阅读说明：本技术 一种烯烃加氢甲酰化方法 (Olefin hydroformylation method ) 是由 胡嵩霜 吴红飞 郑明芳 王霄青 潘峰 于 2020-05-21 设计创作，主要内容包括：本发明公开了一种烯烃加氢甲酰化方法,包括将CO、H-(2)和溶剂进行第一混合,得到第一混合物；将第一混合物与加氢甲酰化催化剂进行第二混合,得到第二混合物；将所述第二混合物与CO、H-(2)以及烯烃进行第三混合,以生成醛产物。该方法通过CO、H-(2)和溶剂的预混及催化剂的预活化,提高了烯烃加氢甲酰化反应中催化剂的活性及醛选择性,降低了生产成本。(The invention discloses an olefin hydroformylation method, which comprises the steps of adding CO and H 2 Carrying out first mixing with a solvent to obtain a first mixture; carrying out second mixing on the first mixture and a hydroformylation catalyst to obtain a second mixture; mixing the second mixture with CO and H 2 And third mixing the olefins to produce the aldehyde product. The method passes CO and H 2 And the premixing of the solvent and the pre-activation of the catalyst improve the activity and the aldehyde selectivity of the catalyst in the olefin hydroformylation reaction and reduce the production cost.)

1. A process for the hydroformylation of olefins comprising the steps of:

1) mixing CO and H₂Carrying out first mixing with a solvent to obtain a first mixture;

2) carrying out second mixing on the first mixture and a hydroformylation catalyst to obtain a second mixture;

3) mixing the second mixture with CO and H₂And third mixing the olefins to produce the aldehyde product.

2. The method of claim 1, wherein the first mixing and the second mixing are performed in different vessels and/or the second mixing and the third mixing are performed in different vessels.

3. The method according to claim 1 or 2, wherein the first mixing is performed in a gas-liquid mixer, the second mixing is performed in a line, and the third mixing is performed in a reactor, wherein the line is arranged between the gas-liquid mixer and the reactor.

4. A method according to any one of claims 1-3, characterized in that in step 1), the temperature of the first mixing is 50-130 ℃, preferably 60-85 ℃; and/or the first mixing pressure is less than or equal to 4MPa, preferably between 0.5 and 3 MPa; and/or the time of the first mixing is less than or equal to 30min, preferably 15-25 min.

5. The process according to any one of claims 1 to 4, characterized in that in step 2), the time of the second mixing is less than or equal to 20min, preferably 1 to 10 min; and/or the temperature of the second mixing is 50 to 130 ℃, preferably 60 to 80 ℃, more preferably the same as the first mixing temperature in step 1).

6. The method according to any one of claims 1 to 5, wherein the temperature of the third mixing in step 3) is 60 to 140 ℃, preferably 70 to 100 ℃; and/or the pressure of the third mixing is 0-4MPa, preferably 1-3 MPa; and/or the time of the third mixing is 30-120min, preferably 60-105 min.

7. The process according to any one of claims 1 to 6, wherein the solvent is an organic solvent, preferably selected from the group consisting of aldehyde solvents, ketone solvents, aromatic hydrocarbon solvents and paraffinic hydrocarbon solvents, more preferably selected from at least one of the following compounds: butyraldehyde, valeraldehyde, caproaldehyde, heptanal, caprylic aldehyde, nonanal, methyl isobutyl ketone, acetophenone, toluene, xylene, chlorobenzene, and heptane.

8. A process according to any one of claims 1 to 7, characterized in that the olefin is a C6+ olefin, preferably octene.

9. The process of any one of claims 1 to 8, wherein the hydroformylation catalyst is an organophosphine modified rhodium catalyst system, preferably the catalyst comprises a rhodium catalyst and an organophosphine compound, preferably the rhodium catalyst is of formula (I):

Rh(L₁)x(L₂)y(L₃)z (I)

wherein L is₁、L₂And L₃Each independently is hydrogen, carbonyl, chlorine, triphenylphosphine or acetylacetone;

x, y and z are each independently an integer of 0 to 5, and at least one of x, y and z is not 0.

10. The process according to claim 9, wherein the rhodium catalyst is added in an amount of 50 to 400ppm in terms of metal rhodium; and/or the molar ratio of organophosphinic compound to metal rhodium in the rhodium catalyst is (0.5-200): 1; and/or the molar ratio of olefin to metal rhodium in the rhodium catalyst is 100000:1 to 500:1, preferably 10000:1 to 1000: 1; and/or said CO and H₂Is 1: 1.

Technical Field

The present invention relates to a process for the hydroformylation of olefins.

