Preparation method and application of bifunctional catalyst for high-selectivity preparation of isobutyraldehyde by propylene hydroformylation

A technology for the hydroformylation of propylene and a bifunctional catalyst is applied in the field of bifunctional catalysts and their preparation, which can solve the problems of inapplicability of isobutyraldehyde and the like, and achieve the effects of improving the degree of dispersion, enriching the stock and avoiding sintering

Active Publication Date: 2021-01-05
RUNTAI CHEM TAIXING CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Therefore, the rhodium-containing catalyst currently used to increase the conversion ratio of n-butyraldehyde is not suitable for the preparation of isobutyraldehyde

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The preparation method of the bifunctional catalyst for preparing isobutyraldehyde with high selectivity in the hydroformylation of propylene in this embodiment comprises the following steps:

[0027] (1) Dissolve 3g of cobalt nitrate hexahydrate in 100mL of ethanol, then add 20g of urea, stir evenly to form a mixed solution;

[0028] (2) The rare earth modified HY molecular sieve was prepared by conventional impregnation method, and the rare earth was CeO 2 ; rare earth CeO 2 The loading in HY molecular sieve is 0.5wt%.

[0029] (3) Immerse the mixed solution in step (1) into 18g CeO 2 The modified HY molecular sieve was left to stand for 12h, and then dried at 120°C for 12h to obtain a catalyst precursor;

[0030] (4) Put the catalyst precursor prepared in step (3) in a high-temperature furnace, feed He gas, raise the temperature from room temperature to 500°C at a rate of 3°C / min, and keep at 500°C for 3 hours to obtain a catalyst.

Embodiment 2

[0032] (1) Dissolve 5g of cobalt nitrate hexahydrate in 100mL of ethanol, then add 30g of melamine, stir to form a mixed solution;

[0033] (2) The rare earth modified HZSM-5 molecular sieve is prepared by conventional impregnation method, and the rare earth is Y 2 o 3 ; Rare earth Y 2 o 3 The loading amount in the HZSM-5 molecular sieve carrier is 0.8wt%.

[0034] (3) Immerse the mixed solution in step (1) to 15g Y 2 o 3 The modified HZSM-5 molecular sieve was left to stand for 18 hours, and then dried at 120°C for 12 hours to obtain a catalyst precursor;

[0035] (4) the catalyst precursor that step (3) is made is placed in high-temperature furnace, passes into N 2 gas, from room temperature to 700°C at a rate of 5°C / min, and kept at 700°C for 2 hours to obtain a catalyst.

Embodiment 3

[0037] (1) Dissolve 8g of cobalt chloride in 200mL of ethanol, then add 50g of dopamine, stir to form a mixed solution;

[0038] (2) The rare earth modified HMCM-36 molecular sieve was prepared by conventional impregnation method, and the rare earth was La 2 o 3 ; Rare earth La 2 o 3 The loading in HMCM-36 carrier was 1.0 wt%.

[0039] (3) Immerse the mixed solution in step (1) to 20g La 2 o 3 The modified HMCM-36 molecular sieve was left to stand for 20 hours, and then dried at 150°C for 12 hours to obtain a catalyst precursor;

[0040] (4) the catalyst precursor that step (3) is made is placed in high-temperature furnace, passes into N 2 gas, from room temperature to 800°C at a rate of 5°C / min, and kept at 800°C for 2 hours to obtain a catalyst.

[0041] The catalyst prepared in Example 1-3 is used for the application in the highly selective preparation of isobutyraldehyde by hydroformylation of propylene, and the specific application method is:

[0042] Put the cataly...

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Abstract

The invention belongs to the technical field of catalysis, and particularly relates to a preparation method and application of a bifunctional catalyst for high-selectivity preparation of isobutyraldehyde by propylene hydroformylation. According to the characteristics of an isobutyraldehyde product, propylene is firstly adsorbed on a rare earth modified acidic carrier to generate secondary positivecarbon ions, then the secondary positive carbon ions are subjected to addition with CO on active center cobalt carbide, and finally the product is generated through addition with active hydrogen. Thebifunctional catalyst is prepared by the steps of dipping cobalt salt and a nitrogen-containing compound precursor into acidic molecular sieve pores, carbonizing at a relatively high temperature, generating active center cobalt carbide highly dispersed in the molecular sieve pores in situ, and generating an N-modified carbon layer on the surface of the cobalt carbide. The carrier in the catalystplays an acidic role, and cobalt carbide activates CO and H2 at the same time. The prepared catalyst enables the yield of isobutyraldehyde to be as high as 79%. The catalyst prepared by the method islow in cost, high in activity, good in catalyst stability and high in isobutyraldehyde selectivity, and has a good industrial prospect.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a bifunctional catalyst for preparing isobutyraldehyde with high selectivity by propylene hydroformylation and a preparation method thereof. Background technique [0002] Olefin hydroformylation is a typical atom economy reaction, which was first discovered by German scientist Otto Roelen in 1938. The aldehyde groups generated by the hydroformylation reaction can be further converted into imines, amines, hemiacetals, acetals, aminals, carboxyl groups, hydroxyl groups, etc. The produced aldehyde compounds are widely used in the synthesis of plasticizers, surfactants, drugs, pesticides, seasonings and other fine chemicals. One representative reaction is the hydroformylation of propylene to butyraldehyde. [0003] The purpose of the existing propylene hydroformylation reaction is to prepare n-butyraldehyde. In order to improve the selectivity of n-butyraldehyde, the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/14B01J29/46B01J29/76B01J37/02B01J37/08C07C45/50C07C47/02
CPCB01J29/146B01J29/46B01J29/76B01J23/002B01J37/0201B01J37/088C07C45/505C07C47/02B01J2229/183B01J2229/186
Inventor 张世元卢小松宋文国
Owner RUNTAI CHEM TAIXING CO LTD
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