KR102686720B1 - Catalyst composition for hydroformylation and method for ptrparing aldehyde - Google Patents

Abstract

A catalyst composition for hydroformylation reaction according to an exemplary embodiment of the present application includes a phosphite-based ligand represented by Chemical Formula 1; A transition metal compound represented by Formula 2 above; and a solvent, and the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is 5 to 45.

Description

Catalyst composition for hydroformylation reaction and method for producing aldehyde using the same {CATALYST COMPOSITION FOR HYDROFORMYLATION AND METHOD FOR PTRPARING ALDEHYDE}

This application relates to a catalyst composition for hydroformylation reaction and a method for producing aldehyde using the same.

Linear (normal) and branched (iso) olefins with the number of carbon atoms increased by one are obtained by reacting various olefins with carbon monoxide (CO), commonly called a synthetic gas, and hydrogen (H ₂ ) in the presence of a homogeneous organometallic catalyst and ligand. ) The hydroformylation reaction that produces aldehydes was first discovered by Otto Roelen in Germany in 1938.

In general, the hydroformylation reaction, known as the 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 through oxo reaction can be transformed into various acids and alcohols containing long alkyl groups by oxidation or hydrogenation after condensation reaction with aldol. In particular, the hydrogenated alcohol of an aldehyde through this oxo reaction is called an oxo alcohol, and oxo alcohols are widely used industrially as solvents, additives, raw materials for various plasticizers, and synthetic lubricants.

In this regard, since the value of linear aldehyde derivatives (normal-aldehyde) among aldehydes produced by oxo reaction was previously high, most catalyst research has been conducted in the direction of increasing the proportion of linear aldehyde derivatives. However, recently, Made from branched aldehyde derivatives (iso-aldehyde), such as isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-1,3-pentanediol (2,2) As the demand for iso-aldehyde increases due to the development of 4-trimethyl-1,3-pentanediol) and isovaleric acid, research is continuing to increase the selectivity of the branched aldehyde derivatives. . Accordingly, there is a need to develop a catalyst that has excellent catalytic stability and activity while lowering the normal/iso selectivity ratio (n/i ratio) of aldehyde.

Republic of Korea Patent Publication No. 10-1150557

This application provides a catalyst composition for hydroformylation reaction and a method for producing aldehyde using the same.

One implementation state of this application is,

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

A transition metal compound represented by the following formula (2); and

Contains a solvent,

A catalyst composition for hydroformylation reaction is provided, wherein the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is 5 to 45.

[Formula 1]

In Formula 1,

R1 is an aryl group substituted with one or more of an alkyl group and an alkoxy group,

R2 to R5 are the same or different from each other and are each independently an alkyl group,

[Formula 2]

M(L1)x(L2)y(L3)z

In Formula 2,

M is rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), or osmium (Os),

L1, L2 and L3 are the same as or different from each other, and each independently represents hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) Or acetylacetonato (AcAc),

The x, y, and z are each independently integers from 0 to 5, and x, y, and z are not 0 at the same time.

In addition, other embodiments of this application are:

A hydroformylation step of producing an aldehyde by reacting an olefin-based compound with a synthesis gas in the presence of the catalyst composition for the hydroformylation reaction,

A method for producing aldehyde is provided in which the synthetic gas contains carbon monoxide and hydrogen.

According to an exemplary embodiment of the present application, a catalyst composition for hydroformylation reaction with excellent catalytic activity and stability can be provided.

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 produced during the hydroformylation reaction of the olefinic compound can be lowered. There are features that can be used.

Hereinafter, this 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 the case where a member is in contact with another member, but also the case where another member exists between the two members.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

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

As in the prior art, when the reaction is performed using a phosphine ligand as a catalyst composition, the n-BAL/i-BAL molar ratio increases, making it difficult to obtain a composition with the desired molar ratio, and the activity is generally low. Additionally, even when using a di-phosphite ligand with a very high molecular weight, a low n-BAL/i-BAL molar ratio cannot be obtained.

Accordingly, in the present application, the n-BAL/i-BAL molar ratio is very low at 3 or less, and in order to exhibit very high activity compared to the conventional phosphine ligand, a catalyst composition containing a ligand of a cyclic phosphite compound is used. I wanted to use it.

A catalyst composition for hydroformylation reaction according to an exemplary embodiment of the present application includes a phosphite-based ligand represented by Chemical Formula 1; A transition metal compound represented by the following formula (2); and solvent.

The alkyl group of Formula 1 may be straight chain 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, and 1-ethylbutyl group. etc., but is not limited to this.

