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Catalyst for hydroformylation reaction and preparation method of catalyst

A catalyst, chemical reaction technology, applied in the preparation of carbon monoxide reaction, preparation of organic compounds, catalysts for physical/chemical processes, etc., can solve the problems of high price of rhodium metal, harshness, poor stability of phosphite, etc.

Active Publication Date: 2014-03-26
WANHUA CHEM GRP CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the difficult problem of harsh reaction conditions (high temperature and high pressure) has not been solved
The appearance of the third-generation oil-soluble carbonyl rhodium phosphine catalyst enables the hydroformylation reaction to be carried out under mild conditions of low temperature and low pressure (110±10°C, 1.6-3.5MPa), which reduces the investment and energy consumption of reaction equipment, but It is only suitable for the hydroformylation reaction of short-chain olefins. When this type of catalyst is applied to the hydroformylation reaction of long-chain olefins, the problem of rhodium catalyst recovery difficulty occurs. The production cost has a crucial impact. In order to solve this problem, the fourth generation of water-soluble rhodium phosphine catalyst has been developed. The application of this catalyst solves the problem of catalyst recovery in the catalytic process of long-chain olefins, making the hydroformylation reaction Substrate extension to C 12 Long chain alkenes above
The second type is phosphite ligands with P-O bonds. Compared with organic bisphosphine ligands, phosphite ligands show good catalytic activity and selectivity in the hydroformylation reaction of olefins, and the synthesis is relatively fast. Easy, a series of single, double, and polymeric phosphite ligands used in the patent CN101681776 catalyze the hydroformylation reaction of olefins, and obtain better selectivity, but the phosphite has poor stability and is easy to hydrolyze, resulting in catalyst System life shortened
However, the reaction substrates involved are narrow and limited to alkenes, and the amount of ligand used is relatively large, which needs to reach 100 times the molar number of rhodium

Method used

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  • Catalyst for hydroformylation reaction and preparation method of catalyst
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specific Embodiment approach

[0039] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS: In order to better understand the present invention, the content of the present invention will be further clarified below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

[0040] In the embodiment, the instrument used for quantitative analysis of various hydroformylation reaction products is gas chromatography, and the analysis conditions are:

[0041]

[0042] The internal standard method was selected for accurate quantification, and the standard substance was methyl acrylate.

[0043] Melting point determination using: MPA100 automatic melting point apparatus

[0044] NMR analysis use: Bruck 400MHz NMR instrument

[0045] Elemental analysis using: Heraeus CHN-O-RAPID

[0046] The rhodium complex used in the catalyst system is selected from H(CO)(PPh 3 ) 3 Rh[tris(triphenylphosphine)hydrocarbonyl rhodium] or Rh(acac)(CO) 2 One of [rhodium acet...

Embodiment

[0051] The preparation process of the phosphoramidite ligand of the present invention is as follows:

[0052] Synthesis of Ligand A:

[0053] a) Synthesis of phosphine-chlorine compounds:

[0054] 5.2g PCl at -65°C under argon protection 3 (38mmol) and 5.1g of pyrrole and 200ml of dry tetrahydrofuran were mixed in a container, 11.5g of triethylamine was added to the mixture, stirred overnight at room temperature, filtered under reduced pressure, and the filtrate was distilled out of tetrahydrofuran and triethylamine at 60°C , the residue was dissolved in 50ml of toluene, and then the remaining precipitated triethylamine hydrochloride was filtered out, and the resulting solution was isolated from air and stored at low temperature. That is, dipyrrole phosphine chloride dissolved in toluene with a yield of 87%. The pure dipyrrolophosphine chloride was obtained after removing the toluene solvent under reduced pressure.

[0055] b) Ligand A synthesis:

[0056] 3.8g (13.3mmol) ...

Embodiment 1

[0116] Hydroformylation of Allyl Alcohol

[0117] Use respectively above-mentioned synthesized catalyst A-A, A-B, A-C, B-D, B-L, A-W, B-O to hydroformylate allyl alcohol, and the reaction process is as follows:

[0118] Add 15ml of the catalyst solution into a 100ml autoclave, and use CO / H 2 = 1:1 syngas to flush the solvent three times, then pressurize to 10bar, heat the autoclave to 65°C under stirring, then add 3.5ml of allyl alcohol, continue to pressurize to 12bar with syngas, under this constant pressure Gas uptake was monitored and when there was no more gas uptake, the autoclave was cooled and depressurized, and the resulting solution was analyzed by gas chromatography to determine the products, the reaction yielded 4-hydroxybutyraldehyde (HBA), 2-methyl-3-hydroxypropanal (HMPA), and propionaldehyde, propanol, propane, etc. C 3 by-product.

[0119] The comparison of catalytic results, such as the results in Table 3, shows that the catalysts A-A to A-C, B-D, and B-L ...

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Abstract

The invention relates to a catalyst for hydroformylation reaction and a preparation method of the catalyst. The catalyst comprises a rhodium complex and a novel bis-phosphoramidite ligand and is prepared by the rhodium complex and the novel bis-phosphoramidite ligand with molar ratio of 2:1-1:10 through mixed reaction. The catalyst can be applied to the hydroformylation reactions of compounds with unsaturated C-C double-bonded structure at any end position and can improve the yield of linear-chain aldehyde in a product, and the service life of the catalyst is remarkably prolonged.

Description

Technical field: [0001] The invention relates to a catalyst for hydroformylation reaction and a preparation method thereof. Background technique: [0002] The hydroformylation reaction, also known as the oxo reaction, is a reaction between olefins and synthesis gas (CO+H 2 ) is a homogeneous catalytic reaction process that generates aldehydes or alcohols under the action of a catalyst, which is an important class of synthetic aldehyde-based reactions. The raw materials used cover from C 2 Fraction ethylene starts up to chain length C 17 of hydrocarbons. According to the addition position of the aldehyde group, there are two types of hydroformylation products: normal and isomeric. Generally speaking, normal aldehyde is required for industrial production and is also the main product of hydroformylation. [0003] Catalysts for hydroformylation reactions have been developed for four generations so far. The first generation is cobalt carbonyl catalyst. The biggest disadvantage...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07F19/00C07B41/06C07C45/50C07C47/19C07C47/02C07C47/198C07C67/343C07C69/67C07C253/30C07C255/17
Inventor 石森张永振李鹏张旭庞计昌程英黎源
Owner WANHUA CHEM GRP CO LTD
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