Deactivation and regeneration of TS-1/SiO<sub>2</sub> catalyst for epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor

doi:10.1007/s11705-013-1328-3

Front Chem Sci Eng

2013, Vol. 7

Issue (2) : 202-209 https://doi.org/10.1007/s11705-013-1328-3

RESEARCH ARTICLE

Deactivation and regeneration of TS-1/SiO₂ catalyst for epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor

Hainan SHI, Yaquan WANG(

), Guoqiang WU, Wenping FENG, Yi Lin, Teng ZHANG, Xing JIN, Shuhai WANG, Xiaoxue WU, Pengxu YAO

Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China

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Abstract

TS-1/SiO₂ catalyst for the epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor has been investigated. The catalyst activity decreases gradually with the online reaction time, but the selectivity of propylene epoxide is kept at about 93%. The fresh, deactivated and regenerated catalysts were characterized with X-ray diffraction, Fourier transform infrared spectroscopy, ultra-violet-visible diffuse reflectance, Brunner-Emmett-Teller method and thermogravimetric analysis, and the deactivated catalyst was regenerated with H₂O₂/methanol solution. Compared with the fresh catalyst, both the framework structure and the content of titanium in the framework of the deactivated and regenerated TS-1/SiO₂ catalysts were not changed. The major reason of the catalyst deactivation was the blockage of the channels of the catalyst by bulky organic by-products, which covered the active centers of titanium in TS-1. The deposited materials on the deactivated TS-1/SiO₂ catalyst could be removed by treatment with hydrogen peroxide/methanol solution or pure methanol; the higher the treatment temperature and the higher the concentration of H₂O₂ in methanol, the higher the extent of the regeneration. The regeneration treatment did not influence the product selectivity in the propylene epoxidation.

Keywords TS-1/SiO₂, epoxidation of propylene, fixed-bed reactor, deactivation regeneration

Corresponding Author(s): WANG Yaquan,Email:yqwang@tju.edu.cn

Issue Date: 05 June 2013

Cite this article:

Hainan SHI,Yaquan WANG,Guoqiang WU, et al. Deactivation and regeneration of TS-1/SiO₂ catalyst for epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor[J]. Front Chem Sci Eng, 2013, 7(2): 202-209.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-013-1328-3
https://academic.hep.com.cn/fcse/EN/Y2013/V7/I2/202

Fig.1 The conversion of HO and the selectivity of products vs. reaction time. Reaction conditions: 2.5 MPa, 40°C, HO (30 wt-%), sodium acetate (100 ppm), CHOH ∶ HO ∶ HO= 6.1 ∶ 1.0 ∶ 2.3 (wt ratio), total WHSV, 1.77 h and WHSV of propylene, 0.85 h

Fig.2 XRD patterns of TS-1/SiO catalysts: (1) fresh catalyst, (2) deactivated catalyst, (3) regenerated catalyst.

Tab.1 Data of XRD and FT-IR spectra of the TS-1/SiO catalysts

Fig.3 FT-IR spectra of TS-1/SiO catalysts: (1) fresh catalyst, (2) deactivated catalyst, and (3) regenerated catalyst

Fig.4 UV-vis spectra of TS-1/SiO catalysts: (1) fresh catalyst, (2) deactivated catalyst, and (3) regenerated catalyst

Tab.2 Specific surface areas and pore volumes of the TS-1/SiO catalysts

Fig.5 N adsorption isotherms of TS-1/SiO catalysts: (1) fresh catalyst, (2) deactivated catalyst, (3) regenerated catalyst

Fig.6 TG curves of TS-1/SiO catalysts: (1) fresh catalyst, (2) deactivated catalyst, (3) regenerated catalyst.

Fig.7 The performances of the deactivated catalyst regenerated at different temperatures for propylene epoxidation. (a) the conversion of HO, and (b) the selectivities of PO and MME. Regeneration conditions: 2.5 MPa, HO (5 wt-%) in methanol, flow rate (1 mL/min), regeneration time 4 h. Reaction conditions: 2.5 MPa, 40°C, methanol (CHOH ∶ HO ∶ HO=6.1 ∶ 1.0 ∶ 2.3, wt ratio), the total WHSV, 2.14 h, and WHSV of CH, 0.85 h

Fig.8 The performances of the deactivated catalyst regenerated with different concentration of HO/methanol solution or pure methanol for propylene epoxidation: (a) the conversion of HO, and (b) the selectivities of PO and MME. Regeneration conditions: 2.5 MPa, 100°C, flow rate (1 mL/min), regeneration time 4 h. Reaction conditions: 2.5 MPa, 40°C, CHOH ∶ HO ∶ HO= 6.1 ∶ 1.0 ∶ 2.3 (wt ratio), the total WHSV, 2.14 h, and WHSV of CH, 0.85 h

Fig.9 The performances of the deactivated catalyst regenerated with different regeneration steps for propylene epoxidation: (a) the conversion of HO, and (b) the selectivities of PO and MME. Regeneration conditions: (1) 2.5 MPa, 150°C, methanol as solvent, flow rate (1 mL/min), regeneration time 8 h, (2) 2.5 MPa, 100°C, aqueous hydrogen peroxide solution (5 wt-%), flow rate (1 mL/min), regeneration time 4 h, then temperature raised 150°C, methanol as solvent, flow rate (1 mL/min), regeneration time 4 h. Reaction conditions: 2.5 MPa, 40°C, CHOH ∶ HO ∶ HO= 6.1 ∶ 1.0 ∶ 2.3 (wt ratio), methanol as solvent, the total WHSV, 2.14 h, and WHSV of CH, 0.85 h

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