Patent Grant
12054454
The present invention relates to the field of carbonylation reactions, and specifically to a method for catalyzing olefin carbonylation.
Butanol and octanol are very widely used bulk chemical raw materials. At present, the industrial synthesis of butyl octanol is mainly through the hydroformylation of propylene to produce n-butyraldehyde and isobutyraldehyde, and then they are used as raw materials for subsequent reactions. The hydroformylation reaction of propylene is a key step in the synthesis of butyl octanol.
So far, there have been many patents reported on the hydroformylation of propylene to synthesize n-butyraldehyde and isobutyraldehyde. These patents, as well as current industrial methods, commonly use catalysts based on metal rhodium. For example, patents WO0200583, EP3712126A1, and CN102826967A use triphenylphosphorus-rhodium as catalyst; a patent JP2002047294 uses cyclooctadiene acetate-rhodium as catalyst; a patent CN110156580 uses 6,6′-((3,3′-di-tert-butyl-5,5′-dimethoxy-[1,1′-biphenyl]-2, bis(oxy))diphenyl and [d,f] [1,3,2]dioxaphospholene-rhodium as catalyst; a patent CN103896748A uses acetylmorpholine-rhodium as catalyst; a patent EP3770144A1 uses acetate-rhodium as catalyst; a patent CN11348995A uses tris [2,4-di-tert-butylphenyl] phosphite-rhodium as catalyst; a patent U.S. Pat. No. 9,550,179 uses long-chain carboxylic acid-rhodium as the catalyst; a patent CN102826973A uses acetylacetone carbonyl-rhodium as catalyst; a patent EP2417094B1 uses triphenylphosphine carbonyl rhodium hydride as catalyst; and a patent EP2417093B1 uses rhodium dimer acetate and triphenyl phosphonium tri sulfonate sodium salt as catalyst. Because metal rhodium has high catalytic activity in the hydroformylation reaction of propylene, the reaction conditions of reaction systems using this as a catalyst are generally mild. Typical reaction temperatures are between 90-132° C., and typical reaction pressures are between 1.6-5 MPa (see Table 1).
Although rhodium metal can be recycled many times in the propylene hydroformylation reaction, the slow loss and deactivation are inevitable. Due to the rapid increase in international rhodium metal prices, the cost of catalysts in the corresponding process has also increased rapidly.
In view of this, the present invention is proposed.
A first objective of the present invention is to provide a method for catalyzing olefin carbonylation. The method combines highly active carbene ligands with metal iridium and uses coordination anions to further adjust the catalyst performance, which gives the catalyst a good catalytic activity. It can lower the reaction temperature, reduce energy consumption and reduce costs.
In order to achieve the above objectives of the present invention, the following technical schemes are adopted.
The method provides a method for catalyzing olefin carbonylation, including the following steps:
The above-mentioned catalyst can be preferably used in the process of the olefin carbonylation reaction, and compared with previous rhodium catalysts, its cost is low, its activity is good, and its catalytic effect is good.
Preferably, as a further embodiment, a reaction solvent includes a mixture of one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran.
Preferably, as a further embodiment, a dosage of the catalyst is 0.005-2 wt % of a dosage of the reaction solvent, preferably 0.05-1 wt %.
Preferably, as a further embodiment, the olefin is propylene, and the other raw materials include carbon monoxide and hydrogen, and a total reaction pressure is between 0.5-5.0 MPa, preferably between 1.0-3.0 MPa. A total reaction pressure can be 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa. 1.0 MPa, etc.
Preferably, as a further embodiment, a reaction temperature is between 60˜180° C., preferably between 80° C.˜140° C. The reaction temperature can be 60° C., 70° C., 80° C. or 90° C.
The scheme of the present invention is more suitable for propylene hydroformylation reaction, and can obtain better reaction effect between the reaction temperature of 60˜180° C. and the reaction pressure of 0.5-5.0 MPa. At the same time, the price of iridium metal is only about one-third of that of rhodium metal. Equivalently, the present invention provides an economical and mild new method for synthesizing n-butyraldehyde and isobutyraldehyde through propylene hydroformylation reaction.
