KR20220053229A - Catalyst composition for hydroformylation and method for ptrparing aldehyde - Google Patents

Abstract

A catalyst composition for hydroformylation reaction according to one exemplary embodiment of the present application comprises: a phosphite-based ligand represented by chemical formula 1; rhodium acetylacetonato carbonyl triphenylphosphine (ROPAC); and a solvent.

Description

Catalyst composition for hydroformylation reaction and production method of aldehyde using the same

The present application relates to a catalyst composition for a hydroformylation reaction and a method for preparing an aldehyde using the same.

In the presence of a homogeneous organometallic catalyst and ligand, various olefins are reacted with carbon monoxide (CO) and hydrogen (H ₂ ), which are often called synthesis gases, to increase the number of carbons by one (linear, normal) and branched (iso) ) The hydroformylation reaction to produce aldehydes was first discovered in 1938 by Otto Roelen of Germany.

In general, a hydroformylation reaction known as an oxo (OXO) reaction is an industrially very important reaction in a homogeneous catalytic reaction, and various aldehydes including alcohol derivatives are produced and consumed worldwide through the oxo process.

Various aldehydes synthesized by the oxo reaction are oxidized or hydrogenated after a condensation reaction such as aldol, and are sometimes transformed into various acids and alcohols containing a long alkyl group. In particular, the hydrogenated alcohol of aldehyde by the oxo reaction is called oxo alcohol, and oxo alcohol is widely used industrially, such as solvents, additives, raw materials for various plasticizers, and synthetic lubricants.

In this regard, conventionally, since the value of the normal-aldehyde among the aldehydes produced by the oxo reaction was high, most of the studies on catalysts have been conducted in the direction of increasing the ratio of the linear aldehyde derivative, but recently Branched aldehyde derivatives (iso-aldehyde) as raw materials, for example, isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-1,3-pentanediol (2,2) ,4-trimethyl-1,3-pentanediol), isovaleric acid, etc. As the demand for isoaldehyde increases due to the development of it, research in the direction of increasing the selectivity of the branched aldehyde derivative is continuing. . Accordingly, there is a need to develop a catalyst having excellent catalyst stability and activity while lowering the aldehyde normal/iso selectivity ratio (n/i ratio).

Republic of Korea Patent Publication No. 10-1150557

The present application provides a catalyst composition for a hydroformylation reaction and a method for preparing an aldehyde having a low n/iso ratio (n/i-ratio) using the same.

An exemplary embodiment of the present application is,

a phosphite-based ligand represented by the following formula (1);

rhodium acetylacetonato carbonyl triphenylphosphine (ROPAC); and

It provides a catalyst composition for hydroformylation reaction comprising a solvent.

[Formula 1]

In Formula 1,

Ar1 and Ar2 are the same as or different from each other, and are each independently an aryl group,

R1 to R4 are the same as or different from each other, and each independently represents an alkyl group.

In addition, another embodiment of the present application is,

a hydroformylation step of reacting an olefin-based compound with a synthesis gas in the presence of the catalyst composition for the hydroformylation reaction to produce an aldehyde;

The synthesis gas provides a method for producing an aldehyde comprising carbon monoxide and hydrogen.

According to an exemplary embodiment of the present application, it is possible to provide a catalyst composition for hydroformylation reaction having excellent catalytic activity and stability.

In addition, according to an exemplary embodiment of the present application, by using the catalyst composition for the hydroformylation reaction, the normal/iso selectivity ratio (n/i ratio) of the aldehyde generated during the hydroformylation reaction of the olefin-based compound can be lowered. There are features that can be

Hereinafter, the present specification will be described in more detail.

In this specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

In the present specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

As described above, in the case of the hydroformylation reaction using propylene and syngas, n-butylaldehyde (n-BAL) and i-butylaldehyde (i-BAL) are produced together. In this application, it was attempted to increase the selectivity of i-butylaldehyde, and to increase the production of the catalyst with a low content by increasing the activity of the reaction.

As in the prior art, when the reaction is carried out using a phosphine ligand as a catalyst composition, the molar ratio of n-BAL/i-BAL is high, so it is difficult to obtain a composition having a desired molar ratio, and the activity is generally low. In addition, even when a Di-phosphite ligand having a very high molecular weight is used, a low n-BAL/i-BAL molar ratio cannot be obtained.

Accordingly, in the present application, in order to exhibit a very low n-BAL/i-BAL molar ratio of 0.95 or less, and very high activity compared to a conventional phosphine ligand, a catalyst composition including a ligand of a cyclic phosphite-based compound was prepared. wanted to use it.

A catalyst composition for a hydroformylation reaction according to an exemplary embodiment of the present application includes a phosphite-based ligand represented by Formula 1; acetylacetonatocarbonyltriphenylphosphinerhodium; and solvents.

The alkyl group of Formula 1 may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group and the like, but is not limited thereto.

The aryl group of Formula 1 preferably has 6 to 20 carbon atoms. Specific examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and the like.

