Photo-Epoxidation of Cyclohexene in Gas-Phase
 
More details
Hide details
1
Department of Chemical Sciences, Federal University Wukari, PMB 1020, Taraba State, Nigeria
 
 
Submission date: 2024-05-21
 
 
Acceptance date: 2024-06-25
 
 
Publication date: 2024-06-30
 
 
Corresponding author
Emmanuel Alhassan Kamba   

eacambah@gmail.com
 
 
Trends in Ecological and Indoor Environmental Engineering, 2024;2(2):24-30
 
KEYWORDS
ABSTRACT
Background:
The production of alkenes as by-products of the oil industry, which poses a threat to public health and natural components of the environment. To prevent negative impacts, these volatile organic compounds (VOCs) must be converted into safe, useful products like epoxides. In addition, this process must be environmentally friendly and energy-efficient. Photoepoxidation of cyclohexene in the gas phase using H2 and O2 gases as redox agents can solve this problem. However, the effectiveness of the process must be studied.

Objectives:
The purpose is to investigate the effectiveness of using cyclohexene photocatalysis as an environmentally friendly, low-energy process for the production of epoxides in the gas phase using H2 and O2 gases as redox agents. It is also expected to obtain a low-cost, efficient process with the ability to control the reaction products.

Methods:
Titanium dioxide (TiO2) and Titanium silicate (TS-1) were prepared using sol gel and wetness impregnation, and used as photocatalysts.

Results:
Stable production of cyclohexene oxide was achieved with the TS-1 while only total mineralisation to CO2 was achieved with the TiO2. The kinetic analysis conducted here showed that the gas-phase reaction mechanism follows the Eley–Rideal mechanism. Gas-phase cyclohexene reacted directly with the intermediate formed through reaction between Ti base and the hydroperoxyl species, to produce cyclohexene oxide. Thus, this step was considered the rate-determining step. The effect of temperature was investigated at various partial pressures of individual gas reactant. An approximate value of 31 kJ/mol of activation energy was achieved. No epoxide was produced in the absence of H2 under the experimental conditions studied here. Total mineralisation of cyclohexene to CO2 was observed when O2 was used alone in the system.

Conclusions:
The results obtained in this work revealed that utilizing H2 and O2 for various oxidation reactions at elevated temperatures is possible.
REFERENCES (25)
1.
Deng, X., Wang, Y., Shen, L., Wu, H., Liu, Y., & He, M. (2013). Low-cost synthesis of titanium silicalite-1 (TS-1) with highly catalytic oxidation performance through a controlled hydrolysis process. Industrial & Engineering Chemistry Research, 52(3), 1190–1196. https://doi.org/10.1021/ie3024....
 
2.
Du, H., Fang, M., Chen, J., & Pang, W. (1996). Synthesis and characterization of a novel layered titanium silicate JDF-L1. Journal of Materials Chemistry, 6(11), 1827–1830.
 
3.
Gao, Y., Yin, J., Ren, G., Liu, H., & Xing, A. (2011). Synthesis of high-activity TiO2/WO3 photocatalyst via environmentally friendly and microwave assisted hydrothermal process. Journal of the Chemical Society of Pakistan, 33(6), 666–670.
 
4.
Joshi, A. M., Delgass, W. N., & Thomson, K. T. (2005). Comparison of the Catalytic Activity of Au3, Au4+, Au5, and Au5-in the Gas-Phase Reaction of H2 and O2 to Form Hydrogen Peroxide: A Density Functional Theory Investigation. The Journal of Physical Chemistry B, 109(47), 22392–22406. https://doi.org/10.1021/jp0526....
 
5.
Katkar, M. A., Rao, S. N., & Juneja, H. D. (2012). Green epoxidation of 1-hexene: O2 utilizing cis-MoO2 Schiff base complex. RSC advances, 2(21), 8071–8078.
 
6.
Khomane, R. B., Kulkarni, B. D., Paraskar, A., & Sainkar, S. R. (2002). Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in micellar media. Materials Chemistry and Physics, 76(1), 99–103. https://doi.org/10.1016/S0254-....
 
7.
Kwon, S., Schweitzer, N. M., Park, S., Stair, P. C., & Snurr, R. Q. (2015). A kinetic study of vapor-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1. Journal of Catalysis, 326, 107–115. https://doi.org/10.1016/j.jcat....
 
8.
Li, H., Xu, B., Deng, B., Yan, X., & Zheng, Y. (2014). Epoxidation of 1-hexene with hydrogen peroxide over nitrogen-incorporated TS-1 zeolite. Catalysis Communications, 46, 224–227. https://doi.org/10.1016/j.catc....
 
9.
Li, J., Xu, J., Dai, W. L., Li, H., & Fan, K. (2008). One-pot synthesis of twist-like helix tungsten–nitrogen-codoped titania photocatalysts with highly improved visible light activity in the abatement of phenol. Applied Catalysis B: Environmental, 82(3–4), 233–243. https://doi.org/10.1016/j.apca....
 
