阅读说明：本技术 一种丙烯醛氢甲酰化合成丁二醛工艺 (Process for synthesizing butanedialdehyde by acrolein hydroformylation ) 是由 梁建平 谭海军 王亚林 赵雯婷 代渝 王玉玫 于 2021-06-30 设计创作，主要内容包括：本发明公开了一种丙烯醛氢甲酰化合成丁二醛工艺,以丙烯醛、合成气为原料,合成气包括氢气和一氧化碳,以丁二醛为溶剂,在溶解了催化剂的丁二醛溶液中,加入丙烯醛和合成气,在一定温度和压力条件下,丙烯醛直接发生氢甲酰化反应合成1,4-丁二醛。本发明的有益效果：采用丙烯醛、氢气、一氧化碳为生产原料,原料易于取得并成本相对低廉；通过催化剂在一定压力和温度下反应,实现丙烯醛直接氢甲酰化合成丁二醛,工艺简单易于操作,适于大规模生产。(The invention discloses a process for synthesizing butanedialdehyde by hydroformylation of acrolein, which takes acrolein and synthesis gas as raw materials, the synthesis gas comprises hydrogen and carbon monoxide, butanedialdehyde is taken as a solvent, the acrolein and the synthesis gas are added into a butanedialdehyde solution dissolved with a catalyst, and the acrolein directly undergoes hydroformylation reaction to synthesize the 1, 4-butanedialdehyde under certain temperature and pressure conditions. The invention has the beneficial effects that: acrolein, hydrogen and carbon monoxide are used as production raw materials, so that the raw materials are easy to obtain and have relatively low cost; the direct hydroformylation of acrolein to form butanedialdehyde is realized by the reaction of the catalyst under certain pressure and temperature, and the process is simple and easy to operate and is suitable for large-scale production.)

1. A process for synthesizing butanedialdehyde from acrolein by hydroformylation features that the acrolein and synthetic gas containing hydrogen and CO are used as raw materials, the butanedial is used as solvent, and the acrolein and synthetic gas are added to the solution of butanedial in which catalyst is dissolved, and under the conditions of temp and pressure, the acrolein is directly hydroformylated to synthesize 1, 4-butanedial.

2. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1, wherein: the acrolein enters the reactor in liquid form.

3. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1 or 2, wherein: the synthesis gas enters the reactor in a gaseous state.

4. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1, wherein: the molar ratio of hydrogen to carbon monoxide in the synthesis gas is (0.9-1.4): 1, the molar ratio of acrolein to synthesis gas is 1: (2-3).

5. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1, wherein: rhodium carbonyl is used as a catalyst, triphenylphosphine is used as a catalyst ligand, and the rhodium carbonyl is dissolved in a succinaldehyde solution.

6. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1, wherein: the concentration of rhodium carbonyl in the reaction solution is 0.001-1 wt%, and the mass ratio of triphenylphosphine to rhodium carbonyl is (15-1000): 1.

7. the process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 6, wherein: the concentration of the triphenylphosphine in the reaction solution is 1-15 wt%.

8. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1, wherein: the reaction pressure is 0.5-5.0 MPaG, and the reaction temperature is 80-200 ℃.

9. The process for the hydroformylation of acrolein to form butanedialdehyde as claimed in claim 1 or 8, wherein: the reaction residence time is 5-20 hours.

Technical Field

The invention belongs to the field of organic chemical synthesis, and particularly relates to a process for synthesizing butanedial by acrolein hydroformylation.

Background

Succinaldehyde is an important fine chemical (medicine) intermediate, and the main production method is that furan is used as raw material, 2, 5-dimethoxy dihydrofuran is obtained through bromination and methoxylation, 2, 5-dimethoxy tetrahydrofuran is obtained through catalytic hydrogenation synthesis, further hydrolysis reaction is carried out through heating, reaction solvent is removed through reduced pressure evaporation, and succinaldehyde is obtained after concentration. The method has the defects of high raw material cost, difficult large-scale production and the like.

Disclosure of Invention

The invention aims to provide a process for synthesizing butanedialdehyde by hydroformylation of acrolein, which solves the problems of high cost and difficult production of the existing production process of the butanedialdehyde.