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, phenyl group, biphenyl group, terphenyl group, and naphthyl group.

The alkoxy group of Formula 1 preferably has 1 to 5 carbon atoms. Specific examples of the alkoxy group include methoxy group and ethoxy group, but are not limited thereto.

In an exemplary embodiment of the present application, R1 in Formula 1 may be a phenyl group substituted with one or more of a methyl group, a tert-butyl group, and a methoxy group.

In an exemplary embodiment of the present application, R2 to R4 in Formula 1 are each independently a methyl group or a tert-butyl group. Additionally, in an exemplary embodiment of the present application, R2 and R5 of Formula 1 are tert-butyl groups, and R3 and R4 are methyl groups.

According to an exemplary embodiment of the present application, a phenyl group substituted with one or more of a methyl group, a tert-butyl group, and a methoxy group is bonded to R1 of Formula 1, thereby providing a catalyst composition for hydroformylation reaction with excellent catalytic activity and stability. can be provided.

In an exemplary embodiment of the present application, the phosphite-based ligand may be represented by any of the following structural formulas.

In an exemplary embodiment of the present application, the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound may be 5 to 45, and may be 8 to 30. When the molar ratio is satisfied, catalytic activity and stability are excellent, and selectivity for i-butyraldehyde and syn gas yield are high. If the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is less than 5, the reaction activity may be greatly reduced, and if it exceeds 45, the selectivity of i-butyraldehyde may be reduced.

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% by weight to 4% by weight, and may be 1% by weight to 3% by weight. there is. By satisfying the content range of the phosphite-based ligand, it is possible to obtain the effect of excellent stability and activity of the catalyst and low normal/iso selectivity of the produced aldehyde.

In an exemplary embodiment of the present application, the transition metal compound is cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonyl rhodium [Rh(AcAc) (CO) ₂ ], acetylacetonatocarbonyl Triphenylphosphine rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium [HRh(CO)(TPP) ₃ ], acetylacetonatodicarbonyl iridium [Ir (AcAc)(CO) ₂ ] and hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP) ₃ ].

In an exemplary embodiment of the present application, the solvent is propanaldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, It may include one or more of theenol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and heptane. In addition, it is more preferable that the solvent contains at least one of butyl aldehyde and valeraldehyde. In this case, purification of the hydroformylation reaction product can be easily performed and side reactions can 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 the activity of the catalyst composition containing the triphenylphosphine compound. , within this range, excellent catalytic activity is achieved.

In addition, the catalyst composition, for example, has a catalyst stability after being deactivated for 15 hours at a deactivation temperature of 90°C or higher, 90°C to 150°C, or 100°C to 120°C, which is equal to the gas consumption of the catalyst composition containing a triphenylphosphine compound. It may be 100% or more, 100% to 500%, or 100% to 250%, and within this range, excellent catalyst stability is achieved.

In addition, another embodiment of the present application includes a hydroformylation step of producing 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 contains carbon monoxide and hydrogen. A method for producing an aldehyde comprising:

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

In an exemplary embodiment of the present application, the molar ratio of carbon monoxide: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, a reaction temperature of 70°C to 110°C, and a pressure of 5 bar to 15 bar. Can be performed under pressure. If the reaction temperature in the hydroformylation step is less than 50°C, the activity of the reaction may decrease or the reaction may not occur, and if it exceeds 130°C, the catalyst and ligand may decompose and reactivity may decrease. there is.

In an exemplary embodiment of the present application, the olefinic compound may be one or more selected from 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 an exemplary embodiment of the present application, the aldehyde may have a molar ratio of n-butyraldehyde to i-butyraldehyde of 3 or less and 2.5 or less.

Hereinafter, in order to explain the present application in detail, examples will be given in detail. However, the embodiments according to the present application may be modified into 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 with average knowledge in the art.

< Example >

< Control example 1>

0.12 g (0.3 mmol) of rhodium acetylacetonato carbonyl triphenylphosphine (Rh(AcAc)(CO)(TPP), ROPAC) and triphenylphosphine (TPP) were mixed with valeraldehyde. (valeraldehyde) was dissolved in a solvent to make the total solution 100g (Rh 250ppm, TTP 2% by weight), and then placed in a 600ml autoclave reactor. Propylene and synthetic gas (CO/H ₂ ) were injected into the reaction solution, the pressure in the reactor was maintained at 8 bar, and the reaction was performed for 1 hour while stirring at 90°C.