Background

In recent years, with the rapid development of plastic processing, automobile industry, cable industry and building industry worldwide, there is an increasing global demand for plasticizers, and further there is an increasing demand for plasticizer alcohols. Nonanol, which is the plasticizer alcohol in which the demand is the fastest growing at present, is mainly prepared by hydrogenation after hydroformylation of octenes.

Organometallic catalysts used in commercial hydroformylation processes typically have cobalt (Co) and rhodium (Rh) as the metal active sites. The industrial production of higher alcohols such as isononyl alcohol is mainly based on Co catalysts, but the comprehensive economic and technical indexes of the cobalt catalytic process are far inferior to those of the Rh catalytic process due to the factors of harsh reaction conditions, poor selectivity, more side reactions, high energy consumption, complex cobalt recovery process and the like, so the research based on the Rh catalytic process is very important.

The disadvantage of using rhodium catalysts for hydroformylation of high carbon chain olefins is that on the one hand Rh is a very expensive noble metal and on the other hand the combination of Rh catalysts with ligands is very sensitive to state change reactions and is subject to rapid deactivation. It is therefore essential to increase the activity and aldehyde selectivity of the Rh/ligand system in the reaction.

The activity of the Rh-based catalyst in the hydroformylation process and the N/I selectivity (ratio of normal aldehyde to iso-aldehyde) produced depend on the combination of the catalyst precursor and the ligand and the process conditions.

US patent 8710276 discloses cyclohexanediphenylphosphine ligands represented by the ligand CHDP, which, although increasing the catalyst stability, have a significantly reduced N/I selectivity; US8507731 discloses in examples 8 to 14 rh (co)2(acac) and calixarene bidentate phosphine ligand combination catalysts which show high N/I selectivity but lower reactivity and, in addition, are complex, complicated in synthesis steps and costly to use. Chinese patent CN103814006 discloses a hydroformylation method with improved catalyst stability in the reaction, which adds a special α, β -unsaturated carbonyl compound to inhibit the decomposition of ligand and catalyst in the hydroformylation reaction, and this method increases the stability of catalyst to some extent, but also increases the reaction cost.

The above hydroformylation methods are all focused on the research of catalysts and additives, and in view of the difficulty in developing new catalyst systems and the problem of reaction cost caused by the addition of additives, it is a more appropriate method to optimize process conditions to improve the catalyst reactivity and selectivity.

Disclosure of Invention

In view of the disadvantages of the prior art, it is an object of the present invention to provide a hydroformylation process by means of CO, H₂The catalyst activity and the aldehyde selectivity can be improved and the production cost can be reduced by premixing the catalyst with a solvent and pre-activating the catalyst.

The invention provides an olefin hydroformylation method, which comprises the following steps:

1) mixing CO and H₂Carrying out first mixing with a solvent to obtain a first mixture;

2) carrying out second mixing on the first mixture and a hydroformylation catalyst to obtain a second mixture;

3) mixing the second mixture with CO and H₂And third mixing the olefins to produce the aldehyde product.

According to some embodiments of the invention, the first mixing and the second mixing are performed in different vessels.

According to some embodiments of the invention, the second mixing and the third mixing are performed in different vessels.

According to some embodiments of the invention, the first mixing is performed in a gas-liquid mixer, the second mixing is performed in a line, and the third mixing is performed in a reactor, wherein the line is arranged between the gas-liquid mixer and the reactor. Continuous feeding and production can be realized by connecting a gas-liquid mixer with the reactor.

According to some preferred embodiments of the invention, the line is connected to the middle or upper part of the reactor. According to some embodiments, the pipeline is connected to the reactor at a level higher than the level of CO, H on the reactor₂And an inlet for olefins.

According to some preferred embodiments of the present invention, the gas-liquid mixer is a stainless steel pressure-resistant gas-liquid mixing device, and may be one or a combination of mechanical stirring and gas flow stirring.

According to some preferred embodiments of the invention, the temperature of the first mixing is 50 to 130 ℃, preferably 60 to 85 ℃.

According to some preferred embodiments of the invention, the pressure of the first mixing is less than or equal to 4MPa, preferably 0.5-3 MPa. According to some embodiments, the pressure of the first mixing is 0.2MPa, 0.3MPa, 1MPa, 1.5MPa, or 2MPa, or the like.

According to some preferred embodiments of the invention, the time of the first mixing is less than or equal to 30min, preferably 15-25 min. According to some embodiments, the time of the first mixing is 10min, 15min, 20min, 25min, or 30 min.

According to some preferred embodiments of the invention, the temperature of the second mixing is the same as the temperature of the first mixing. According to some embodiments, the temperature control of the second mixing is achieved by adding a thermal insulation or temperature control device to its container. Preferably, the line connecting the mixer to the reactor is provided with a thermal insulation or temperature control device.

