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Preparation method of polymer ligand multi-metal cage catalyst and application of polymer ligand multi-metal cage catalyst in carbonylation synthesis of acetic acid or acetic anhydride

A polymer and multi-metal technology, applied in the direction of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, carbon monoxide reaction to prepare carboxylic acid, etc., can solve the problems of soaring and expensive precious metals, and achieve delay Dramatic changes, prolonging catalytic life, and reducing the effect of rhodium precipitation

Pending Publication Date: 2022-05-31
JIANGSU SOPO CHEM +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In recent years, especially after 2020, the price of precious metals has soared, especially the price of metal rhodium has increased by nearly 10 times, exceeding the mark of 4,000 yuan / gram. As the mainstream catalytic system for domestic acetic acid production, rhodium-based catalysts are expensive The price and the characteristics of easy to generate precipitation have become unbearable burdens for acetic anhydride production enterprises

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027]0.25 moles of 2-vinylpyridine, 0.25 moles of acrylic acid, 0.5 moles of methyl acrylate and trace crosslinker (wherein the crosslinker is 0.4% of the total number of monomer moles), mixed, added to the benzene solvent stirred, slowly added monomer moles 1% of the azo diisobutyronitrile as the initiator, reacted at 65 °C for 1h, after the solution is cooled, filtered by ether precipitation, then dissolved with acetone, repeatedly dissolved and precipitated 3-4 times, placed in vacuum to reduce pressure to constant weight, to obtain polymer ligand 1.

[0028] 0.03g lithium hydroxide and 1g polymer ligand 1 was dissolved in a 95% volume fraction ethanol water mixed solvent (water volume content of 5%), stirred at room temperature for 1h, and then added excess ether precipitation, placed in vacuum decompression to constant weight to obtain product A;

[0029] Place 0.03g NiCl 2 Dissolved in ethanol together with product A, under conditions of 50 °C, protected with CO gas, reflux...

Embodiment 2

[0032] In a 250ml pressure kettle, 1.34g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in solution is about 800ppm), methanol 1.1mol, iodomethane 0.2mol (co-catalyst), acetic acid 0.75mol (usually retain a certain amount of acetic acid as a solvent to maintain the stability of the catalyst during the continuous reaction process); after passing through carbon monoxide, heat up to 150 °C, stirring speed of 500 rpm, Control the reaction pressure 3.5MPa, the reaction time is 15 minutes, to obtain acetic acid.

[0033] The conversion rate of single methanol is 71.5%, after the laboratory simulation flash process, the catalyst is reused for catalytic reaction, the reaction conditions remain unchanged, after the catalyst is used 50 times, the conversion rate of single methanol can still reach 68.7%, and the attenuation is not obvious. The rhodium content of the reaction liquid after the initial and 50 cycles was tested by atomic absorption spectroscopy, and it wa...

Embodiment 3

[0039] In a 250ml pressure kettle, 0.81g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in solution is about 500ppm), methanol 1.1mol, iodomethane 0.02mol, acetic acid 1.12mol (in the continuous reaction process usually retains a certain amount of acetic acid as the solvent to maintain the stability of the catalyst);

[0040] The conversion rate of single methanol is 52.3%, after the laboratory simulation flash process, the catalyst is reused for catalytic reaction, the reaction conditions are unchanged, after the catalyst is used 50 times, the conversion rate of single methanol can still reach 51.7%, and the attenuation is not obvious. Through the atomic absorption spectroscopy to test the rhodium content of the reaction solution after 50 cycles, it was found that the rhodium content after 50 cycles still reached 95.6% of the initial state (the test method was to measure the amount of rhodium in the reaction liquid by atomic absorption spectroscopy, divide...

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Abstract

The invention belongs to the field of carbonylation synthesis of acetic acid and acetic anhydride, and discloses a preparation method of a polymer ligand multi-metal cage catalyst and application of the polymer ligand multi-metal cage catalyst in carbonylation synthesis of acetic acid or acetic anhydride. A micro-crosslinked hydrophilic polymer is prepared to serve as a metal rhodium ligand, meanwhile, other inorganic metal ions are introduced to serve as a cocatalyst, a system expands into a cage-shaped structure in a reaction solution, and due to the ionization effect and the water holding effect of the system, the evaporation speed of a solution in the cage-shaped system can be greatly delayed, and therefore rhodium precipitation is effectively inhibited. The introduction of other inorganic metal ions can effectively reduce the consumption of metal rhodium and reduce the cost of the catalyst, and meanwhile, due to the comprehensive action of the system, the catalytic activity and selectivity cannot be obviously reduced, so that the catalyst system has the characteristics of low cost, good stability and high efficiency.

Description

Technical field [0001] The present invention belongs to the field of carbonylated synthesis of acetic acid and acetic anhydride, specifically relates to the preparation method of polymer ligand polymetallic cage catalyst and its application in carbonylated synthesis of acetic acid or acetic anhydride. Background [0002] The carbonylation reaction of methanol and carbon monoxide under the action of homogeneous rhodium catalyst to prepare acetic acid was the invention of Paulik et al. (US3769329) of Monsanto Company in the United States in the early 1970s, which opened up a new and important process route for the carbonyl synthesis of methanol. On this basis, later Halcon (BE819455), Ealtman, Ajinamoto (JapanKokai50 / 30, 820), ShowaDenko (JapanKokai50 / 47,922), BP (B. VonSchlotheim, Chem.Industrie1994, 9 / 89. 80) and Hoechst (DE2450965) made breakthroughs in the study of the same [Rh(CO)2I2]-anionic structure form of catalyst active species for the preparation of acetic anhydride by ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18B01J31/22C07C51/12C07C53/08C07C51/56C07C53/12C08F220/14C08F226/06C08F220/06
CPCB01J31/1815B01J31/2217C07C51/12C07C51/56C08F220/14B01J2531/822B01J2531/847B01J2531/0238B01J2531/0213C08F226/06C08F220/06C07C53/08C07C53/12Y02P20/584
Inventor 邵守言闫丰文朱桂生代松涛黄志军王忠华袁国卿刘云梅许炎唐丽
Owner JIANGSU SOPO CHEM
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