阅读说明：本技术 加氢甲酰化的方法 (Hydroformylation process ) 是由 胡嵩霜 吴红飞 郑明芳 潘峰 王霄青 于 2020-05-21 设计创作，主要内容包括：本发明提供了一种加氢甲酰化的方法,包括：步骤A：将一氧化碳和氢气与溶剂进行混合,得到预混物。本发明的加氢甲酰化方法还包括：步骤B：将预混物与催化剂体系混合,进行预反应,得到预反应物；步骤C：将预反应物与高碳烯烃混合,进行反应。本发明的方法通过气相与液相预混,并对催化剂体系进行预活化提高了催化剂的活性和醛选择性,从而提高了铑催化剂利用效率,降低了生产成本。(The invention provides a hydroformylation method, which comprises the following steps: step A: carbon monoxide and hydrogen are mixed with a solvent to obtain a premix. The hydroformylation process of the present invention also comprises: and B: mixing the premix with a catalyst system, and carrying out pre-reaction to obtain a pre-reactant; and C: mixing the pre-reactant with the high-carbon olefin to react. The method improves the activity and the aldehyde selectivity of the catalyst by premixing the gas phase and the liquid phase and pre-activating the catalyst system, thereby improving the utilization efficiency of the rhodium catalyst and reducing the production cost.)

1. A hydroformylation process comprising:

step A: carbon monoxide and hydrogen are mixed with an organic solvent to obtain a premix.

2. The method according to claim 1, characterized in that the temperature of the mixing is 50-130 ℃, preferably 60-80 ℃; and/or the pressure of said mixing is between 0 and 4MPa, preferably between 0.5 and 3 MPa; and/or the mixing time is 0.1-30min, preferably 15-25 min; and/or the molar ratio of carbon monoxide to hydrogen is (0.1-20): 1, preferably (1-10): 1.

3. the method according to claim 1 or 2, characterized in that the method further comprises:

and B: contacting the premix with a catalyst system for pre-reaction to obtain a pre-reactant;

and C: and (3) contacting the pre-reactant with high-carbon olefin to react.

4. The process according to any one of claims 1 to 3, wherein the pre-reaction time is from 0.1 to 20min, preferably from 1 to 10 min.

5. The process according to any one of claims 1 to 4, wherein the temperature of the reaction in step C is 60 to 140 ℃, preferably 70 to 100 ℃; and/or the reaction time in step C is 30-120min, preferably 60-105 min; and/or the pressure of the reaction in step C is higher than the pressure of the mixing in step a, preferably the pressure of the reaction in step C is at least 0.5MPa higher than the pressure of the mixing in step a; and/or the pressure of the reaction in step C is between 0 and 4MPa, preferably between 1 and 3 MPa.

6. The process according to any one of claims 1 to 5, characterized in that the higher olefin is an olefin of C6 or more, preferably an olefin of C8-C20, more preferably octene.

7. The process of any one of claims 1 to 6, wherein the catalyst system comprises a rhodium catalyst and an organophosphinic compound, preferably wherein the rhodium catalyst is represented by formula (I):

Rh(L¹)_x(L²)_y(L³)_z(Ⅰ)

wherein L is¹、L²And L³Each independently selected from hydrogen, CO, halogen, preferably chlorine, triphenylphosphine and acetylacetone; x, y and z are each independently selected from integers of 0 to 5, at least one of x, y and z being other than 0; and/or

The organic phosphine compound is selected from organic phosphine compounds containing C6-C10 aryl, preferably organic phosphine compounds containing phenyl.

8. The process according to any one of claims 1 to 7, wherein the organic solvent is selected from at least one of aldehyde compounds, ketone compounds, benzene, substituted benzene, alkane and substituted alkane, preferably from at least one of butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, caprylic aldehyde, nonanal, methyl isobutyl ketone, acetophenone, toluene, xylene, chlorobenzene and heptane, more preferably from toluene and/or nonanal.

9. The process according to any one of claims 1 to 7, wherein the rhodium catalyst is added in an amount of 50 to 400ppm, based on the metal rhodium; and/or

The molar ratio of the organic phosphine compound to the rhodium catalyst is 0.5:1-200:1 calculated by metal rhodium; and/or

The molar ratio of the higher olefin to the rhodium catalyst is 100000:1 to 500:1, preferably 10000:1 to 2000:1, calculated as rhodium metal.

10. Use of a process according to any one of claims 1 to 9 in the hydroformylation of higher olefins to produce aldehydes.

Technical Field

The invention relates to a hydroformylation method, in particular to a hydroformylation method capable of improving the activity of a rhodium catalyst system and the selectivity of aldehyde.

