Carbonylation of Methanol Over Nickel-Copper Based Supported Catalysts
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Carbonylation of Methanol Over Nickel‑Copper Based Supported Catalysts Andriy Yu. Kapran1 · Valeriy I. Chedryk1 · Lidiya M. Alekseenko1 · Svitlana M. Orlyk1 Received: 10 July 2020 / Accepted: 20 August 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract The results are reported concerning the production of methyl acetate in the halide-free vapor-phase methanol carbonylation (MC) over N iCl2–CuCl2 based catalysts on activated carbons and honeycomb cordierite supports. The formation of the MeOAc with the yield of 18% over nickel-copper chlorides on the BAC-A grade carbon support is shown to be facilitated by the optimal combination of the characteristics of the porous structure (mesopores with an average diameter of ~ 7 nm) and the surface acidity of the catalyst. 15% of MeOAc yield over NiCl2–CuCl2/cordierite, commensurate with the YMeOAc for NiCl2–CuCl2/AC, is achieved due to advantages of structured systems in comparison with the highly porous granular ones, including more efficient mass transfer and heat removal as well as the increased outputs per active components loadings. Using CuO–ZnO–NiO/Al2O3/cordierite (to generate CO as a carbonylation agent by MeOH decomposition) and N iCl2– CuCl2/AC(or cordierite) catalysts placed in series-connected flow-type reactors or in a single reactor with two different temperature zones provides producing methyl acetate in a carbon monoxide free gas feedstock with the MeOAc yields of 13–16.5% in “self-carbonylation” tandem process. Graphic Abstract
Keywords Methanol · Vapor-phase carbonylation · Methyl acetate · Nickel and copper chlorides · Activated carbon · Cordierite · Combination of decomposition and carbonylation * Andriy Yu. Kapran [email protected] Extended author information available on the last page of the article
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1 Introduction Methanol carbonylation (MC), based on homogeneous Monsanto and BP Chemicals Cativa™ processes, performed under high pressure in the liquid phase using Rh(Ir) catalysts and halide cocatalysts/promoters, is of industrial importance as a large-scale route to acetic acid [1–3]:
MeOH + CO → MeCOOH (ΔH◦ 298 K = −137.4 kJ/mol)
(1)
Beside HOAc, methyl acetate is also of interest as a carbonylation product which is widely used in industry as a solvent, feedstock in the synthesis of valuable organics, flavoring agent [4]: 2MeOH + CO → MeCOOMe + H2 O (ΔH◦ 298 K = −138.2 kJ/mol)
(2)
Despite the high yields of acetyl compounds, obvious are such shortcomings of the homogeneous systems as the complexity of separation of the catalyst and the reaction products, the high cost of catalysts based on the platinum group metals (PGM), and highly corrosivity of extremely toxic carcinogenic halogen-containing reaction medium. The halide-free heterogeneous-catalytic MC process in the vapor phase using catalysts, containing no precious metals, provides several advantages, including easy separation and reusability of catalysts, among which the most efficient are Ni-based on
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