Method for catalyzing olefin carbonylation

Abstract

The present invention discloses a method for catalyzing olefin carbonylation, including the following steps: using cyclic alkylcarbene iridium as a catalyst and an olefin as a raw material to carry out carbonylation reaction to generate aldehydes, wherein a structural formula of the cyclic alkylcarbene iridium is as follows: ##STR00001## wherein Dipp is 2,6-diisopropylbenzene; R1 and R2 are methyl or ethyl; X is Cl, Br, CH3CO2, NO3, BF4, PF6 or SbF6; wherein the olefin comprises one or more of ethylene, propylene, butylene and higher carbon olefins. According to the method for catalyzing olefin carbonylation of the present invention, by adopting an iridium catalyst, the catalytic activity is good, reaction energy consumption is reduced, and reaction temperature is fully lowered.

Claims

1. A method for catalyzing olefin carbonylation, comprising the following steps: using cyclic alkylcarbene iridium as a catalyst and olefin as a raw material to carry out carbonylation reaction to generate aldehydes, wherein a structural formula of the cyclic alkylcarbene iridium is as follows: ##STR00003## wherein Dipp is 2,6-diisopropylbenzene; R.sub.1 and R.sub.2 are methyl or ethyl; X is Cl, Br, CH.sub.3CO.sub.2, NO.sub.3, BF.sub.4, PF.sub.6 or SbF.sub.6; wherein the olefin comprises one or more of ethylene, propylene, butylene and higher carbon olefins.

2. The method for catalyzing olefin carbonylation according to claim 1, wherein a reaction solvent includes a mixture of one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran.

3. The method for catalyzing olefin carbonylation according to claim 2, wherein a dosage of the catalyst is 0.005-2 wt % of a dosage of the reaction solvent.

4. The method for catalyzing olefin carbonylation according to claim 2, wherein a dosage of the catalyst is 0.05-1 wt % of a dosage of the reaction solvent.

5. The method for catalyzing olefin carbonylation according to claim 1, wherein the olefin is propylene, and the other raw materials comprise carbon monoxide and hydrogen, and a total reaction pressure is between 0.5-5.0 MPa.

6. The method for catalyzing olefin carbonylation according to claim 1, wherein a total reaction pressure is between 1.0-3.0 MPa.

7. The method for catalyzing olefin carbonylation according to claim 5, wherein a partial pressure ratio of propylene to carbon monoxide is between 1:1-1:10.

8. The method for catalyzing olefin carbonylation according to claim 5, wherein a partial pressure ratio of propylene to carbon monoxide is between 1:2-1:5.

9. The method for catalyzing olefin carbonylation according to claim 5, wherein a partial pressure ratio of propylene to hydrogen is between 1:1-1:10.

10. The method for catalyzing olefin carbonylation according to claim 5, wherein a partial pressure ratio of propylene to hydrogen is between 1:2-1:5.

11. The method for catalyzing olefin carbonylation according to claim 5, wherein a reaction temperature is between 60-180? C.

12. The method for catalyzing olefin carbonylation according to claim 5, wherein a reaction temperature is between 80? C.?140? C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) 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:

(2) FIG. 1 is a nuclear magnetic resonance carbon spectrum diagram of the catalyst CAAC (C 2C 2)-IrCl provided in Embodiment 1 of the present invention.

(3) FIG. 2 is a nuclear magnetic resonance hydrogen spectrum diagram of the catalyst CAAC (C 2C 2)-IrCl provided in Embodiment 1 of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(4) 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.

(5) 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.

Embodiment 1

(6) In a 50 ml high-pressure reaction kettle, add 10 ml of toluene solution containing 0.25 wt % CAAC (C 2 C 2)-IrCl. 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 FIG. 1-FIG. 2.

Embodiments 2-7

(7) The propylene hydroformylation reaction method of Embodiment 1 is adopted while changing the coordination anion of CAAC(C2C2)-IrX ions, and the results are shown in Table 2.

(8) TABLE-US-00002 TABLE 2 Effects of coordination anions of CAAC(C2C2)-Ir-X on propylene hydroformylation reaction. Selectivity of n- butyraldehyde Propylene and conversion isobutyraldehyde n-butyraldehyde: Embodiment X rate (%) (%) isobutyraldehyde 2 Br 92.6 99.9 3.5:1 3 CH.sub.3CO.sub.2 90.7 99.9 5.3:1 4 NO.sub.3 86.5 99.9 4.1:1 5 BF.sub.4 93.9 99.9 5.6:1 6 PF.sub.6 92.3 99.9 6.5:1 7 SbF.sub.6 94.6 99.9 7.2:1

Embodiments 8-12

(9) 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.

(10) TABLE-US-00003 TABLE 3 Effects of temperature on propylene hydroformylation reaction. Selectivity of n- butyraldehyde Temper- Propylene and ature conversion isobutyraldehyde n-butyraldehyde: Embodiment (? C.) rate (%) (%) isobutyraldehyde 8 60 92.7 99.9 3.2:1 9 80 93.1 99.9 3.2:1 10 100 93.2 99.9 3.3:1 11 120 93.6 99.9 3.3:1 12 140 94.1 99.9 3.4:1

Embodiments 13-16

(11) The propylene hydroformylation reaction method of Embodiment 1 is adopted while changing the pressure of gas, and the results are shown in Table 4.

(12) TABLE-US-00004 TABLE 4 Effects of pressure on propylene hydroformylation reaction. Pro- Selectivity pylene of con- n-butyraldehyde n-butyral- Em- version and dehyde: bodi- Acrylic CO H.sub.2 rate isobutyraldehyde isobutyral- ment (bar) (bar) (bar) (%) (%) dehyde 13 3 4 4 92.2 99.9 3.5:1 14 3 6 6 92.5 99.9 3.3:1 15 3 10 10 93.5 99.9 3.2:1 16 3 12 12 95.1 99.9 3.2:1

(13) 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.

(14) 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.