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 operating 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; U.S. Pat. No. 8507731 discloses Rh (CO) in examples 8 to 14₂The catalyst (acac) and the calixarene bidentate phosphine ligand combined catalyst shows higher N/I selectivity, but has lower reaction activity, and in addition, the ligand is more complex, the synthesis steps are complicated, and the use cost is higher. In addition, chinese patent CN101293818 discloses a hydroformylation method by reacting a mixed butaneThe alkene hydroformylation is carried out two-stage reaction, the problem of reaction difference of two kinds of alkene is well solved, the utilization rate of the alkene is improved, but the method is only limited to the hydroformylation of the low-carbon alkene. 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.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a hydroformylation method for improving the stability and the activity of a rhodium catalyst system in a reaction, and a reasonable process flow is designed so as to improve the stability and the activity of the rhodium catalyst system modified by organic phosphine in the reaction process, further improve the use efficiency of the rhodium catalyst and reduce the production cost.

The invention provides a hydroformylation method capable of improving the activity of a rhodium catalyst system in a reaction, and particularly relates to a method for preparing aldehyde by taking high-carbon olefin as a raw material in the presence of an organic phosphine modified rhodium hydroformylation catalyst system, wherein carbon monoxide, hydrogen and a solvent are premixed in a reaction kettle under a certain condition, and then the catalyst system is added to react with the high-carbon olefin as the raw material.

The present invention applies a pressure step to the reaction stage of the process of the present invention such that the pressure increases from the lower pressure of the premix stage to the higher pressure of the reaction stage. In particular, the pressure in the reaction stage of the process of the invention is controlled to be at least 0.5MPa higher than the pressure in the premixing stage.

In a first aspect the present invention provides a hydroformylation process comprising:

step A: carbon monoxide and hydrogen are mixed with an organic solvent to obtain a premix.

According to some embodiments of the invention, the temperature of the mixing is 50-130 ℃, e.g. 50 ℃, 80 ℃, 90 ℃.

According to a preferred embodiment of the invention, the temperature of the mixing is 60-80 ℃.

According to some embodiments of the invention, the pressure of the mixing is 0 to 4 Mpa.

According to a preferred embodiment of the invention, the pressure of the mixing is between 0.5 and 3 MPa.

According to a preferred embodiment of the invention, the pressure of the mixing is between 0.5 and 2.5MPa, such as 0.5MPa, 1MPa, 1.5 MPa.

According to some embodiments of the invention, the time of mixing is 0.1-30min, such as 10min, 20min, 30 min.

According to a preferred embodiment of the invention, the mixing time is 15-25 min.

According to some embodiments of the invention, the molar ratio of carbon monoxide to hydrogen is (0.1-20): 1.

according to a preferred embodiment of the invention, the molar ratio of carbon monoxide to hydrogen is (1-10): 1.

According to one embodiment of the invention, the molar ratio of carbon monoxide to hydrogen is 1: 1.

According to some embodiments of the invention, the method further comprises:

and B: contacting the premix with a catalyst system for pre-reaction to obtain a pre-reactant;

and C: and (3) contacting the pre-reactant with high-carbon olefin to react.

According to some embodiments of the invention, the pre-reaction time is 0.1 to 20 min.

According to a preferred embodiment of the invention, the pre-reaction time is 1-10min, such as 2min, 5min, 10 min.

According to some embodiments of the invention, the temperature of the reaction in step C is 60-140 ℃.

According to a preferred embodiment of the invention, the temperature of the reaction in step C is in the range of 70 to 100℃, for example 80℃.

According to some embodiments of the invention, the time of the reaction in step C is 30-120 min.

According to a preferred embodiment of the invention, the time of the reaction in step C is 60-105min, such as 60 min.

According to some embodiments of the invention, the pressure of the reaction in step C is higher than the pressure of the mixing in step a.

According to a preferred embodiment of the invention, the pressure of the reaction in step C is at least 0.5MPa higher than the pressure of the mixing in step A.

According to some embodiments of the invention, the pressure of the reaction in step C is 0 to 4 MPa.

According to a preferred embodiment of the invention, the pressure of the reaction in step C is between 1 and 3MPa, such as 1.5MPa, 2MPa, 3 MPa.

According to some embodiments of the invention, the higher olefin is an olefin of C6 or greater.

According to a preferred embodiment of the invention, the higher olefin is a C8-C20 olefin.

According to a preferred embodiment of the invention, the higher olefin is octene.

According to some embodiments of the invention, the catalyst system comprises a rhodium catalyst and an organophosphinic compound.

According to some embodiments of the invention, the rhodium catalyst is represented by formula (i):

Rh(L¹)_x(L²)_y(L³)_z (Ⅰ)

wherein L is¹、L²And L³Each independently selected from hydrogen, CO, chlorine, triphenylphosphine and acetylacetone; x, y and z are each independently selected from integers of 0 to 5, at least one of x, y and z being other than 0.

According to some embodiments of the invention, the organophosphinic compound is selected from the group consisting of organophosphinic compounds containing a C6-C10 aryl group.