< Example 1 to 9 and Comparative example 1~5>

The same method as in Control Example 1, except that instead of triphenylphosphine (TPP) as a ligand, a cyclic phosphite compound or a phosphine compound listed in Table 1 was added in the weight % indicated. It was carried out as follows.

Afterwards, through GC (gas chromatography) analysis, the n-BAL content was divided by the i-BAL content to indicate the n/i-BAL molar ratio.

< GC Analysis conditions>

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

② Injection volume: 1㎕

③ Inlet Temp.: 260 ℃, Pressure: 6.92psi, Total flow: 64.2ml/min, Split flow: 60ml/min, spill 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 reaction according to Control Example 1, the total amount of normal and isobutyl aldehyde produced by reaction according to each Example and Comparative Example was compared and calculated using the following equation 1 and expressed as a percentage.

[Equation 1]

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

<Catalyst stability (Normal stability, % )>

After reacting according to Control Example 1, the consumption of propylene gas used in the reaction was measured, the catalyst solutions prepared in Examples and Comparative Examples were deactivated at an inactivation temperature for 15 hours, and then hydroformylated in the same manner. After the reaction, the propylene gas consumption used in the reaction was measured, and the propylene gas consumption before deactivation of Control Example 1 and the propylene gas consumption after 15 hours of deactivation of Control Example 1, Examples, or Comparative Examples ( gas) consumption was compared and calculated using Equation 2 below and expressed as a percentage.

[Equation 2]

Catalyst stability = propylene gas consumption in the reaction after deactivation for 15 hours in Control Example 1, Example or Comparative Example / propylene gas consumption before deactivation in Control Example 1 × 100

[Table 1]

[TPP, triphenylphosphine]

[TDMPP, tris(2,4-dimethylphenyl)phosphite]

[TPTP, tri-p-tolylphosphine]

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

As shown in the above results, according to an exemplary embodiment of the present application, a catalyst composition for hydroformylation reaction with excellent catalytic activity and stability can be provided.

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 produced during the hydroformylation reaction of the olefinic compound can be lowered. There are features that can be used.

Claims (10)

A phosphite-based ligand represented by the following formula (1);
A transition metal compound represented by the following formula (2); and
Contains a solvent,
A catalyst composition for hydroformylation reaction, wherein the molar ratio of the phosphite-based ligand to the transition metal of the transition metal compound is 5 to 45:
[Formula 1]

In Formula 1,
R1 is an aryl group substituted with one or more of an alkyl group and an alkoxy group,
R2 to R5 are the same or different from each other and are each independently an alkyl group,
[Formula 2]
M(L1)x(L2)y(L3)z
In Formula 2,
M is rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), or osmium (Os),
L1, L2 and L3 are the same as or different from each other, and each independently represents hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) Or acetylacetonato (AcAc),
The x, y, and z are each independently integers from 0 to 5, and x, y, and z are not 0 at the same time. The catalyst composition for hydroformylation reaction according to claim 1, wherein the phosphite-based ligand is represented by any one of the following structural formulas:

The catalyst composition for hydroformylation reaction according to claim 1, wherein the content of the phosphite-based ligand is 1% by weight to 4% by weight, based on the total weight of the catalyst composition for hydroformylation reaction. The method of claim 1, wherein the transition metal compound is cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonyl rhodium [Rh(AcAc) (CO) ₂ ], acetylacetonatocarbonyltriphenylphosphine. Rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium [HRh(CO)(TPP) ₃ ], acetylacetonatodicarbonyl iridium [Ir(AcAc)( CO) ₂ ] and hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP) ₃ ]. A catalyst composition for hydroformylation reaction containing one or more kinds. The method of 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. A catalyst composition for hydroformylation reaction comprising one or more of toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and heptane. Comprising a hydroformylation step of producing an aldehyde by reacting an olefin-based compound with a synthesis gas in the presence of the catalyst composition for hydroformylation reaction of any one of claims 1 to 5,
A method for producing aldehyde, wherein the synthetic gas contains carbon monoxide and hydrogen. The method of claim 6, wherein the molar ratio of carbon monoxide to hydrogen is 5:95 to 70:30. The method of claim 6, wherein the hydroformylation step is performed at a reaction temperature of 50°C to 130°C and a pressure of 5 bar to 25 bar. The method of claim 6, wherein the olefin-based compound is propylene, and the aldehyde is butyraldehyde. The method of claim 9, wherein the aldehyde has a molar ratio of n-butyraldehyde to i-butyraldehyde of 3 or less.