Catalysis system for synthesizing methyl propionate and application method thereof

Abstract

The invention discloses a catalysis system for synthesizing methyl propionate and an application method thereof. The catalysis system is prepared from a ruthenium-cluster carbonyl complex, imidazoliumionic liquid and an inorganic salt accelerator, or the ruthenium-cluster carbonyl complex and the imidazolium ionic liquid, wherein the mole ratio of the imidazolium ionic liquid to the ruthenium-cluster carbonyl complex is (100-250):1; when the catalysis system comprises the accelerator, the mole ratio of the accelerator to the ruthenium-cluster carbonyl complex is (1-75):1; the accelerator is carbonate, halogenated lithium or transitional metallic chloride. The system uses the imidazolium ionic liquid to consume water produced in the reaction to accelerate the reaction to be performed towards the forward direction; by the adding of the inorganic salt accelerator, the catalytic activity is further improved, so as to catalyze ethylene, CO2 and methanol to prepare the methyl propionate. The catalysis system obviously shortens the reaction time, so that the yield of the methyl propionate is increased.

Description

Technical field: [0001] The invention belongs to the field of organic chemical products synthesized by hydroesterification reaction, and in particular relates to a method for synthesizing methyl propionate through ethylene carbonylation. Background technique: [0002] Methyl propionate is a colorless and transparent organic liquid, which can be used as spices, solvents, extractants, organic intermediates and plasticizers, and is widely used in adhesives, coatings, textiles, rubber, plastics and other industries . Methyl propionate can produce propionate, propionic acid, propionate (benzyl propionate, isoamyl propionate, etc.) and other products through esterification reaction, hydrolysis reaction and transesterification reaction, so methyl propionate The development of ester synthesis process is beneficial to the progress and development of propionic acid, propionate, propionate and other process technologies. [0003] Germany's Reppe has proposed ethylene hydroesterificat...

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Problems solved by technology

[0003] Germany's Reppe has proposed ethylene hydroesterification method to directly synthesize methyl propionate or ethyl propionate technology, and it uses Ni series catalyst, and reaction condition is harsh, and equipment requirement is higher; Patent (CN87110635) relates to palladium (II) / The aryl-substituted phosphine / acid catalyst system has higher activity in catalyzing ethylene / methanol carbonylation, but the phosphine ligand in this kind of ligand system is easy to decompose and cause catalyst deactivation; literature (R.F.Heck, J.A.m.Chem.Soc., 1963,85; W.Keim.J.Mol.Catal.,1989,54(1)) showed that complex catalysts such as ruthenium, nickel, cobalt, etc. were active in oxo-synthesizing methyl propionate from ethylene / CO / methanol

However, the reaction conditions are harsh, the conversion rate is low, and the selectivity is poor; in the patent (CN103319337), palladium acetate is used as the main catalyst, and metal ions such as cobalt, nickel or ruthenium are cocatalysts. The conditions are mild and the selectivity is high, but due to the expensive palladium metal, the production cost is high; Hidai et al. (J.Mol.Catal., 1987,40(2):243-254) found that Ru 3 (CO) 12 With ionic iodide as a cocatalyst, ethylene / CO / methanol is catalyzed to synthesize methyl propionate with high selectivity, but these catalytic systems need CO as raw material, which is toxic, flammable and difficult to store

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