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

A methanol carbonylation and heterogeneous catalysis technology, applied in the field of bimetallic heterogeneous catalysis system, can solve the problems of reducing the number of conversions, catalyst deactivation, no discovery, etc., and achieves uniform pore size, uniform pore distribution, and simple reaction device. Effect

Inactive Publication Date: 2004-08-04
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0020] Example 1, take 0.203 gram of nickel chloride hexahydrate, 0.156 gram of lanthanum chloride heptahydrate, and dissolve them in methanol simultaneously, then take 5 grams of carbonized polyvinylidene chloride balls, soak them in the above solution, stir and absorb evenly, and dry After drying, put it into a quartz tube, reduce it with hydrogen diluted with nitrogen at 200-400°C, and perform high-temperature treatment (600-1000°C) under the protection of argon for 2-3 hours to obtain 1.0% nickel and 0.33 lanthanum. % bimetallic catalysts. Then part of the catalyst is loaded into the fixed-bed reactor, the air in the system is excluded, the temperature of the system is raised to 200°C, and the carbon monoxide partial pressure is kept at 1.0Mpa, and the mixed solution of methanol and methyl iodide (mol, 10:1 ) into the reaction column at a rate of 0.1ml / min. The cooled reaction product was collected from the outlet of the reaction column. The product content was analyzed ...

example 2

[0021] Example two, get 0.203 gram of nickel chloride hexahydrate, 0.156 gram of lanthanum chloride heptahydrate, dissolve in methanol simultaneously, then take 5 grams of carbonized polyacrylonitrile balls, soak in the above solution, absorb evenly through stirring, and dry After drying, put it into a quartz tube, reduce it with hydrogen diluted with nitrogen at 200-400°C, and perform high-temperature treatment (600-1000°C) under the protection of argon for 2-3 hours to obtain 1.0% nickel and 0.33 lanthanum. % bimetallic catalysts. Then part of the catalyst is loaded into the fixed-bed reactor, the air in the system is excluded, the temperature of the system is raised to 200 ° C, and the partial pressure of carbon monoxide is kept at 1.0 MPa, and the mixed solution of methanol and methyl iodide (mol, 10:1 ) into the reaction column at a rate of 0.1ml / min. The cooled reaction product was collected from the outlet of the reaction column. The product content was analyzed by ga...

example 3

[0022] Example three, get 0.203 gram of nickel chloride hexahydrate, 0.156 gram of lanthanum chloride heptahydrate, dissolve in methanol respectively, then get 5 grams of carbonized polyvinylidene chloride balls, and soak them in methanol solution of nickel chloride hexahydrate earlier, After stirring and absorbing evenly, dry it; then soak it in methanol solution of lanthanum chloride heptahydrate, put it into a quartz tube after vacuum drying, reduce it with hydrogen diluted with nitrogen at 200-400 ° C, and carry out high temperature treatment under the protection of argon ( 600-1000° C.) for 2-3 hours to obtain a bimetallic catalyst containing 1.0% nickel and 0.33% lanthanum. Then part of the catalyst is loaded into the fixed-bed reactor, the air in the system is excluded, the temperature of the system is raised to 200°C, and the carbon monoxide partial pressure is kept at 1.0Mpa, and the mixed solution of methanol and methyl iodide (mol, 10:1 ) into the reaction column at...

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PUM

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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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/83B01J32/00B01J37/00C07C51/12C07C53/08
Inventor 袁国卿李峰波黄军邹瑾
Owner INST OF CHEM CHINESE ACAD OF SCI
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