The quick development of biodiesel industries has created a huge surplus of glycerol. Glycerol is a renewable Bioenergy material, which is widely used in the chemical industry. For environmental protection, its environmental performance is excellent. Under this situation, considerable attention has been focused on finding reasonable and effective ways to convert glycerol into chemicals. Currently, the most promising method for converting glycerol is the hydrogenolysis of glycerol which produces 1,3-propanediol. In the process of producing 1,3-PDO by traditional chemical industrial synthesis, the intermediate acrolein itself is highly toxic and harmful to human health. The preparation of 1,3-propanediol through glycerol conversion is an environmentally friendly and cost-effective route, with very broad applications and great development prospects. However, one of the biggest challenges that this method needs to overcome is to develop a catalyst with high yield and low cost, so that the main product of glycerol hydrogenation reaction is 1,3-PDO and relatively high yield can be achieved. This paper studies the role of noble metal Pt in catalyzing hydrogenation and hydrolysis of glycerol to produce 1,3-PDO in the Pt/WO3 system using DFT calculations. The spatial distributions of electron densities on the catalyst surface and Mulliken population analysis indicate that Pt can enhance the acid strength of Brønsted acid sites at the ortho position on the WO3 surface, lower the activation energy for active-phase reactions, reduce the activation energy for glycerol hydrogenation, and heighten the selectivity to hydrogenate the secondary hydroxyl group. As per the frontier molecular orbital theory, there is a high match of orbitals between the Brønsted acid sites in the vicinity of Pt on the WO3 surface and the secondary hydroxyl group of the glycerol molecule, and a small energy level difference between the frontier orbitals, thus lowering the activation energy to protonate the intermediate secondary hydroxyl group of glycerol and increasing the selectivity to 1, 3-PDO. In order to achieve high 1,3-PDO selectivity and yields, an appropriate combination of Pt loading and Brønsted acid sites should be adopted in the design of catalyst. Furthermore, a suitable number of Brønsted acid sites in the vicinity of Pt should be added so as to selectively activate the intermediate secondary hydroxyl group of glycerol and increase the yields and selectivity of 1,3-PDO, which not only solves the problem of glycerol excess, but also provides a green way to produce 1,3-propanediol, providing basic data for the industrial application of catalysts.

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DFT Study on Green and Environmentally Friendly Production of 1,3-PDO Through Glycerol Catalytic Hydrogenation on the Pt/WO3(1 0 0) Surface

  • Yakun Qu,
  • Xiaoguang Zhao,
  • Lixin Wang,
  • Chao Jin

摘要

The quick development of biodiesel industries has created a huge surplus of glycerol. Glycerol is a renewable Bioenergy material, which is widely used in the chemical industry. For environmental protection, its environmental performance is excellent. Under this situation, considerable attention has been focused on finding reasonable and effective ways to convert glycerol into chemicals. Currently, the most promising method for converting glycerol is the hydrogenolysis of glycerol which produces 1,3-propanediol. In the process of producing 1,3-PDO by traditional chemical industrial synthesis, the intermediate acrolein itself is highly toxic and harmful to human health. The preparation of 1,3-propanediol through glycerol conversion is an environmentally friendly and cost-effective route, with very broad applications and great development prospects. However, one of the biggest challenges that this method needs to overcome is to develop a catalyst with high yield and low cost, so that the main product of glycerol hydrogenation reaction is 1,3-PDO and relatively high yield can be achieved. This paper studies the role of noble metal Pt in catalyzing hydrogenation and hydrolysis of glycerol to produce 1,3-PDO in the Pt/WO3 system using DFT calculations. The spatial distributions of electron densities on the catalyst surface and Mulliken population analysis indicate that Pt can enhance the acid strength of Brønsted acid sites at the ortho position on the WO3 surface, lower the activation energy for active-phase reactions, reduce the activation energy for glycerol hydrogenation, and heighten the selectivity to hydrogenate the secondary hydroxyl group. As per the frontier molecular orbital theory, there is a high match of orbitals between the Brønsted acid sites in the vicinity of Pt on the WO3 surface and the secondary hydroxyl group of the glycerol molecule, and a small energy level difference between the frontier orbitals, thus lowering the activation energy to protonate the intermediate secondary hydroxyl group of glycerol and increasing the selectivity to 1, 3-PDO. In order to achieve high 1,3-PDO selectivity and yields, an appropriate combination of Pt loading and Brønsted acid sites should be adopted in the design of catalyst. Furthermore, a suitable number of Brønsted acid sites in the vicinity of Pt should be added so as to selectively activate the intermediate secondary hydroxyl group of glycerol and increase the yields and selectivity of 1,3-PDO, which not only solves the problem of glycerol excess, but also provides a green way to produce 1,3-propanediol, providing basic data for the industrial application of catalysts.