In the exemplary embodiment of the present application, Ar1 and Ar2 of Formula 1 are each independently a phenyl group or a naphthyl group.

In the exemplary embodiment of the present application, R1 to R4 in Formula 1 are each independently a methyl group or a tert-butyl group. In addition, in an exemplary embodiment of the present application, R1 to R4 in Formula 1 are tert-butyl groups.

According to an exemplary embodiment of the present application, since all aryl groups are bonded to ortho positions of the phenyl group bonded to the oxygen atom of Formula 1, an aldehyde having an n-BAL/i-BAL molar ratio of 0.95 or less can be prepared using the aryl groups.

In an exemplary embodiment of the present application, the phosphite-based ligand may be represented by Formula 2 below.

[Formula 2]

In an exemplary embodiment of the present application, the molar ratio of the phosphite-based ligand to rhodium of the acetylacetonatocarbonyltriphenylphosphine rhodium may be 50 to 150, and may be 80 to 140. When the molar ratio is satisfied, catalyst activity and stability are excellent, and selectivity of i-butylaldehyde and syn gas yield are high. When the molar ratio of the phosphite-based ligand to rhodium is less than 50, the reaction activity may decrease, and if it exceeds 150, the selectivity of i-butylaldehyde may decrease.

In an exemplary embodiment of the present application, based on the total weight of the catalyst composition for the hydroformylation reaction, the content of the phosphite-based ligand may be 1 wt% to 10 wt%, and 4 wt% to 8 wt% there is. By satisfying the content range of the phosphite-based ligand, it is possible to obtain the effect of having excellent catalyst stability and activity and low normal/isoselectivity of the aldehyde produced.

In an exemplary embodiment of the present application, based on the total weight of the catalyst composition for the hydroformylation reaction, the content of the acetylacetonatocarbonyltriphenylphosphine rhodium may be 1ppm to 300ppm, and may be 10ppm to 250ppm. . By satisfying the content range of the acetylacetonatocarbonyltriphenylphosphine rhodium, it is possible to obtain the effect of having excellent catalyst stability and activity and low normal/isoselectivity of the aldehyde produced.

In an exemplary embodiment of the present application, the solvent is propane aldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, and at least one of thenicanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane. In addition, it is more preferable that the solvent includes at least one of butyl aldehyde and valer aldehyde, and in this case, the hydroformylation reaction product may be easily purified and side reactions may be minimized.

In an exemplary embodiment of the present application, the catalyst composition may have, for example, 300% or more, 500% or more, or 500% to 1,000% of catalytic activity based on the activity of the catalyst composition including the triphenylphosphine compound, , there is an excellent effect of catalytic activity within this range.

In addition, the catalyst composition is, for example, 90 ℃ or more, 90 ℃ to 150 ℃, or 100 ℃ to the gas consumption of the catalyst composition containing the triphenylphosphine compound after deactivation for 15 hours at an inactivation temperature of 100 ℃ to 120 ℃ It may be 100% or more, 100% to 500%, or 100% to 250% based on, and there is an excellent effect of catalyst stability within this range.

In addition, another exemplary embodiment of the present application includes a hydroformylation step of preparing an aldehyde by reacting an olefin-based compound with a synthesis gas in the presence of the catalyst composition for the hydroformylation reaction, wherein the synthesis gas includes carbon monoxide and hydrogen It provides a method for producing an aldehyde comprising.

The method for producing an aldehyde according to an exemplary embodiment of the present application may use a method known in the art, except for using the catalyst composition for the hydroformylation reaction described above.

In an exemplary embodiment of the present application, the molar ratio of carbon monoxide to hydrogen may be 5:95 to 70:30, and 40:60 to 60:40.

In an exemplary embodiment of the present application, the hydroformylation step may be performed at a reaction temperature of 50° C. to 130° C., and a pressure of 5 bar to 25 bar, and a reaction temperature of 70° C. to 110° C., and 5 bar to 15 bar. It can be carried out under pressure. If the reaction temperature of the hydroformylation step is less than 50 ℃, the activity of the reaction may decrease or the reaction may not be made, and if it exceeds 130 ℃, there is a possibility that the catalyst and ligand may be decomposed, and the reactivity may be reduced. there is.

In an exemplary embodiment of the present application, the olefin-based compound may be at least one selected from among ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and styrene, but is not limited thereto. . More preferably, the olefin-based compound may be propylene, and the aldehyde may be butyraldehyde.

In the exemplary embodiment of the present application, the molar ratio of n-butylaldehyde to i-butylaldehyde may be 0.95 or less, and 0.93 or less.

Hereinafter, examples will be given to describe the present application in detail. However, the embodiments according to the present application may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described in detail below. The embodiments of the present application are provided to more completely explain the present application to those of ordinary skill in the art.

<Example>

<Example 1>

HTS (manufactured by Autoclave, USA, High Throughpur screen, multi-clave device capable of simultaneously proceeding 10 reactions) was used as the experimental device, and an autoclave reactor with a capacity of 20ml was used in the experimental device.

