催化学报 ›› 2014, Vol. 35 ›› Issue (5): 663-669.DOI: 10.1016/S1872-2067(14)60069-3

• 研究论文 • 上一篇    下一篇

Glycerol chlorination in a gas-liquid semibatch reactor:New catalysts for chlorohydrin production

R. Vitiello, V. Russo, R. Turco, R. Tesser, M. Di Serio, E. Santacesaria   

  1. Department of Chemicals Sciences, University of Study of Naples "Federico Ⅱ", 80126 Naples, Italy
  • 收稿日期:2014-02-24 修回日期:2014-03-07 出版日期:2014-04-18 发布日期:2014-04-24
  • 通讯作者: R. Tesser

Glycerol chlorination in a gas-liquid semibatch reactor:New catalysts for chlorohydrin production

R. Vitiello, V. Russo, R. Turco, R. Tesser, M. Di Serio, E. Santacesaria   

  1. Department of Chemicals Sciences, University of Study of Naples "Federico Ⅱ", 80126 Naples, Italy
  • Received:2014-02-24 Revised:2014-03-07 Online:2014-04-18 Published:2014-04-24
  • Contact: R. Tesser

摘要:

Glycerol from biodiesel production can be an important industrial feedstock for chemical commodities as it can be used in the food, cosmetic, pharmaceutical and tobacco industries. However, crude glycerol derived from biodiesel production has a low value because of impurities. The purification of this glycerol into a high grade involves high costs and is not economically feasible for small and medium size plants. The glycerol conversion into chlorohydrins was studied using new homogeneous catalysts and hydrochloric acid as chlorination agent. This is an interesting alternative route to epichlorohydrin and then to epoxy resins. The behavior of two series of homologous catalysts, glycolic acid series (glycolic acid, di-glycolic acid and thio-glycolic acid) and amminoacid series (glutamic acid, aspartic acid and cysteine), were investigated for their activity and selectivity. Glycolic acids were more active than amminoacids. The pKa values had a strong influence on selectivity (mono-chlorohydrins/di-chlorohydrins) for the amminoacid series, which was not observed for the glycolic acids. A kinetic model and reaction mechanism developed in a previous work were used for interpreting the kinetic runs.

关键词: Glycerol chlorination, Chlorohydrins, Epichlorohydrin, Hydrochloric acid gas

Abstract:

Glycerol from biodiesel production can be an important industrial feedstock for chemical commodities as it can be used in the food, cosmetic, pharmaceutical and tobacco industries. However, crude glycerol derived from biodiesel production has a low value because of impurities. The purification of this glycerol into a high grade involves high costs and is not economically feasible for small and medium size plants. The glycerol conversion into chlorohydrins was studied using new homogeneous catalysts and hydrochloric acid as chlorination agent. This is an interesting alternative route to epichlorohydrin and then to epoxy resins. The behavior of two series of homologous catalysts, glycolic acid series (glycolic acid, di-glycolic acid and thio-glycolic acid) and amminoacid series (glutamic acid, aspartic acid and cysteine), were investigated for their activity and selectivity. Glycolic acids were more active than amminoacids. The pKa values had a strong influence on selectivity (mono-chlorohydrins/di-chlorohydrins) for the amminoacid series, which was not observed for the glycolic acids. A kinetic model and reaction mechanism developed in a previous work were used for interpreting the kinetic runs.

Key words: Glycerol chlorination, Chlorohydrins, Epichlorohydrin, Hydrochloric acid gas