The purpose of the invention is realized by the following technical scheme:

a process for synthesizing 1, 4-butanedial by hydroformylation of acrolein includes such steps as preparing raw materials of acrolein and synthetic gas containing hydrogen and CO, adding butanedial as solvent to the solution of butanedial in which catalyst is dissolved, and hydroformylation of acrolein at a certain temp and pressure to obtain 1, 4-butanedial.

Further, the acrolein is introduced into the reactor in a liquid state.

Further, the synthesis gas enters the reactor in a gaseous state.

Further, the molar ratio of hydrogen to carbon monoxide in the synthesis gas is (0.9-1.4): 1, the molar ratio of acrolein to synthesis gas is 1: (2-3).

Furthermore, rhodium carbonyl is used as a catalyst, triphenylphosphine is used as a catalyst ligand, and the rhodium carbonyl is dissolved in the succinaldehyde solution.

Furthermore, the concentration of rhodium carbonyl in the reaction solution is 0.001-1 wt%, and the mass ratio of triphenylphosphine to rhodium carbonyl is (15-1000): 1.

further, the concentration of triphenylphosphine in the reaction solution is 1-15 wt%.

Further, the reaction pressure is 0.5-5.0 MPaG, and the reaction temperature is 80-200 ℃.

Furthermore, the reaction residence time is 5-20 hours.

The invention has the beneficial effects that: acrolein, hydrogen and carbon monoxide are used as production raw materials, so that the raw materials are easy to obtain and have relatively low cost; the direct hydroformylation of acrolein to form butanedialdehyde is realized by the reaction of the catalyst under certain pressure and temperature, and the process is simple and easy to operate and is suitable for large-scale production.

The main scheme and the further selection schemes can be freely combined to form a plurality of schemes which are all adopted and claimed by the invention; in the invention, the selection (each non-conflict selection) and other selections can be freely combined. The skilled person in the art can understand that there are many combinations, which are all the technical solutions to be protected by the present invention, according to the prior art and the common general knowledge after understanding the scheme of the present invention, and the technical solutions are not exhaustive herein.

Detailed Description

The following non-limiting examples serve to illustrate the invention.

Example 1:

acrolein and synthesis gas (H)₂+ CO) molar ratio of 1:2.3, H in the synthesis gas₂The mol ratio of/CO is 1.15; taking succinaldehyde as a solvent, wherein the concentration of rhodium carbonyl in a reaction solution is 0.5 wt%, the concentration of triphenylphosphine in the reaction solution is 15 wt%, and the mass ratio of triphenylphosphine to rhodium carbonyl is 30: 1; the reaction pressure is 2.7MPaG, and the reaction temperature is 120 ℃; the reaction residence time was 10 hours. The conversion rate of acrolein is 96 percent and the selectivity of the butanedial is 91 percent.

Example 2:

acrolein and synthesis gas (H)₂+ CO) molar ratio of 1:3, H in the synthesis gas₂The mol ratio of/CO is 1.4; taking succinaldehyde as a solvent, wherein the concentration of rhodium carbonyl in a reaction solution is 1 wt%, the concentration of triphenylphosphine in the reaction solution is 15 wt%, the mass ratio of triphenylphosphine to rhodium carbonyl is 15:1, the reaction pressure is 0.5MPaG, and the reaction temperature is 200 ℃; the reaction residence time was 20 hours. The conversion rate of acrolein is 98 percent and the selectivity of the butanedial is 90 percent.

Example 3:

acrolein and synthesis gas (H)₂+ CO) molar ratio of 1:2, H in the synthesis gas₂The mol ratio of/CO is 0.9; taking succinaldehyde as a solvent, the concentration of rhodium carbonyl in a reaction solution is 0.001 percent by weight, and triphenylphosphine in the reaction solutionThe concentration is 1 wt%, and the mass ratio of triphenylphosphine to rhodium carbonyl is 1000: 1; the reaction pressure is 5MPaG, and the reaction temperature is 80 ℃; the reaction residence time was 5 hours. The conversion rate of acrolein is 95% and the selectivity of the butanedial is 95%.

The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.