Acetylacetonato carbonyl triphenylphosphine (rhodium acetylacetonato carbonyl triphenylphosphine, Rh(AcAc)(CO)(TPP), ROPAC) as a catalyst was aliquoted in an amount corresponding to the Rh concentration described in Table 1 below, and Table 1 Ligand was fractionated according to the weight % described in , dissolved in valeraldehyde solvent, and then added to the autoclave reactor by 10 ml each.

A mixed gas mixed at a molar ratio of propylene, carbon monoxide, and hydrogen at a molar ratio of 1: 1: 1 (C ₃ H ₆ : CO: H ₂ ) was injected into the reaction solution to maintain the pressure in the reactor at 8 bar, and at 80° C., 900 rpm The reaction was carried out for 4 hours and 15 minutes at a stirring rate of The reaction solution was analyzed by gas chromatography (GC), and n/i-ratio values obtained by ratio of the amounts of n-butylaldehyde and i-butylaldehyde produced are shown in Table 1 below.

<Comparative Examples 1 to 8>

It was carried out in the same manner as in Example 1, except that the catalyst or ligand described in Table 1 was applied.

Then, the n/i-BAL molar ratio was expressed by dividing the n-BAL content by the i-BAL content through gas chromatography (GC) analysis.

<GC analysis conditions>

1) Column: HP-1(L:30m, ID:0.32mm, film:1.05m)

2) Injection volume: 1 μl

3) Inlet Temp.: 260 ℃, Pressure: 6.92psi, Total flow: 64.2ml/min, Split flow: 60ml/min, spilt ratio: 50:1

4) Column flow: 1.2ml/min

5) Oven temp.: 70℃/3min-10℃/min-280℃/41min (Total 65min)

6) Detector temp.: 280℃, H2: 35ml/min, Air: 300ml/min, He: 20ml/min

7) GC Model: Agilent 6890

<Catalyst activity (Normal activity, %)>

Based on 100% of the total amount of normal and isobutyl aldehyde produced by the reaction according to Example 1, the total amount of normal and isobutyl aldehyde produced by the reaction according to each Example and Comparative Example is compared and calculated by Equation 1 below and expressed as a percentage.

[Equation 1]

Catalytic activity = total amount of normal and isobutyl aldehyde of Example or Comparative Example / total amount of normal and isobutyl aldehyde of Example 1 × 100

[Table 1]

Rh(cod)(acac): Acetylacetonato(1,5-cyclooctadiene)rhodium

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

[Compound 7]

[Compound 8]

As described above, according to an exemplary embodiment of the present application, it is possible to provide a catalyst composition for hydroformylation reaction having excellent catalytic activity and stability.

In particular, according to an exemplary embodiment of the present application, the phosphite-based ligand represented by Formula 1; And by simultaneously applying acetylacetonatocarbonyltriphenylphosphinerhodium, it is possible to lower the selectivity ratio (n/i ratio) of normal/iso of aldehydes generated during the hydroformylation reaction of olefinic compounds to 0.95 or less. Rather, it is possible to obtain a characteristic excellent in catalytic activity.

Claims (9)

a phosphite-based ligand represented by the following formula (1);
rhodium acetylacetonato carbonyl triphenylphosphine (ROPAC); and
Catalyst composition for hydroformylation reaction comprising a solvent:
[Formula 1]

In Formula 1,
Ar1 and Ar2 are the same as or different from each other, and are each independently an aryl group,
R1 to R4 are the same as or different from each other, and each independently represents an alkyl group. The catalyst composition for a hydroformylation reaction according to claim 1, wherein the phosphite-based ligand is represented by the following Chemical Formula 2:
[Formula 2]

The catalyst composition for a hydroformylation reaction according to claim 1, wherein the content of the phosphite-based ligand is 1 wt% to 10 wt%, based on the total weight of the catalyst composition for the hydroformylation reaction. The catalyst composition for the hydroformylation reaction according to claim 1, wherein the content of the acetylacetonatocarbonyltriphenylphosphinrhodium is 1ppm to 300ppm based on the total weight of the catalyst composition for the hydroformylation reaction. The method according to claim 1, wherein the solvent is propanaldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, thesanol, benzene , toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and a catalyst composition for a hydroformylation reaction comprising at least one of heptane. A hydroformylation step of preparing an aldehyde by reacting an olefin-based compound with a synthesis gas in the presence of the catalyst composition for the hydroformylation reaction of any one of claims 1 to 5,
The synthesis gas is a method for producing an aldehyde comprising carbon monoxide and hydrogen. The method according to claim 6, wherein the hydroformylation step is performed under a reaction temperature of 50 °C to 130 °C, and a pressure of 5 bar to 25 bar. The method according to claim 6, wherein the olefin-based compound is propylene, and the aldehyde is butyraldehyde. The method according to claim 8, wherein the aldehyde has a molar ratio of n-butylaldehyde to i-butylaldehyde of 0.95 or less.