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Double active species catalyst and its application

A catalyst and dual-activity technology, applied in physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, carbon monoxide reaction to prepare carboxylic acid, etc., can solve the problems of water gas reaction acceleration, consumption, and increased equipment investment

Active Publication Date: 2005-09-28
THE HONG KONG POLYTECHNIC UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In order to solve this problem, at present, in the production process of acetic acid, it is necessary to maintain a relatively high content of water and hydroiodic acid in the reaction system to achieve the purpose of increasing the solubility of the catalyst and improving the activity of the catalyst. The water gas reaction is accelerated, and the raw material carbon monoxide is consumed
At the same time, due to the strong corrosiveness of the reaction medium, the requirements for the material of the equipment are increased, and the investment of the equipment is also increased.

Method used

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  • Double active species catalyst and its application
  • Double active species catalyst and its application
  • Double active species catalyst and its application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] The preparation method of the transition metal complex of the anion part of the catalyst takes the nickel complex of sodium pyridine-3-formate as an example.

[0042] Weigh 0.02 mol of pyridine-3-carboxylic acid and NaOH, dissolve them in 2 mol of water, heat to 70°C for 1 h, cool, precipitate with excess acetone, and dry to obtain sodium pyridine-3-carboxylate.

[0043] Weigh 0.01mol of sodium pyridine-3-formate and dissolve it in a mixture of 1mol of methanol and 0.5mol of water, add 0.01mol of NiCl 2 , heated to reflux under stirring for 1h, cooled, precipitated with acetone, and dried to obtain pyridine-3-formic acid sodium-nickel complex.

[0044] Iron, Copper, Cobalt and Ru Complexes. The nickel, iron, copper, cobalt and ruthenium complexes of sodium aminoacetate, sodium 3-aminopropionate, sodium 4-aminobutyrate, sodium anthranilate, sodium m-aminobenzoate and sodium anthranilate were prepared by the above method.

Embodiment 2

[0046] The preparation of the dual-active species catalyst is an example of a pyridine-3-formic acid rhodium-pyridine-3-formic acid nickel dual-active species catalyst.

[0047] Weigh 0.02mol of pyridine-3-carboxylic acid and 0.01mol of [Rh(CO) 2 Cl] 2 Dissolve in 3mol of methanol, stir and react at 70°C for 1h, then add methanol-water mixture containing 0.01mol of pyridine-3-formic acid sodium-nickel complex (the molar ratio of methanol to water is 2:1), continue at 70°C The reaction was stirred for 1 h. After cooling, it was precipitated with ether and filtered. Wash twice with methanol water (2:1 mol) mixed solution at 0°C, and dry at room temperature to constant weight to obtain brown pyridine-3-carboxylate rhodium-pyridine-3-carboxylate nickel dual-active species catalyst.

[0048] Adopt above-mentioned method to prepare the cobalt, iron, copper and ruthenium of pyridine carboxylic acid listed in embodiment 1 and aminocarboxylate nickel, cobalt, iron, copper dual activ...

Embodiment 3

[0052] Add 0.3 g of rhodium pyridine-2-carboxylate-nickel pyridine-3-carboxylate catalyst, 1.24 mol of methanol, 0.87 mol of acetic acid, and 0.24 mol of methyl iodide into a 250 ml zirconium autoclave, heat up to 150 ° C after feeding CO, and maintain the reaction pressure 4.0MPa, stirring speed 500 rpm, reaction time 30min. The conversion rate of methanol is 100%, the content of methyl acetate is 0.02 mol, the increment of acetic acid is 1.19 mol, and the space-time yield of acetic acid is 20.7 mol AcOH / L·h.

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Abstract

The present invention is catalyst capable of catalyzing the carbonylation of methanol into acetic acid and the carbonylation of methyl acetate into acetic anhydride in high speed, high selectivity and relatively mild condition. By means of design of catalyst molecule structure, non-rhodium metal with certain catalytic activity or obvious catalysis assisting activity on carbonylation reaction is introduced into catalyst with rhodium as active component to form new double active component catalyst. Of the catalyst, the positive ion active component may be square planar cis-bicarbonyl structure formed with organic compound or polymer containing N and O donor atom and Rh(I); and the negative ion active component may be coordination compound structure formed with organic carboxylic acid compound containing N and O donor atom and transition metal salt.

Description

technical field [0001] The invention proposes a novel catalyst, which is characterized in that the catalyst is a positive and negative ion catalyst with dual active species. The positive and negative ion catalyst with dual active species can be a catalyst applied to carbonylation of methanol to synthesize acetic acid and acetic anhydride. Background technique [0002] The invention (US 3 769 329) of Paulik et al. of Monsanto Company for methanol carbonylation to synthesize homogeneous rhodium catalyst in the early 1970s has opened up a new implementation path for the carbonylation process. After continuous improvement and perfection, the low-pressure oxo synthesis technology has become the most important technical route in the acetic acid and acetic anhydride industries. [0003] In the research of catalysts, rhodium's square planar negative ion structure complexes have been successfully applied to industrial production. This type of complex structure mode has high catalyt...

Claims

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Application Information

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IPC IPC(8): B01J31/02B01J31/16B01J31/18C07C51/12C07C53/08C07C53/12
Inventor 陈新滋袁国卿
Owner THE HONG KONG POLYTECHNIC UNIV
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