Study of the Methanol Conversion into Dimethyl Ether Obtained in the Process of Biomimetic Methane Monooxidation by Hydrogen Peroxide

Abstract:

The monooxidation of methane into methanol was carried out on biomimetic heterogeneous catalyst – iron pentafluorotetraphenylporphyrin on Al₂O₃ (ImtOH), at atmospheric pressure and temperatures of 200-350°C, which resulted in liquid one-carbon compounds CH₃OH (19.2%), CH₂O (1.55%), CH₃OCH₃ (8.2%) with high selectivity and are widely used in the chemical industry. In order to establish the routes of these products formation and the mechanism for the methane conversion into them, the investigation of the methanol conversion reaction was carried out, as an intermediate compound of the methane oxidation, under identical conditions on the same catalyst.The result was only dimethyl ether with 100% selectivity. This proved that in this reaction system, methanol obtained from the methane monooxidation is converted only into dimethyl ether, and formaldehyde, in parallel with methanol, is formed from methane. The mechanisms of the elementary stages of the formation of methanol, formaldehyde and dimethyl ether on the surface of the bioimitator through the formation of an active complex (ImtOOH) are presented, in which the unity of the mechanisms of redox and acid-base catalysis traced within the framework of the principle of the bond redistribution chain (BRC), similar to enzymatic reactions.

• Periodical: Materials Science Forum (Volume 1121)
• Pages: 119-128
• DOI: https://doi.org/10.4028/p-35bWu0
• Online since: May 2024
• Authors: Gulshan Nahmatova*, Latifa Gasanova, Tofig Nagiev
• Keywords: Biomimetic Catalyst, Coherent-Synchronized Reactions, Dehydration, Dimethylether, Methanol

References

[1] Johnson, D. Global, Methanol Market Review, IHS Inc. (2012). Available online: http://www.ptq.pemex.com/ productosyservicios/eventosdescargas/Documents/Foro (accessed on 1 June 2020).

[2] Lima Neto EP., Almeida ELF., Bomtempo JV Restructuring the cadeias the chemical and energy: the way methanol., Revista Brasileira de Energia, (2008) V.14, №2, pp.127-149.

[3] Han, S.; Sik, C. Applicability of dimethyl ether (DME) in a compression ignition engine as an alternative fuel. Energy Convers. Manag. (2014) 86, p.848–863.

DOI: 10.1016/j.enconman.2015.06.015

[4] V.M. Abbasov., H.C. Ibrahimov., S.R. Haciyeva., S.A. Mammadxanova., E.I. Abdullayev F.A. Amirov .Chemistry technology of oil and gas treatment processes., Science publishing house, Baki, ISBN 978-9952-495-15-7, (2014) 408p.

[5] Duncan Seddon, Methanol and dimethyl ether (DME) production from synthesis gas, 2010,DUNCAN SEDDON & ASSOCIATES PTY. LTD. JANUARY

DOI: 10.1533/9780857093783.4.363

[6] Dr Sobhan Ghosh, PRODUCTION OF METHANOL AND DME August (2016) 123p.

[7] Arcoumanis, C.; Bae, C.; Crookes, R.; Kinoshita, E. The potential of dimethyl ether (DME) as an alternative fuel for compression-ignition engines: A review. Fuel (2008) 87, p.1014–1030.

DOI: 10.1016/j.fuel.2007.06.007

[8] Trippe, F.; Fröhling, M.; Schultuann,F.; Stahl, R.; Henrich, E.,; Dalai,A. Comprehensive techno-economic assessment of dimethyl ether (DME) synthesis and Fischer-Tropsch synthesis as alternative process steps within biomass to liquid production. Fuel Process. Technol. (2013) 106, p.577–586.

DOI: 10.1016/j.fuproc.2012.09.029

[9] Azizi, Z.; Rezaeimanesh, M.; Tohidian, T.; Rahimpour, M.R. Dimethyl ether: A review of technologies and production challenges. Chem. Eng. Process. Process Intensif. (2014) 82, p.150–172.

DOI: 10.1016/j.cep.2014.06.007

[10] Vanessa M.Lebarbier, Robert A.Dagle, Libor Kovarik, Jair A.Lizarazo-Adarme, David L.King and Daniel R. Palo.Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts. Catalysis Science and Technology. (2012) vol. 2, iss. 10, p.2116.

DOI: 10.1039/c2cy20315d

[11] P.G. Musich, L.N. Kurina, A.V. Vosmerikov, Katalizatory pryamogo polucheniya dimetilovogo efira iz sintez gaza, Kataliz v khimicheskoy i neftekhimicheskoy promyshlennosti (in Russian) No 6, (2014) pp.33-37.