10.
Lousada, C. M., Johansson, A. J., Brinck, T., & Jonsson, M. (2012). Mechanism of H2O2 decomposition on transition metal oxide surfaces. The Journal of Physical Chemistry C, 116(17), 9533–9543. https://doi.org/10.1021/jp3002....
 
11.
Machado, T. C., Pizzolato, T. M., Arenzon, A., Segalin, J., & Lansarin, M. A. (2015). Photocatalytic degradation of rosuvastatin: Analytical studies and toxicity evaluations. Science of the Total Environment, 502, 571–577. http://dx.doi.org/10.1016/j.sc....
 
12.
Nguyen, V. H., Lin, S. D., Wu, J. C. S., & Bai, H. (2014). Artificial sunlight and ultraviolet light induced photo-epoxidation of propylene over V-Ti/MCM-41 photocatalyst. Beilstein Journal of Nanotechnology, 5(1), 566–576. https://doi.org/10.3762/bjnano....
 
13.
Nijhuis, T. A., & Weckhuysen, B. M. (2005). The role of water in the epoxidation over gold–titania catalysts. Chemical Communications, (48), 6002–6004. https://doi.org/10.1039/b51261....
 
14.
Ohno, T., Nakabeya, K., & Matsumura, M. (1998). Epoxidation of olefins on photoirradiated titanium dioxide powder using molecular oxygen as an oxidant. Journal of Catalysis, 176(1), 76–81. https://doi.org/10.1006/jcat.1....
 
15.
Ojeda, M., & Iglesia, E. (2009). Catalytic epoxidation of propene with H₂O–O₂ reactants on Au/TiO₂. Chemical Communications, 2009, 352–354. https://doi.org/10.1039/B81358....
 
16.
Perez Ferrandez, D. M., de Croon, M. H., Schouten, J. C., & Nijhuis, T. A. (2013). Gas-phase epoxidation of propene with hydrogen peroxide vapor. Industrial & Engineering Chemistry Research, 52(30), 10126–10132. https://doi.org/10.1021/ie4010....
 
17.
Pędziwiatr, P. (2018). Decomposition of hydrogen peroxide-kinetics and review of chosen catalysts. Acta Innovations, 26, 45–52.
 
18.
Ramakul, P., Yanachawakul, Y., Leepipatpiboon, N., & Sunsandee, N. (2012). Biosorption of palladium (II) and platinum (IV) from aqueous solution using tannin from Indian almond (Terminalia catappa L.) leaf biomass: Kinetic and equilibrium studies. Chemical Engineering Journal, 193, 102–111. https://doi.org/10.1016/j.cej.....
 
19.
Ren, Y., Che, Y., Ma, W., Zhang, X., Shen, T., & Zhao, J. (2004). Selective photooxidation of styrene in organic–water biphasic media. New Journal of Chemistry, 28(12), 1464–1469. https://doi.org/10.1039/B41103....
 
20.
Satterfield, C., & Stein, T. (1957). Decomposition of hydrogen peroxide vapor on relatively inert surfaces. Industrial & Engineering Chemistry, 49(7), 1173–1180. https://doi.org/10.1021/ie5057....
 
21.
Sever, R. R., & Root, T. W. (2003). DFT study of solvent coordination effects on titanium-based epoxidation catalysts. Part two: Reactivity of titanium hydroperoxo complexes in ethylene epoxidation. The Journal of Physical Chemistry B, 107(17), 4090–4099. https://doi.org/10.1021/jp0260....
 
22.
Shima, H., Tatsumi, T., & Kondo, J. N. (2010). Direct FT-IR observation of oxidation of 1-hexene and cyclohexene with H2O2 over TS-1. Microporous and Mesoporous Materials, 135(1–3), 13–20. https://doi.org/10.1016/j.micr....
 
23.
Yoon, C. W., Hirsekorn, K. F., Neidig, M. L., Yang, X., & Tilley, T. D. (2011). Mechanism of the decomposition of aqueous hydrogen peroxide over heterogeneous TiSBA15 and TS-1 selective oxidation catalysts: insights from spectroscopic and density functional theory studies. ACS Catalysis, 1(12), 1665–1678. https://doi.org/10.1021/cs2003....
 
24.
Zhang, L., Zhang, Z., He, X., Zhang, F., & Zhang, Z. (2017). Regulation of the products of styrene oxidation. Chemical Engineering Research and Design, 120, 171–178. https://doi.org/10.1016/j.cher....
 
25.
Zhao, Q., Li, P., Li, D., Zhou, X., Yuan, W., & Hu, X. (2008). Synthesis and characterization of titanium silicate-1 supported on carbon nanofiber. Microporous and Mesoporous Materials, 108(1-3), 311–317. https://doi.org/10.1016/j.micr....
 
Journals System - logo
Scroll to top