阅读说明：本技术 一种催化剂进行烯烃羰基化的方法 (Method for olefin carbonylation by catalyst ) 是由 胡兴邦 张志炳 姚晨飞 周政 李磊 于 2021-10-27 设计创作，主要内容包括：本发明提供了一种催化剂进行烯烃羰基化的方法,包括如下步骤：以环状烷基卡宾铱为催化剂,烯烃为原料羰基化反应生成醛,所述环状基卡宾铱的结构式为：其中,Dipp为2,6-二异丙基苯,R-(1)、R-(2)为甲基或乙基,X为Cl、Br、CH-(3)CO-(2)、NO-(3)、BF-(4)、PF-(6)或SbF-(6)；所述烯烃包括乙烯、丙烯、丁烯以及高碳烯烃中的其中一种或几种。本发明的烯烃羰基化的方法通过采用铱催化剂,催化活性好,降低反应能耗,充分降低了反应温度。(The invention provides a method for olefin carbonylation by using a catalyst, which comprises the following steps: taking cyclic alkyl carbene iridium as a catalyst, taking olefin as a raw material, and carrying out carbonylation reaction to generate aldehyde, wherein the structural formula of the cyclic alkyl carbene iridium is as follows: wherein Dipp is 2, 6-diisopropylbenzene, R 1 、R 2 Is methyl or ethyl, X is Cl, Br, CH 3 CO 2 、NO 3 、BF 4 、PF 6 Or SbF 6 (ii) a The olefin comprises one or more of ethylene, propylene, butylene and high-carbon olefin. The method for olefin carbonylation has good catalytic activity, reduces reaction energy consumption and fully reduces reaction temperature by adopting the iridium catalystAnd (4) degree.)

1. A process for the carbonylation of olefins over a catalyst, comprising the steps of: taking cyclic alkyl carbene iridium as a catalyst, taking olefin as a raw material, and carrying out carbonylation reaction to generate aldehyde, wherein the structural formula of the cyclic alkyl carbene iridium is as follows:

wherein Dipp is 2, 6-diisopropylbenzene, R₁、R₂Is methyl or ethyl, X is Cl, Br, CH₃CO₂、NO₃、BF₄、PF₆Or SbF₆；

The olefin comprises one or more of ethylene, propylene, butylene and high-carbon olefin.

2. The method of claim 1, wherein the reaction solvent comprises one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene, and tetrahydrofuran.

3. The process according to claim 2, characterized in that the catalyst is used in an amount of 0.005-2 wt.%, preferably 0.05-1 wt.%, based on the amount of reaction solvent.

4. The process according to claim 1, wherein the olefin propylene, the other raw material comprises carbon monoxide and hydrogen, and the total reaction pressure is between 0.5 and 5.0MPa, preferably between 1.0 and 3.0 MPa.

5. Process according to claim 4, characterized in that the partial pressure ratio of propylene to carbon monoxide is between 1:1 and 1:10, preferably between 1:2 and 1: 5.

6. Process according to claim 4, characterized in that the partial pressure ratio of propylene to hydrogen is between 1:1 and 1:10, preferably between 1:2 and 1: 5.

7. The process according to claim 4, wherein the reaction temperature is between 60 and 180 ℃, preferably between 80 and 140 ℃.

Technical Field

The invention relates to the field of carbonylation reactions, in particular to a method for carrying out olefin carbonylation by using a catalyst.

Background

Butanol and octanol are large chemical raw materials with wide application. Currently, butanol and octanol are industrially synthesized by preparing n-butyraldehyde and isobutyraldehyde mainly through propylene hydroformylation reaction, and then performing subsequent reaction by using the n-butyraldehyde and isobutyraldehyde as raw materials. The hydroformylation of propylene is a key step in the synthesis of butanol and octanol.

To date, there have been many patents reported on the hydroformylation of propylene to synthesize n-butyraldehyde and isobutyraldehyde, and these patents, as well as the current industrial processes, generally employ a catalyst based on metallic rhodium. For example, WO0200583, EP3712126a1, CN102826967A use triphenylphosphine-rhodium as catalyst; JP2002047294 uses cyclooctadiene acetic acid-rhodium as a catalyst; CN110156580 uses 6,6'- ((3,3' -di-tert-butyl-5, 5 '-dimethoxy- [1,1' -biphenyl ] -2, bis (oxy)) dibenzo [ d, f ] [1,3,2] dioxaphosphene-rhodium as a catalyst, CN103896748A uses acetylmorpholine-rhodium as a catalyst, EP3770144A1 uses acetic acid-rhodium as a catalyst, CN111348995A uses tris [2, 4-di-tert-butylphenyl ] phosphite-rhodium as a catalyst, US9550179 uses long-chain carboxylic acid-rhodium as a catalyst, CN102826973A uses acetylacetonatocarbonyl-rhodium as a catalyst, EP2417094B1 uses triphenylphosphine carbonyl rhodium hydride as a catalyst, EP2417093B1 uses dimeric acetic acid rhodium + triphenylphosphine sodium salt as a sodium salt, since metal rhodium has higher propylene hydroformylation reaction catalytic activity, the reaction conditions of the reaction system using the catalyst are generally mild, typical reaction temperatures are between 90 and 132 ℃ and typical reaction pressures are between 1.6 and 5MPa (see Table 1).

