Comparative Study of 1,3,5-Trinitrobenzene and 2,4,6-Trinitrotoluene Hydrogenation over Copper-Aluminum Oxide Catalyst in a Flow Reactor

A. L. Nuzhdin; Нуждин А. Л.; I. А. Shchurova; Щурова И. А.; M. V. Bukhtiyarova; Бухтиярова М. В.; P. E. Plyusnin; Плюснин П. Е.; N. A. Alekseyeva; Алексеева Н. А.; S. V. Sysolyatin; Сысолятин С. В.; G. A. Bukhtiyarova; Бухтиярова Г. А.

doi:10.31857/S0453881123010045

Comparative Study of 1,3,5-Trinitrobenzene and 2,4,6-Trinitrotoluene Hydrogenation over Copper-Aluminum Oxide Catalyst in a Flow Reactor

Authors: Nuzhdin A.L.¹, Shchurova I.А.¹^,2, Bukhtiyarova M.V.¹, Plyusnin P.E.³, Alekseyeva N.A.¹^,2, Sysolyatin S.V.², Bukhtiyarova G.A.¹
Affiliations:
1. Boreskov Institute of Catalysis SB RAS
2. Institute for Problems of Chemical and Energetic Technologies SB RAS
3. Nikolaev Institute of Inorganic Chemistry SB RAS
Issue: Vol 64, No 1 (2023)
Pages: 31-38
Section: ARTICLES
URL: https://ruspoj.com/0453-8811/article/view/660261
DOI: https://doi.org/10.31857/S0453881123010045
EDN: https://elibrary.ru/KHAEGN
ID: 660261

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Abstract

The catalytic properties of a copper-aluminum oxide catalyst obtained from double layered hydroxide have been studied in hydrogenation of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) in a flow reactor. The reaction was carried out at temperature of 120°C, total pressure of 30 bar and substrate concentration of 0.10–0.15 M, using methanol as a solvent. 1,3,5-Triaminobenzene (TAB) and 2,4,6-triaminotoluene (TAT) were isolated from the reaction mixture in the form of double salts with sulfuric acid TAB⋅2H₂SO₄ and TAT⋅2H₂SO₄, the yield of which was 92 and 98%, respectively. At an initial trinitroarene concentration of 0.10 M, the hydrolysis of triaminobenzene salts made it possible to synthesize phloroglucinol and methylphloroglucinol in 78 and 91% yields. Increasing the concentration to 0.15 M reduces the yield to 71 and 88%, respectively. According to thermal analysis data, the observed differences in the yields of triaminobenzene salts and polyphenols are explained by the formation of different amounts of resinous by-products on the catalyst surface during hydrogenation of trinitroarene. Hydrogenation of TNT produces less resin, resulting in higher yields of TAT⋅2H₂SO₄ and methyl phloroglucinol. This is probably due to the presence of an electron-donating methyl substituent, which slows down polycondensation of TAT molecules.

Keywords

hydrogenation, Cu-Al oxide catalyst, 1,3,5-trinitrobenzene, 2,4,6-trinitrotoluene, triaminobenzenes, phloroglucinol derivatives, flow reactor

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