Pt-H2SO4/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

doi:10.1016/j.cjche.2017.04.004

Chinese Journal of Chemical Engineering ›› 2017, Vol. 25 ›› Issue (12): 1771-1776.DOI: 10.1016/j.cjche.2017.04.004

• 第25届中国过程控制会议专栏 • 上一篇下一篇

Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

Yuedong Zhou, Fengfu Li, Junwei Liu, Zhi Yun, Xia Gui

College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

收稿日期:2016-12-23 修回日期:2017-04-05 出版日期:2017-12-28 发布日期:2018-01-18
通讯作者: Zhi Yun,E-mail address:zyun9999@163.com.
基金资助:
Supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

Yuedong Zhou, Fengfu Li, Junwei Liu, Zhi Yun, Xia Gui

College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

Received:2016-12-23 Revised:2017-04-05 Online:2017-12-28 Published:2018-01-18
Contact: Zhi Yun,E-mail address:zyun9999@163.com.
Supported by:
Supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

摘要/Abstract

摘要： The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D₄) was investigated over Pt-H₂SO₄/Zrmontmorillonite catalyst. Montmorillonite (Mt), Zr-Mt, H₂SO₄/Mt, H₂SO₄/Zr-Mt and Pt-H₂SO₄/Zr-Mt were also detected for evaluation. The catalysts were characterized by X-ray fluorescence, X-ray diffraction, nitrogen adsorption-desorption, NH₃-TPD and pyridine-FTIR measurements. In comparison to activate clay which is used in the industry of catalyst, Zr-Mt catalyst displayed stronger acidity and more excellent catalytic activity in the polymerization of D₄, polymethylhydrosiloxane (D₄^H) and hexamethyldisiloxane (MM) to low-hydro silicone oil. Relative to Zr-Mt, the acidity of H₂SO₄/Zr-Mt was noticeably improved and the catalyst exhibited a higher capability of ring-opening of D₄ conversion and yield of low-hydro silicone oil. To enhance the stability of H₂SO₄/Zr-Mt catalyst, a small amount of metals (Pt) was doped. The nitrogen adsorption-desorption results indicated that pore textural parameters of the Pt-H₂SO₄/Zr-Mt had not changed with larger specific surface area. Compared with H₂SO₄/Zr-Mt, the total acidity of Pt-H₂SO₄-Zr/Mt catalyst retained, but the content of the Brønsted acid increased and the content of the Lewis acid decreased. The Pt-H₂SO₄-Zr/Mt catalyst displayed higher catalyst reproducibility. After 40 h reaction of polymerization, the yield of low-hydro silicone oil decreased from 93% to 42% over H₂SO₄/Zr-Mt catalyst, while the yield of low-hydro silicone oil reduced from 93% to 78% over Pt-H₂SO₄/Zr-Mt catalyst. A sharp decrease in catalytic activity after 35 h of Pt-H₂SO₄/Zr-Mt catalyst was detected. Furthermore, Pt-H₂SO₄/Zr-Mt was completely regenerated under appropriate condition and appeared good repeatability in the D₄, D₄^H and MM to low-hydro silicone oil.

关键词: Pt-H₂SO₄/Zr-montmorillonite, Low-hydro silicone oil, Catalyst, Stability, Regeneration

Abstract: The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D₄) was investigated over Pt-H₂SO₄/Zrmontmorillonite catalyst. Montmorillonite (Mt), Zr-Mt, H₂SO₄/Mt, H₂SO₄/Zr-Mt and Pt-H₂SO₄/Zr-Mt were also detected for evaluation. The catalysts were characterized by X-ray fluorescence, X-ray diffraction, nitrogen adsorption-desorption, NH₃-TPD and pyridine-FTIR measurements. In comparison to activate clay which is used in the industry of catalyst, Zr-Mt catalyst displayed stronger acidity and more excellent catalytic activity in the polymerization of D₄, polymethylhydrosiloxane (D₄^H) and hexamethyldisiloxane (MM) to low-hydro silicone oil. Relative to Zr-Mt, the acidity of H₂SO₄/Zr-Mt was noticeably improved and the catalyst exhibited a higher capability of ring-opening of D₄ conversion and yield of low-hydro silicone oil. To enhance the stability of H₂SO₄/Zr-Mt catalyst, a small amount of metals (Pt) was doped. The nitrogen adsorption-desorption results indicated that pore textural parameters of the Pt-H₂SO₄/Zr-Mt had not changed with larger specific surface area. Compared with H₂SO₄/Zr-Mt, the total acidity of Pt-H₂SO₄-Zr/Mt catalyst retained, but the content of the Brønsted acid increased and the content of the Lewis acid decreased. The Pt-H₂SO₄-Zr/Mt catalyst displayed higher catalyst reproducibility. After 40 h reaction of polymerization, the yield of low-hydro silicone oil decreased from 93% to 42% over H₂SO₄/Zr-Mt catalyst, while the yield of low-hydro silicone oil reduced from 93% to 78% over Pt-H₂SO₄/Zr-Mt catalyst. A sharp decrease in catalytic activity after 35 h of Pt-H₂SO₄/Zr-Mt catalyst was detected. Furthermore, Pt-H₂SO₄/Zr-Mt was completely regenerated under appropriate condition and appeared good repeatability in the D₄, D₄^H and MM to low-hydro silicone oil.

Key words: Pt-H₂SO₄/Zr-montmorillonite, Low-hydro silicone oil, Catalyst, Stability, Regeneration

Yuedong Zhou, Fengfu Li, Junwei Liu, Zhi Yun, Xia Gui. Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil[J]. Chinese Journal of Chemical Engineering, 2017, 25(12): 1771-1776.

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Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

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