Although rhodium metal can be recycled in propylene hydroformylation for many times, slow loss and deactivation in the reaction process cannot be avoided. The catalyst cost of the corresponding process is also rapidly increased due to the rapid increase of the price of the international rhodium metal.

TABLE 1 reaction pressure of the prior art

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention is to provide a method for olefin carbonylation by using a catalyst, which further regulates the performance of the catalyst by matching high-activity carbene ligands with metal iridium and adopting coordination anions, and endows the catalyst with good catalytic activity. And the reaction temperature can be reduced, the energy consumption is reduced, and the cost is reduced.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

the invention provides a method for olefin carbonylation by using a catalyst, which comprises the following steps: taking cyclic alkyl carbene iridium as a catalyst, taking olefin as a raw material, and carrying out carbonylation reaction to generate aldehyde, wherein the structural formula of the cyclic alkyl carbene iridium is as follows:

wherein Dipp is 2, 6-diisopropylbenzene, R₁、R₂Is methyl or ethyl, X is Cl, Br, CH₃CO₂、NO₃、BF₄、PF₆Or SbF₆；

The olefin comprises one or more of ethylene, propylene, butylene and high-carbon olefin.

The catalyst can be better applied to the olefin carbonylation reaction process, and compared with the prior rhodium catalyst, the catalyst has the advantages of low cost, good activity and good catalytic effect.

Preferably, as a further practicable scheme, the reaction solvent includes one or a mixture of several of n-butyraldehyde, isobutyraldehyde, toluene, benzene, and tetrahydrofuran.

Preferably, as a further implementable variant, the amount of catalyst used is from 0.005 to 2% by weight, preferably from 0.05 to 1% by weight, based on the amount of reaction solvent.

Preferably, as a further practicable scheme, the olefin propylene and other raw materials comprise carbon monoxide and hydrogen, and the total reaction pressure is between 0.5 and 5.0MPa, preferably between 1.0 and 3.0 MPa. The total reaction pressure may be 0.6MPa, 0.7MPa, 0.9MPa, 1.0MPa, etc.

Preferably, as a further implementable scheme, the reaction temperature is between 60 and 180 ℃, preferably between 80 and 140 ℃. The reaction temperature can be 60 deg.C, 70 deg.C, 80 deg.C, and 90 deg.C.

The scheme of the invention is more suitable for propylene hydroformylation reaction, and can obtain better reaction effect at 60-180 ℃ and 0.5-5.0 MPa. Meanwhile, the price of the iridium metal is only about one third of that of rhodium metal. The invention provides an economical and mild new method for synthesizing n-butyraldehyde and isobutyraldehyde by propylene hydroformylation.

Preferably, as a further implementable variant, the partial pressure ratio of propene to carbon monoxide is between 1:1 and 1:10, preferably between 1:2 and 1: 5.

Preferably, as a further implementable variant, the partial pressure ratio of propylene to hydrogen is between 1:1 and 1:10, preferably between 1:2 and 1: 5.

All the operating parameters in the reaction process are controlled within a proper proportion range, so that the reaction effect can be obviously improved.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the carbonylation reaction method, the carbene ligand with too high activity is matched with the metal iridium, and the coordination anion is adopted to further adjust the performance of the catalyst, so that the catalyst is endowed with good catalytic activity;

(2) the invention has low catalytic reaction temperature, low energy consumption and low cost of the adopted catalyst.

Drawings

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 only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:

FIG. 1 shows a CAAC (C) catalyst provided in example 1 of the present invention₂C₂) -Ir-Cl nuclear magnetic resonance carbon spectrum;

FIG. 2 shows an embodiment of the present invention1 catalyst CAAC (C)₂C₂) -Ir-Cl NMR hydrogen spectrum.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Example 1

In a 50ml autoclave, a solution containing 0.25 wt% CAAC (C)₂C₂) Introducing 10ml of-Ir-Cl toluene solution, introducing hydrogen for three times for replacement, sequentially introducing 3bar of propylene, 8bar of carbon monoxide and 8bar of hydrogen, and heating to 90 ℃ under stirring. The reaction was stirred at this temperature for 8h and the reaction was cooled to 0 ℃. After the pressure was slowly released, a sample was taken and subjected to gas chromatography, and the results showed that the propylene conversion was 92.1% and the n-and i-butyraldehyde selectivities were 99.9% (3.3: 1: n-butyraldehyde: i-butyraldehyde), and the confirmation spectrum nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum of the catalyst used in this example are shown in fig. 1-2.

Examples 2 to 7

Using the hydroformylation of propylene process of example 1, the CAAC (C) was varied₂C₂) -a coordinating anion of Ir-X, the results are shown in table 2:

TABLE 2 CAAC (C)₂C₂) Effect of coordinated anions of-Ir-X on hydroformylation of propene

Examples 8 to 12

The hydroformylation process of propylene of example 1 was carried out while varying the temperature, and the results are shown in Table 3:

TABLE 3 Effect of temperature on hydroformylation of propene

Examples 13 to 16

The hydroformylation process of propylene of example 1 was carried out while changing the gas pressure, and the results are shown in Table 4:

TABLE 4 influence of pressure on the hydroformylation of propene

As can be seen from the above table, the iridium catalyst has good reaction selectivity and reaction conversion rate even under low temperature and low pressure conditions during the catalytic reaction process, so the invention adopts a novel catalyst to perform catalytic reaction, and after searching the reaction conditions, realizes the reaction under low energy consumption, and has high reaction efficiency.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.