According to some embodiments of the invention, the organophosphinic compound is selected from the group consisting of phenyl-containing organophosphinic compounds.

According to some embodiments of the invention, the organic solvent is selected from at least one of aldehydes, ketones, benzene substitutes, alkanes and substituted alkanes.

According to a preferred embodiment of the present invention, the organic solvent is at least one selected from the group consisting of butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, caprylic aldehyde, nonanal, methyl isobutyl ketone, acetophenone, toluene, xylene, chlorobenzene, and heptane.

According to a preferred embodiment of the invention, the organic solvent is selected from toluene and/or nonanal.

According to some embodiments of the invention, the rhodium catalyst is added in an amount of 50 to 400ppm, based on the metal rhodium.

According to some embodiments of the invention, the molar ratio of the organophosphinic compound to the rhodium catalyst is from 0.5:1 to 200:1, calculated as rhodium metal.

According to some embodiments of the invention, the molar ratio of the higher olefin to the rhodium catalyst is 100000:1 to 500:1, calculated as rhodium metal.

According to a preferred embodiment of the present invention, the molar ratio of the higher olefin to the rhodium catalyst is 10000:1 to 2000:1 in terms of metal rhodium.

In another aspect of the invention there is provided the use of a process according to the first aspect in the hydroformylation of higher olefins to produce aldehydes.

According to some embodiments of the invention, the higher olefin is an olefin of C6 or greater.

According to a preferred embodiment of the invention, the higher olefin is a C8-C20 olefin.

According to a preferred embodiment of the invention, the higher olefin is octene.

The invention has the beneficial effects that: the invention can improve the activity and aldehyde selectivity of the catalyst by premixing the gas phase and the liquid phase and pre-activating the catalyst system, thereby improving the utilization efficiency of the rhodium catalyst and reducing the production cost.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.

Example 1

In a glove box under inert atmosphere, 8.9mg of tris (triphenylphosphine) carbonyl rhodium hydride and 330mg of triphenylphosphine were mixed and dissolved in 2ml of toluene, and the mixture was added into a feeding bottle of a reaction kettle for standby. The reaction device adopts a 50ml autoclave reaction device. Heating the autoclave to 80 deg.C, evacuating, and introducing synthesis gas (CO: H)₂1:1) were replaced several times, the vent valve was opened, 20.86ml of toluene was quickly added to the reaction vessel, the pressure was set at 1.5MPa, and synthesis gas (CO: H) was introduced into the reaction vessel₂1:1), premixing and stirring for 20min, then opening a sample injection device, completely adding 2mL of catalyst system into the reaction kettle, closing the sample injection device, and continuing stirring for 5 min. The pressure was adjusted to 2MPa, and 12.14ml of 1-octene was added to carry out a reaction for 60 min. After the reaction was completed, the reaction solution was collected. The liquid phase product from which the catalyst was filtered out was subjected to chromatography, and the results of the reaction were found to be shown in Table 1.

Example 2

The experimental method was the same as in example 1, the premixing pressure was changed to 1.0MPa, 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, the premixing pressure was changed to 0.5MPa, 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 premixing temperature was changed to 50 ℃, the reaction temperature was still 80 ℃, the rest of the 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 premixing temperature was changed to 90 ℃, the reaction temperature was still 80 ℃, the rest of the 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 premixing time of the solvent and the synthesis gas is changed to 10min, the rest experimental conditions are unchanged, and the test results are shown in table 1.

Example 7

The experimental method is the same as that of example 1, the premixing time of the solvent and the synthesis gas is changed to 30min, the rest experimental conditions are unchanged, and the test results are shown in table 1.

Example 8

The experimental method is the same as example 1, the pre-reaction time of the mixed solution and the catalyst is changed to 2min, the rest experimental conditions are not changed, and the test results are shown in table 1.

Example 9

The experimental method is the same as that of example 1, the pre-reaction time of the mixed solution and the catalyst is changed to 10min, the rest experimental conditions are not changed, and the test results are shown in table 1.

Example 10

The experimental method was the same as in example 1, the premixing pressure was changed to 3.0MPa, the other experimental conditions were unchanged, and the test results are shown in Table 1.

Example 11

The experimental method is the same as that of example 1, the stirring time after the catalyst is added is changed to 20min, the rest experimental conditions are unchanged, and the test results are shown in table 1.

Example 12

The experimental method is the same as that of example 1, 1-octene is added under 1.5MPa for reaction without changing pressure, and the rest experimental conditions are unchanged, and the test results are shown in Table 1.

Comparative example 1

The experimental procedure is the same as in example 1, wherein the catalyst system is not pre-reacted, and the catalyst and 1-octene are added to the reactor at the same time, and the experimental results are as follows: 87.7 percent; aldehyde selectivity: 89.7 percent.

As can be seen from the comparative examples, the catalyst reactivity and the aldehyde selectivity were low without pre-reacting the catalyst system.

TABLE 1

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.