Preferably, as a further embodiment, a partial pressure ratio of propylene to carbon monoxide is between 1:1-1:10, preferably between 1:2-1:5.
Preferably, as a further embodiment, a partial pressure ratio of propylene to hydrogen is between 1:1-1:10, preferably between 1:2-1:5.
By controlling each operating parameter in the above reaction process within an appropriate proportion range can significantly improve the reaction effect.
Compared with the prior art, the beneficial effects of the present invention are:
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are for the purpose of illustrating preferred embodiments only and are not to be construed as limiting the present invention. Also, throughout the drawings, the same reference characters are used to designate the same components. In the drawings:
The schemes of the present invention will be described in detail below with reference to embodiments, however, those skilled in the art will understand that the following embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention.
If the specific conditions are not specified in the embodiments, the conditions should be carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be purchased commercially.
In a 50 ml high-pressure reaction kettle, add 10 ml of toluene solution containing 0.25 wt % CAAC (C 2 C 2)-Ir—Cl. After hydrogen replacement three times, 3 bar propylene, 8 bar carbon monoxide, and 8 bar hydrogen are introduced in sequence, and the temperature is raised to 90° C. with stirring. The reaction is stirred at this temperature for 8 hours, and the reaction solution is cooled to 0° C. After slowly releasing the pressure, samples are taken for gas chromatography analysis. The results show that the propylene conversion rate is 92.1%, and the selectivity of n-butyraldehyde and isobutyraldehyde is 99.9% (n-butyraldehyde:isobutyraldehyde=3.3:1). The confirmed nuclear magnetic resonance hydrogen spectrum diagram and the nuclear magnetic resonance carbon spectrum diagram of the catalyst used in the specific embodiment are shown in
The propylene hydroformylation reaction method of Embodiment 1 is adopted while changing the coordination anion of CAAC(C2C2)-Ir—X ions, and the results are shown in Table 2.
The propylene hydroformylation reaction method of Embodiment 1 is adopted while changing different temperatures to carry out the reaction, and the results are shown in Table 3.
The propylene hydroformylation reaction method of Embodiment 1 is adopted while changing the pressure of gas, and the results are shown in Table 4.
As can be seen from the above tables that: by using iridium catalyst for catalytic reaction, even under low-temperature and low-pressure conditions, it still has good reaction selectivity and good reaction conversion rate. Therefore, the present invention adopts a new catalyst to carry out the catalytic reaction and explores the reaction conditions, thereby realizing the reaction under the conditions of low energy consumption and high reaction efficiency.
Finally, it should be noted that the above embodiments are only used to illustrate the technical schemes of the present invention, rather than to limit the present invention. Although the present invention has been described in detail with reference to the above-mentioned embodiments, those of ordinary skill in the art should understand that they can still modify the technical schemes recorded in the above-mentioned embodiments or make equivalent substitutions for some or all of the technical features. However, these modifications or substitutions do not cause the essence of the corresponding technical scheme to depart from the scope of the technical scheme of each embodiment of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111256876.9 | Oct 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/130913 | 11/16/2021 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2023/070760 | 5/4/2023 | WO | A |
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|---|---|---|---|
| 5227522 | Denis | Jul 1993 | A |
| 5420346 | Denis | May 1995 | A |
| 5847204 | Nobel | Dec 1998 | A |
| 20160068458 | Mandimutsira et al. | Mar 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 104001548 | Aug 2014 | CN |
| 111068785 | Apr 2020 | CN |
| 112457178 | Mar 2021 | CN |
| 1367623 | Sep 1974 | GB |
| Entry |
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| International Search Report—ISA/CN; PCT/CN2021/130913; Mailed Jul. 27, 2022; 3 pgs. |