According to some preferred embodiments of the invention, the time of the second mixing is less than or equal to 20min, preferably from 1 to 10 min. According to some embodiments, the time of the second mixing is 2 min. According to some embodiments, the second mixing is 4min, 5min, 6min, 7min, 8min, 9min, or 10 min.

According to some preferred embodiments of the invention, the third mixing temperature is 60 to 140 ℃, preferably 70 to 100 ℃. According to some embodiments, the temperature of the third mixing is 75 ℃, 80 ℃ or 85 ℃.

According to some preferred embodiments of the invention, the third mixing pressure is 0-4MPa, preferably 1-3 MPa. According to some embodiments, the third mixing pressure is 1.5 MPa.

According to some preferred embodiments of the invention, the third mixing time is 30-120min, preferably 60-105 min. According to some embodiments, the third mixing time is 60 min.

According to some preferred embodiments of the present invention, the solvent used in the reaction is an organic solvent, preferably selected from the group consisting of aldehyde solvents, ketone solvents, aromatic hydrocarbon solvents and paraffinic hydrocarbon solvents, more preferably selected from at least one of the following compounds: butyraldehyde, valeraldehyde, caproaldehyde, heptanal, caprylic aldehyde, nonanal, methyl isobutyl ketone, acetophenone, toluene, xylene, chlorobenzene, and heptane. According to some embodiments, the solvent is toluene or nonanal.

According to some preferred embodiments of the invention, the alkene is a C6+ alkene, preferably octene.

According to some preferred embodiments of the present invention, the catalyst used in the hydroformylation reaction is an organophosphine modified rhodium catalyst system.

Preferably, the catalyst comprises a rhodium catalyst and an organophosphinic compound. Preferably, the rhodium catalyst is of the formula (I):

Rh(L₁)x(L₂)y(L₃)z (I)

wherein L is₁、L₂And L₃Each independently is hydrogen, carbonyl, chlorine, triphenylphosphine or acetylacetone;

x, y and z are each independently an integer of 0 to 5, and at least one of x, y and z is not 0.

According to a preferred embodiment of the invention, the rhodium catalyst is added in an amount of 50 to 400ppm, calculated as metallic rhodium.

According to a preferred embodiment of the present invention, the molar ratio of the organophosphinic compound to the metal rhodium in the rhodium catalyst is (0.5-200): 1.

According to a preferred embodiment of the invention, the molar ratio of the olefin to the metal rhodium in the rhodium catalyst is from 100000:1 to 500:1, preferably from 10000:1 to 1000: 1.

According to a preferred embodiment of the invention, the first, second and third mixed gases are CO and H₂Is 1: 1.

According to some embodiments, the hydroformylation process of the present invention comprises:

a) a part of CO and H₂Premixing the solvent and the solvent in a gas-liquid mixer;

b) conveying the gas-liquid mixture in the gas-liquid mixer to a reactor through a pipeline, wherein a catalyst solution is introduced into a liquid outlet of the gas-liquid mixer, so that the catalyst solution and the gas-liquid mixture are uniformly mixed and enter the reactor together;

c) introducing another part of CO and H into the reactor₂And adding olefin to react with CO and H₂The hydroformylation reaction is carried out under the action of a catalyst, and the aldehyde obtained by the reaction is dissolved in a solvent and flows out through an outlet of the reactor.

The invention improves the reaction unit in the hydroformylation process, and the process adopts a mode that a gas-liquid mixing container is connected with a reactor, thereby realizing continuous feeding and production. The gas-liquid mixing container can realize CO and H₂And solvent is premixed, so that the part of the solvent contains certain concentration of CO and H when the part of the solvent is in the gas-liquid mixing container₂On the one hand, the catalyst is convenient to pre-activate in a pipeline, the activity of the catalyst and the selectivity of aldehyde are improved, and on the other hand, the catalyst can play a role in time when meeting olefins in the process of hydroformylation reaction, so that the hydroformylation reaction is rapidly carried out, and the production cost is reduced.

Drawings

FIG. 1 is a schematic process diagram of the hydroformylation reaction of the present invention.

Description of the labeling: 1-solvent inlet, 2-first CO, H₂A feed inlet, a 3-catalyst feed inlet, a 4-catalyst, CO, H₂A solvent mixed liquid inlet, a 5-olefin inlet, and 6-second CO and H₂A feeding port, 7-a product discharging port, 8-a gas-liquid mixing device, 9-a heat preservation or temperature control system and 10-a reactor

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to the scope disclosed in the following examples.

