Methanol carbonylation nickel lanthanum bimetal multiphase catalytic system and its manufacturing method and application

Abstract

A multi-phase bimetal catalyst system for carbonylating reaction of methanol to obtain acetic acid and methyl acetate is composed of cocatalyst (iodomethane) and primary catalyst Ni-La/Ys, where Ys is the carbonified high polymer. Its preparing process includes preparing carrier of primary catalyst, carbonifying carrier, and preparing primary catalyst.

Description

technical field [0001] The invention relates to a bimetallic heterogeneous catalytic system, in particular to a nickel-lanthanum bimetallic heterogeneous catalytic system for methanol carbonylation reaction. [0002] The present invention also relates to the preparation method of the main catalyst in the above catalytic system. [0003] The present invention also relates to the application of the above catalyst system in the hydroxylation reaction of methanol. Background technique [0004] Now, the method of using iridium and rhodium homogeneous catalysts to catalyze the carbonylation of methanol into acetic acid, represented by British BP and Mosanto, has formed a large scale of production. However, due to the complex equipment requirements for homogeneous catalysts, the difficulty in product separation, and the serious corrosion of the equipment by the reaction medium during the reaction process, it has brought great difficulties to industrial production. [0005] The us...

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Problems solved by technology

Activated carbon is a frequently used catalyst carrier (Catal. Today. 40 (1998) 397-404), as well as widely used alumina carrier (ACS Symposium Series, Vol 328 American Chemical Society), and zeolites and some inorganic salts are also used It is used as the carrier of this type of catalyst (German patent DE 3606 169, 1987), but their activity is far from the requirements of industrialization

The second is that there is no way to prevent the active metal from falling off in large quantities from the surface of the carrier during the reaction process.

Although activated carbon is inert against acid and alkali, it is easy to sinter during long-term reaction and deactivate the catalyst

The 3rd, have not found a kind of co-catalyst that can greatly promote the catalytic activity of nickel catalyst, once people have studied the co-catalyst performance (Ing.Eng.Chem.Res.1994,33,488- 492), but it does not change the low activity of nickel-based catalysts. Lanthanum has no catalytic carbonylation performance, but we found that when nickel and lanthanum form a bimetallic catalyst, lanthanum exhibits excellent catalytic performance

The fourth is that the particle size of the carrier is difficult to control to obtain the desired uniform particles. At the same time, the pore size distribution on the particles is also difficult to achieve unity with the high surface area, that is, it cannot reach the ideal performance requirements of the catalyst used in the production of acetic acid in industry.

In addition, in the existing catalytic research reaction system, some research works use a certain amount of acetic acid as an additive to increase the polarity of the system to increase the conversion rate of methanol carbonylation, but the presence of acetic acid reduces the effective reaction space of methanol , reducing the number of conversions per unit time