Non-noble metal homogeneous catalysis system for alcohol oxidation carbonylation and using method thereof

Abstract

The invention belongs to the field of chemical industry and discloses a non-noble metal homogeneous catalysis system for alcohol oxidation carbonylation and a using method thereof. The system consists of a composite catalyst MNC and a solvent NS (IV) which dissolves the composite catalyst, wherein the composite catalyst MNC is compounded by a metal complex MXn-Lm (I), a metal salt synergistic aid N (II) and / or an alkaline aid C (III). The general formula of the system is I+II+III+IV, I+II+IV, or I+III+IV. The catalyst has the advantages of simple process, mild reaction, high catalytic activity, good selectivity and stability, and low corrosion on production equipment. Meanwhile, the homogeneous system formed by the composite catalyst and the solvent can perform liquid phase circulation and has industrial application prospects.

Description

technical field [0001] The invention belongs to the field of chemical industry, and relates to a non-precious metal homogeneous catalyst system for homogeneous oxidative carbonylation of alcohols to synthesize dialkyl carbonates and co-production of organic esters. Background technique [0002] Carbonate (Carbonate), the general formula is: R and R' are alkane or aromatic groups, and R and R' can be the same or different; they can also be cyclic carbonates: R, R' may be an alkyl group, an alkoxy group, or the like. [0003] Carbonate is known as a "green" chemical product and a "new building block" for chemical synthesis. Due to its unique physical and chemical properties, its synthesis and application have received extensive attention at home and abroad this year. Important carbonates are dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate. Dimethyl carbonate (DMC), which has been widely studied ...

AI Technical Summary

Problems solved by technology

[0008] However, the catalysts used in the above methods are all based on CuCl with poor stability, containing high-concentration and highly corrosive chloride ions, and there are technical problems such as equipment corrosion, large catalyst usage, and poor stability.

[0009] Chinese patent CN1376665A proposes a new type of polymer complex catalyst, which uses a divalent copper system with better stability, and uses a high molecular polymer containing heteroatoms as a ligand. Low corrosiveness, but there are problems such as complex catalyst preparation, high toxicity of reaction medium and high reaction pressure

[0010] Chinese patent CN1962602A uses N-picoline tetrafluoroborate and other ionic liquids as reaction solvents on the basis of copper salt catalysts. The activity of copper salt catalysts is improved, but there are complex preparations of ionic liquids and difficulties in the separation of catalysts and ionic liquids. And other issues

However, since the carbonylation process uses noble metals / iodides as homogeneous catalysts, the shortage and high cost of precious metal resources have been plaguing the industrial application of the carbonylation reaction; Strong, low price, but its strong oxidizing property can easily lead to side reactions, and it will seriously corrode equipment

In 1994, Calafat et al. (Applied Catalysis A: General.1995, 133(1): 67-79) reported for the first time the study on the gas-phase carbonylation of methanol to MA on the sulfided CoMo / AC catalyst, but the conversion rate of methanol and low product selectivity