿日期:2007-03-02 出版日期:2007-10-25 发布日期:2007-10-25
  • 通信作者: 纪红兵(1970-) ,男,教授,博士生导师,主要从事绿色化学化工与催化研究 E-mail:cehbji@scut. edu.cn
  • 作者简介:纪红兵(1970-) ,男,教授,博士生导师,主要从事绿色化学化工与催化研究
  • 基金资助:

    国家自然科学基金资助项目(20576045 ,20306009) ;新世纪优秀人才支持计划资助项目( NCET-06-740)

Synthesis of Fine Chemicals via Green Oxidation

Ji Hong-bing  Qian Yu  Li Zhong  Wang Le-fu   

  1. School of Chemical and Energy Engineering , South China Univ. of Tech. , Guangzhou 510640 , Guangdong , China
  • Received:2007-03-02 Online:2007-10-25 Published:2007-10-25
  • Contact: 纪红兵(1970-) ,男,教授,博士生导师,主要从事绿色化学化工与催化研究 E-mail:cehbji@scut. edu.cn
  • About author:纪红兵(1970-) ,男,教授,博士生导师,主要从事绿色化学化工与催化研究
  • Supported by:

    国家自然科学基金资助项目(20576045 ,20306009) ;新世纪优秀人才支持计划资助项目( NCET-06-740)

摘要: 氧化反应广泛应用于精细化学品的合成中,对氧化过程实现绿色化可有效地减少精细化学品合成中的污染物排放,提高其原子经济性.笔者以分子氧和过氧化氢等为氧化剂,开发了可循环回收反复使用的固体催化剂、高效的均相金属叶、琳和酥菁催化剂,以及无全属的环糊精催化剂体系.结果发现钉改性的铁链夫晶石、钉改性的水滑石类催化剂和钉改性的全硅分子筛均为有效的仅使用氧气为氧化剂的高效催化剂;在以非贵金属为活性中心构筑固体催化剂方面,制 备了以镍和在钒为活性中心的有效催化剂体系;通过对仿生催化氧化体系的研究发现,简羊的金属卟啉可有效地转化环己烷到己二酸、促进烯烃的环氧化以及由硫醚生成亚砜,金属酞菁可将对硝基甲苯氧化转化为对硝基苯甲酸;在开发无金属催化氧化体系方面,采用β-环糊精作为催化剂,成功地实现了在水中多种有机物温和条件下的催化氧化转化.因此可以认为固体催化剂和仿生催化剂均为在温和条件下可活化分子氧或过氧化氢、实现绿色氧化合成的有效催化剂.

关键词: 精细化学品, 绿色氧化, 合成, 固体催化剂, 仿生氧化

Abstract:

As oxidation is widely used in the synthesis of fine chemicals , employing green methods into oxidation processes can effectively reduce the pollution and improve the atom economy. In this paper , some catalyst systems , such as recyclable and reused solid catalysts , efficient homogeneous metalloporphyrins and metal phthalocyanines , and the metal-free cyclodextrin catalyst system , were developed by using molecular oxygen and hydrogen peroxide as the oxidants. The results show that (1) when ruthenium is used as the active center , Ru-modified ferrite spinels , Ru-modified hydrotalcite and Ru-modified HMS zeolites are all proved to be effective catalysts in the presence of molecular oxygen; (2) when non-precious metals are used as active centers , nickel and vanadium are well fabricated to be effective catalysts; (3) as to the biomimetic oxidation , metalloporphyrins with simple structure can effectively convert cyclohexane to adipic acid , alkenes to epoxides and sulfides to sulfoxides; (4) metal phthalocyanines are also effective catalysts towards nitrotoluene oxidation to para-nitro benzoic acid; and (5) as a metal-free catalyst , β-cyclodextrin can oxidize various organic compounds in water under mild conditions. All the above-mentioned findings indicate that solid catalysts and biomimetic catalysts can activate molecular oxygen or hydrogen peroxide to furthermore achieve green oxidation under mild conditions.

Key words: fine chemical, green oxidation, synthesis, solid catalyst, biomimetic oxidation