Positive-negative ion type bimetal catalyst, and its preparing method and use

A bimetallic catalyst, positive and negative ion technology, applied to the preparation of carboxylic acid by carbon monoxide reaction, chemical instruments and methods, physical/chemical process catalysts, etc., can solve problems such as deactivation, achieve easy generation, improve catalytic activity and stability, The effect of promoting the effect of catalysis is improved

Active Publication Date: 2005-07-20
INST OF CHEM CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although this type of catalyst structure pattern has good catalytic activity, it

Method used

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  • Positive-negative ion type bimetal catalyst, and its preparing method and use
  • Positive-negative ion type bimetal catalyst, and its preparing method and use
  • Positive-negative ion type bimetal catalyst, and its preparing method and use

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0032] Example 1

[0033] Preparation of catalyst anion part non-rhodium metal complex:

[0034] Weigh 0.02 mol of aminobenzoic acid and NaOH in 2 mol of water and heat to 70°C to react for 1 hour. After cooling, precipitate with excess acetone. After drying, sodium aminobenzoate is obtained. The reaction and structural formula are as follows:

[0035]

[0036] Weigh 0.01 mol of sodium aminobenzoate and dissolve it in a mixture of 1 mol of methanol and 0.5 mol of water, and add 0.01 mol of RuCl 3 , The reaction was heated and refluxed under stirring for 1 hour, after cooling, precipitated with acetone, and dried to obtain the sodium aminobenzoate ruthenium complex, the reaction and complex structure are as follows:

[0037]

[0038] The chromium, tin, lead and zirconium complexes of aminobenzoic acid sodium salt can also be obtained according to the above method. In this example, for the sake of brevity, they are not listed one by one.

[0039] Preparation of positive and nega...

Example Embodiment

[0045] Example 2

[0046] In a 250ml zirconium autoclave was added 0.32g of the rhodium-ruthenium bimetallic catalyst prepared in Example 1 with anthranilic acid as ligand, 1.24mol of methanol, 0.87mol of acetic acid, and 0.24mol of methyl iodide, and the temperature was raised after the introduction of CO To 150°C, keep the reaction pressure 4.0 MPa, the stirring speed 500 rpm, and the reaction time 30 min. The methanol conversion rate is 100%, the methyl acetate content is 0.02 mol, the acetic acid increment is 1.20 mol, and the acetic acid space-time yield is 20.7 mol AcOH / L·h.

Example Embodiment

[0047] Example 3

[0048]Add 0.32g of rhodium-chromium bimetallic catalyst with anthranilic acid as ligand prepared according to the method of Example 1 into the autoclave, 1.24mol of methanol, 0.87mol of acetic acid, and 0.24mol of methyl iodide. After passing CO, the temperature is raised to 180°C, keep reaction pressure 4.0MPa, stirring speed 500rpm, reaction time 20min, methanol conversion rate 100%, methyl acetate content is 0.04mol, acetic acid increment is 1.1mol, acetic acid space-time yield is 31.34mol AcOH / L·h.

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Abstract

The present invention relates to a new type positive and negative ion type bimetallic active species catalyst for oxo synthesis to prepare acetic acid. The positive ion active species of said catalyst is square planar cis-dicarbonyl structure which contains N and O donor atoms and is formed from aminobenzoic acid and Rh(I), and the negative ion active species is complex structure which also contains N and O donor atoms and is formed from aminobenzoic acid and non-rhodium metal ruthenium, stannum, chromium, lead and zirconium. In the oxo synthesis reaction said catalyst has high activity under the relative moderate condition, at the same time has good selectivity in the process of catalyzing methyl alcohol carbonylation to prepare acetic acid.

Description

technical field [0001] The invention relates to a positive and negative ion metal catalyst. [0002] The present invention also relates to a method for preparing the above-mentioned catalyst. [0003] The present invention also relates to the application of the above-mentioned catalyst in the synthesis of acetic acid from methanol hydroxyl group. Background technique [0004] The reaction of carbon monoxide with methanol to prepare acetic acid under the action of a catalyst is an oxo synthesis method developed in the 1940s and 1950s. In the early 1970s, Paulik et al. of Monsanto Company invented a homogeneous rhodium catalyst for oxo synthesis (US 3 769 329), which opened up a new implementation path for the oxo synthesis process. After continuous improvement and perfection, the oxo synthesis technology using rhodium as a catalyst has become the most important production process route with the largest output in the acetic acid industry. [0005] In current industrialized ...

Claims

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Application Information

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IPC IPC(8): B01J31/16C07C51/12
Inventor 袁国卿钱庆利潘平来石秀丽张抒峰邵守言凌晨
Owner INST OF CHEM CHINESE ACAD OF SCI
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