[12] Vibin Vargheese, Yasukazu Kobayashi, S Ted Oyama, The Direct Partial Oxidation of Methane to Dimethyl Ether over Pt/Y2O3 Catalysts Using an NO/O2 Shuttle, Angewandte Chemie, (2020) 132 (38) pp.16787-16793.

DOI: 10.1002/ange.202006020

[13] I Tyrone Ghampson, Gwang-Nam Yun, Arisa Kaneko, Vibin Vargheese, Kyoko K Bando, Tetsuya Shishido, S Ted Oyama, Effect of Support and Pd Cluster Size on Catalytic Methane Partial Oxidation to Dimethyl Ether Using a NO/O2 Shuttle, ACS Catalysis (2022) 12 (18), pp.11190-11205.

DOI: 10.1021/acscatal.2c02887

[14] Sun, K.; Lu, W.; Qiu, F.; Liu, S.; Xu, X. Direct synthesis of DME over bifunctional catalyst: Surface properties and catalytic performance. Appl. Catal. A Gen. (2003) 252, p.243–249.

DOI: 10.1016/s0926-860x(03)00466-6

[15] Bahmanpour, A.M.; Héroguel, F.; Baranowski, C.J.; Luterbacher, J.S.; Kröcher, O. Selective synthesis of dimethyl ether on eco-friendly K10 montmorillonite clay. Appl. Catal. A Gen. (2018) 560, p.165–170.

DOI: 10.1016/j.apcata.2018.05.006

[16] Rownaghi, A.A.; Rezaei, F.; Stante, M.; Hedlund, J. Selective dehydration of methanol to dimethyl ether on ZSM-5 nanocrystals. Appl. Catal. B Environ. (2012) 119–120, p.56–61.

DOI: 10.1016/j.apcatb.2012.02.017

[17] N.A. Stephenson, A.T. Bell, Effects of porphyrin composition on the activity and selectivity of the iron (III) porphyrin catalysts for the epoxidation of cyclooctene by hydrogen peroxide, Journal of Molecular Catalysis A: Chemical, Elsevier, July (2007) V. 272, No 1-2, pp.108-117.

DOI: 10.1016/j.molcata.2007.03.030

[18] Nagiev T.M. Coherent Synchronized Oxidation Reactions by Hydrogen Peroxide. Amsterdam: Elsevier, (2007) 325 p.

[19] Sariyya Aghamammadova, Inara Nagieva, Latifa Gasanova, Tofik Nagiev Catalytic monooxidation of cyclohexane by hydrogen peroxide in the gas phase // Reaction Kinetics, Mechanisms and Catalysis 2019, v 126, p.701–715

DOI: 10.1007/s11144-018-01525-1

[20] Nasirova U.V., Nagieva I.T., Gasanova L.M., Nagiev T.M. Kinetics and Mechanism of Coherent-Synchronized Ethylene Monooxidation by Hydrogen Peroxide on a Biomimetic Catalyst, per-FTPhPFe(III)OH/Al2O3. Journal of Materials Science and Engineering, April (2012) V. 2, No 4, pp.306-312.

DOI: 10.1134/s0036024411120235

[21] Patent AZ, № İ 20220060, T.M. Nagiev, L.M. Gasanova, G.Ch. Nahmatova., "Method of methanol obtaining", 27.09.2022.

[22] Gulshan Nahmatova, Latifa Gasanova, Olga Vodyankina, Eldar Dakhnavi, Tofik Nagiev, Coherently synchronized reaction of methane oxidation by green oxidizing agent – hydrogen peroxide over the biomimetic catalyst – iron pentafluorotetraphenylporphyrin deposited on alumina, Reaction Kinetics, Mechanisms and Catalysis, (2022) V.135, pp.3285-3301. https: doi.org/.

DOI: 10.1007/s11144-022-02300-z

[23] Ahmad Bahrein, Elham Ameri Thermodynamic İnvestigation of Temperature Effects on Dimethyl Ether Reforming//International Journal ol Basic Sciences, Applied Research, V.3 (SP), (2014) pp.187-190.

[24] Poltorak O.M., Chukrai E.S. Fiziko-khimicheskie osnovy fermentativnogo kataliza. M:.Vysshaya Shkola, (1971) 312 p.

[25] Mercedes Alfonso-Prieto, Xevi Biarne´s, Pietro Vidossich, and Carme Rovira, The Molecular Mechanism of the Catalase Reaction. American Chemical Society, (2009) V.131, 33, p.11751–11761.

DOI: 10.1021/ja9018572