Catalytic Performance of Cu‑Doped Calcium Aluminum Layered Double Hydrotalcites for the Oxidation of Cumene to Cumene Hydrogen Peroxide

doi:10.19894/j.issn.1000-0518.210291

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (6): 941-948.DOI: 10.19894/j.issn.1000-0518.210291

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Catalytic Performance of Cu‑Doped Calcium Aluminum Layered Double Hydrotalcites for the Oxidation of Cumene to Cumene Hydrogen Peroxide

You-San ZHOU¹^,², Yi-Cheng ZHANG¹, Si-Yu WU¹, Fei ZHA¹(), De-Jun CHEN², Yue CHANG¹

^1.College of Chemistry & Chemical Engineering，Northwest Normal University，Lanzhou 730070，China
^2.Lanzhou Auxiliary Agent Plant Co. ，Ltd. ，Lanzhou 730079，China

Received:2021-06-16 Accepted:2021-08-31 Published:2022-06-01 Online:2022-06-27
Contact: Fei ZHA
About author:zhafei@nwnu.edu.cn
Supported by:
the National Natural Science Foundation of China(21865031)

Abstract

Abstract:

Cu-doped calcium aluminum hydrotalcites of Ca₄Cu _x Al-LDHs （x=0， 0.1， 0.3， 0.5， 0.8，1.0） were prepared by a coprecipitation method， and its catalytic activity for liquid phase oxidation of cumene to cumene hydroperoxide （CHP） was investigated. Ca₄Cu _x Al-LDHs were characterized by X-ray diffraction， Fourier transform infrared spectroscopy， scanning electron microscope and thermal analysis. The prepared Ca₄Cu _x Al-LDHs remain the layered structure of hydrotalcite. The copper doping results in a smaller pore size and a larger specific surface area. When the feed ratio （catalyst/cumene） is 7.5 mg/mL， the reaction temperature is 85 ℃， the flow rate of oxygen is 15 mL/min， and the reaction time is 7 h， Ca₄Cu_0.5Al-LDHs shows excellent catalytic activity， the conversion of cumene is 34.5% and the selectivity of CHP is 86.9%. After being used for five cycles， the conversion of cumene is 31.2% and the selectivity of CHP is 83.3%. The study is useful for developing the production method for cumene hydrogen peroxide.

Key words: Hydrotalcite, Cu-doping, Cumene, Cumene hydroperoxide, Catalytic peroxidation

CLC Number:

O643.3

You-San ZHOU, Yi-Cheng ZHANG, Si-Yu WU, Fei ZHA, De-Jun CHEN, Yue CHANG. Catalytic Performance of Cu‑Doped Calcium Aluminum Layered Double Hydrotalcites for the Oxidation of Cumene to Cumene Hydrogen Peroxide[J]. Chinese Journal of Applied Chemistry, 2022, 39(6): 941-948.

Figures/Tables 10

Fig.1 XRD patterns of （a） Ca4Al-LDHs，（b） Ca4Cu0.3Al-LDHs，（c） Ca4Cu0.5Al-LDHs，（d） Ca4Cu0.8Al-LDHs and （e） Ca4Cu1.0Al-LDHs

Fig.2 FT-IR spectra of （a） Ca4Al-LDHs，（b） Ca4Cu0.3Al-LDHs，（c） Ca4Cu0.5Al-LDHs，（d） Ca4Cu0.8Al-LDHs and （e） Ca4Cu1.0Al-LDHs

Fig.3 TG curves of Ca4Cu x Al-LDHs

Table 1 The catalytic activity of Ca4Cu x Al?LDHs for cumene oxidation

样品 Sample	比表面积 S/（m²·g^-1）	孔容 Pore volume/（cm³·g^-1）	孔径 Bore diameter/nm
Ca₄Al?LDHs	10.47	0.002 4	36.37
Ca₄Cu_0.3Al?LDHs	11.66	0.002 7	21.03
Ca₄Cu_0.5Al?LDHs	42.30	0.007 0	30.35
Ca₄Cu_0.8Al?LDHs	27.65	0.002 0	32.52
Ca₄Cu_1.0Al?LDHs	15.42	0.003 1	34.27

Fig.4 SEM images and EDS analysis of Ca4Cu0.5Al-LDHs

Table 2 The catalytic activity of Ca4Al?LDHs for cumene oxidation

样品 Sample	转化率 Conversion/%	选择性 Selectivity/%
样品 Sample	转化率 Conversion/%	CHP	CA	AP
Ca₄Al?LDHs	2.0	100	0	0
Ca₄Cu_0.3Al?LDHs	12.7	85.8	14.1	0.1
Ca₄Cu_0.5Al?LDHs	34.5	86.9	12.0	1.1
Ca₄Cu_0.8Al?LDHs	31.7	87.1	11.7	1.2
Ca₄Cu_1.0Al?LDHs	17.8	83.5	16.1	0.4

Fig.5 Effect of temperature on the oxidation reaction

Fig.6 Effect of the reaction time on the oxidation reaction

Fig.7 Reusability of the catalyst

Fig.8 The products of liquid phase oxidation of cumene

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Catalytic Performance of Cu‑Doped Calcium Aluminum Layered Double Hydrotalcites for the Oxidation of Cumene to Cumene Hydrogen Peroxide

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