Facile Synthesis of Cyclohexanone Oxime via Solvent-Free Catalytic Oxidation of Cyclohexylamine Using Phosphorus-Modified TiO2/SBA-15

doi:10.19894/j.issn.1000-0518.240278

Chinese Journal of Applied Chemistry ›› 2026, Vol. 43 ›› Issue (1): 96-107.DOI: 10.19894/j.issn.1000-0518.240278

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Facile Synthesis of Cyclohexanone Oxime via Solvent-Free Catalytic Oxidation of Cyclohexylamine Using Phosphorus-Modified TiO₂/SBA-15

Xiao-Peng DENG, Shui-Lin LIU(), Yuan-Peng LI, Shan-Tong ZHANG

School of Chemical and Environmental Engineering，Hunan Institute of Technology，Hengyang 421002，China

Received:2024-08-28 Accepted:2025-01-20 Published:2026-01-01 Online:2026-01-26
Contact: Shui-Lin LIU
About author:shuilin89@126.com
Supported by:
the Research Foundation of Education Bureau in Hunan Province(22A0631);Natural Science Foundation in Hunan Province(2024JJ7127);Hunan Province College Students' Innovation and Entrepreneurship Training Program Project(S202411528205);Hunan Province First-Class Undergraduate Major Construction Project(DS2002)

Abstract

Abstract:

A highly efficient P-TiO₂/SBA-15_{catalyst using titanium butoxide and phosphoric as raw materials was synthesized by liquid phase hydrolysis method， and the physio-chemical properties of the catalysts were characterized by X-ray photoelectron spectroscopy （XPS）， fourier transform infrared spectroscopy （FT-IR）， transmission electron microscope （TEM）， X-ray powder diffraction （XRD）， and N₂ adsorption-desorption specific surface analyzer （BET） characterization techniques. The catalytic performance of P-TiO₂/SBA-15 in the solvent-free oxidation of cyclohexylamine to cyclohexanone oxime was further studied. And the reaction conditions such as temperature and pressure were systematically optimized. Furthermore， a probable dual pathway mechanism of cyclohexylamine catalytic oxidation was also suggested. The results indicated that surface modified P-TiO₂ nanoparticles could achieve high dispersion loading on SBA-15， which was beneficial for improving its catalytic efficiency. The best catalytic effect was achieved when the P-TiO₂ loading was 10%. Under the premise of equal loading of active components， the 10% P-TiO₂/SBA-15 composite exhibited significant catalytic performance advantages. Compared to the unloaded P-TiO₂， the catalytic conversion efficiency of cyclohexylamine increased by 3.2 times to 68.3%， and the selectivity of the target product cyclohexanone oxime increased by 15.3% simultaneously. Under standardized reaction conditions （90 ℃， 1.0 MPa， 4 h）， the efficient conversion could be achieved using 0.3 g of composite catalyst， confirming the dispersion strengthening effect of ordered mesoporous carriers on active components. In addition， the titanium hydroxyl groups on the surface of P-TiO₂/SBA-15 were the active centers for catalytic oxidation of cyclohexylamine. The method provides a novel and green route for the highly efficient preparation of cyclohexanone oxime， and has certain prospects for industrial applications.}

Key words: Cyclohexanone oxime, Solvent-free, Catalytic oxidation, Cyclohexylamine, P-TiO₂

CLC Number:

O643.3

Xiao-Peng DENG, Shui-Lin LIU, Yuan-Peng LI, Shan-Tong ZHANG. Facile Synthesis of Cyclohexanone Oxime via Solvent-Free Catalytic Oxidation of Cyclohexylamine Using Phosphorus-Modified TiO₂/SBA-15[J]. Chinese Journal of Applied Chemistry, 2026, 43(1): 96-107.

Figures/Tables 12

References 40

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Sample	Surface area/（m²·g^-1）	Pore volume/（cm³·g^-1）	Pore diameter/nm
P-TiO₂	348.6	0.5	5.8
SBA-15	526.6	1.2	10.0
5% P-TiO₂/SBA-15	494.6	1.2	10.1
10% P-TiO₂/SBA-15	467.6	1.1	10.4
20% P-TiO₂/SBA-15	433.5	1.1	10.2

Sample	Surface area/（m²·g^-1）	Pore volume/（cm³·g^-1）	Pore diameter/nm
P-TiO₂	348.6	0.5	5.8
SBA-15	526.6	1.2	10.0
5% P-TiO₂/SBA-15	494.6	1.2	10.1
10% P-TiO₂/SBA-15	467.6	1.1	10.4
20% P-TiO₂/SBA-15	433.5	1.1	10.2

Catalyst	Conversion/%	Selectivity/%
Catalyst	Conversion/%	CHO	CH	NCH	CCA	Others ^b
None	5.3	24.2	2.1	0.6	61.9	11.2
SBA-15	22.9	72.1	3.2	1.2	17.5	6.0
P-TiO₂ （n（Ti）∶n（P）=1∶1）	38.3	78.9	1.6	3.9	11.3	4.3
P-TiO₂ （n（Ti）∶n（P）=2∶1）	45.0	80.6	3.0	5.9	4.8	5.7
P-TiO₂ （n（Ti）∶n（P）=3∶1）	45.8	79.4	2.9	6.8	5.1	5.8
P-TiO₂ （n（Ti）∶n（P）=2∶1） ^c	21.2	71.3	4.1	1.1	18.4	5.1
10%P₂O₅/SBA-15	24.1	74.5	3.3	2.4	15.3	4.5
10%TiO₂/SBA-15	49.8	81.4	1.8	4.6	7.0	5.2
5% P-TiO₂/SBA-15	38.4	79.5	1.7	3.7	11.5	3.6
10% P-TiO₂/SBA-15	68.3	86.6	2.1	6.8	2.4	2.1
20% P-TiO₂/SBA-15	61.9	85.4	2.7	6.5	2.8	2.6
10% P-TiO₂/SBA-15 ^d	7.2	51.2	2.4	0.8	37.8	7.8

Catalyst	Conversion/%	Selectivity/%
Catalyst	Conversion/%	CHO	CH	NCH	CCA	Others ^b
None	5.3	24.2	2.1	0.6	61.9	11.2
SBA-15	22.9	72.1	3.2	1.2	17.5	6.0
P-TiO₂ （n（Ti）∶n（P）=1∶1）	38.3	78.9	1.6	3.9	11.3	4.3
P-TiO₂ （n（Ti）∶n（P）=2∶1）	45.0	80.6	3.0	5.9	4.8	5.7
P-TiO₂ （n（Ti）∶n（P）=3∶1）	45.8	79.4	2.9	6.8	5.1	5.8
P-TiO₂ （n（Ti）∶n（P）=2∶1） ^c	21.2	71.3	4.1	1.1	18.4	5.1
10%P₂O₅/SBA-15	24.1	74.5	3.3	2.4	15.3	4.5
10%TiO₂/SBA-15	49.8	81.4	1.8	4.6	7.0	5.2
5% P-TiO₂/SBA-15	38.4	79.5	1.7	3.7	11.5	3.6
10% P-TiO₂/SBA-15	68.3	86.6	2.1	6.8	2.4	2.1
20% P-TiO₂/SBA-15	61.9	85.4	2.7	6.5	2.8	2.6
10% P-TiO₂/SBA-15 ^d	7.2	51.2	2.4	0.8	37.8	7.8

Facile Synthesis of Cyclohexanone Oxime via Solvent-Free Catalytic Oxidation of Cyclohexylamine Using Phosphorus-Modified TiO₂/SBA-15

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