Example 1

As shown in figure 1, the technological process for preparing nonanal by hydroformylation of 1-octene is as follows: adopts acetylacetonatodicarbonyl rhodium as a main catalyst, and 2, 2-bis [ (diphenylphosphino) methyl]1, 1-biphenyl (BISBI) as ligand, the molar ratio of procatalyst (rhodium) to ligand being 1:5, 1-octene: the molar ratio of Rh was 1000:1, and the concentration of Rh was 1.6 mmol/L. Using N as a closed reaction system₂After purging, with syngas (CO: H)₂1:1) replacement several times and opening the temperature control system of the system to maintain the temperature of the whole system at 80 ℃, synthesis gas (CO: H)₂1:1) were introduced into a gas-liquid mixer and a reactor, respectively, while maintaining the pressure in the gas-liquid mixer at 1.0MPa and the pressure in the reactor at 1.5 MPa. Toluene is added to a gas-liquid mixer to mix toluene with syngas (CO: H)₂1:1) and the residence time of toluene in the gas-liquid mixer was 20 min. Will be mixed with synthesis gas (CO: H)₂1:1) of toluene was discharged from the gas-liquid mixer, and the catalyst was introduced by opening the catalyst inlet 3 to mix the catalyst with synthesis gas (CO: H)₂1:1) of toluene was thoroughly mixed to start preactivation, and the preactivation time was 5 min. 1-octene is introduced into the reactor through olefin inlet 5 and is mixed with catalyst, CO and H₂And the solvent mixed solution is contacted to initiate hydroformylation reaction for 60min, the reacted materials are discharged from a product discharge port 7, sampling analysis is carried out on the materials, and the measured reaction results are shown in table 1.

Example 2

The experimental method was the same as in example 1, except that the pressure in the gas-liquid mixer was changed to 0.5MPa, and the other experimental conditions were unchanged, and the test results are shown in table 1.

Example 3

The experimental method was the same as in example 1, except that the pressure in the gas-liquid mixer was changed to 0.25MPa, and the other experimental conditions were unchanged, and the test results are shown in Table 1.

Example 4

The experimental method was the same as in example 1, the temperature of the gas-liquid mixer and the line connecting the gas-liquid mixer and the reactor was changed to 50 ℃, the temperature of the reactor was still 80 ℃, the other experimental conditions were unchanged, and the test results are shown in table 1.

Example 5

The experimental method was the same as in example 1, the temperature of the gas-liquid mixer and the line connecting the gas-liquid mixer and the reactor was changed to 90 ℃, the temperature of the reactor was still 80 ℃, the other experimental conditions were unchanged, and the test results are shown in table 1.

Example 6

The experimental method is the same as that of example 1, the retention time of the solvent in the gas-liquid mixer is changed to 10min, the rest experimental conditions are not changed, and the test results are shown in table 1.

Example 7

The experimental method is the same as that of example 1, the retention time of the solvent in the gas-liquid mixer is changed to 30min, the rest experimental conditions are not changed, and the test results are shown in table 1.

Example 8

The experimental method is the same as that of example 1, the retention time of the gas-liquid mixed liquid and the catalyst in the pipeline is changed to 2min, the rest experimental conditions are unchanged, and the test results are shown in table 1.

Example 9

The experimental method is the same as that of example 1, the retention time of the gas-liquid mixed liquid and the catalyst in the pipeline is changed to 10min, the rest experimental conditions are unchanged, and the test results are shown in table 1.

Comparative example 1

The experimental procedure is as in example 1, wherein CO and H are not introduced into the gas-liquid mixer₂Only introducing CO and H into the reactor₂And the rest experimental conditions are unchanged, and the experimental results are as follows: 1-octene conversion: 76.1 percent; aldehyde selectivity: 87.7 percent.

Comparative example 2

The experimental method was the same as in example 1, wherein the gas-liquid mixer and the line connecting the gas-liquid mixer and the reactor were operated at room temperature, and the other experimental conditions were unchanged, and the test results were as follows: 1-octene conversion: 82.8 percent; aldehyde selectivity: 89.2 percent.

Comparative example 3

The experimental procedure is as in example 1, wherein CO and H are not introduced into the gas-liquid mixer₂Only introducing CO and H into the reactor₂And simultaneously, the gas-liquid mixer and the pipeline connecting the gas-liquid mixer and the reactor are all kept to be operated at room temperature, other experimental conditions are unchanged, and the experimental results are as follows: 1-octene conversion: 78.7 percent; aldehyde selectivity: 89.7 percent.

TABLE 1

As is clear from the results of the experiments, in the reaction for producing an aldehyde by hydroformylation of an olefin, CO and H were introduced₂And the catalyst is premixed with a solvent, so that the catalyst is conveniently preactivated in a pipeline, and the activity of the catalyst and the selectivity of aldehyde can be improved.

What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.