KR20220026295A - Method for producing aldehyde and method for producing alcohol - Google Patents

Abstract

A preparation method of an aldehyde according to one exemplary embodiment of the present application comprises: a step of preparing methyl isobutyl ketone (MIBK) using acetone; a step of preparing a C6 olefin using the methyl isobutyl ketone (MIBK); and a step of performing a hydroformylation reaction on the C6 olefin to prepare a C7 aldehyde.

Description

A method for producing an aldehyde and a method for producing an alcohol

The present application relates to a method for producing an aldehyde and a method for producing an alcohol.

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.

The hydroformylation reaction, commonly known as the 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.

Currently, the catalysts used in the oxo process are mainly cobalt (Co) and rhodium (Rh) series, and the ratio of linear (normal) to branched (ratio of linear (normal) to branched (ratio of linear (normal) to branched ( iso) isomers) are different. Currently, more than 70% of oxo plants around the world are adopting the Low Pressure OXO Process using a rhodium-based catalyst.

In addition to cobalt (Co) and rhodium (Rh) as the central metal of the oxo catalyst, iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), nickel (Ni) ) can be applied. However, since it is known that each metal exhibits catalytic activity in the order of Rh >> Co > Ir, Ru > Os > Pt > Pd > Fe > Ni, most of the processes and research are focused on rhodium and cobalt.

Ligands include phosphine (Phosphine, PR ₃ , R is C ₆ H ₅ , or nC ₄ H ₉ ), phosphine oxide (Phosphine Oxide, O=P(C ₆ H ₅ ) ₃ ), phosphite, Amine (Amine), amide (Amide), isonitrile (Isonitrile) and the like are applicable.

A typical example of hydroformylation is to prepare octanol (2-ethylhexanol) from propylene using a rhodium-based catalyst.

Octanol is mainly used as a raw material for PVC plasticizers such as DOP (Dioctyl Phathalate), and is also used as an intermediate raw material for synthetic lubricants and surfactants. Propylene is fed into the oxo reactor using a catalyst together with synthesis gas (CO/H ₂ ) to produce n-butylaldehyde and iso-butylaldehyde. The resulting aldehyde mixture is sent to a separation system together with the catalyst mixture to be separated into hydrocarbon and catalyst mixture, the catalyst mixture is circulated to the reactor, and the hydrocarbon component is transferred to a stripper. The hydrocarbons in the stripper are stripped by the freshly supplied synthesis gas, unreacted propylene and synthesis gas are recovered to the oxo reactor, and butyraldehyde is transferred to a fractionation column and separated into n- and iso-butylaldehyde, respectively. Normal-butylaldehyde at the bottom of the fractionation column is introduced into the aldol condensation reactor to produce 2-ethylhexanal by condensation and dehydration reaction, and then transferred to the hydrogenation reactor, and octanol (2-ethylhexanol) is produced by hydrogenation. do. The reactants at the outlet of the hydrogenation reactor are transferred to a fractionation column to separate the soft/hard ends to produce an octanol product.

The hydroformylation reaction can be carried out continuously, semi-continuously or batchwise, typical hydroformylation reaction processes are gas or liquid recycle systems. In the hydroformylation reaction, it is important to increase the reaction efficiency by allowing the starting materials in liquid phase and gas phase to contact smoothly. For this purpose, conventionally, a continuous stirred tank reactor (CSTR) in which liquid and gaseous components are stirred to uniformly contact in the reactor has been mainly used.

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. .

Republic of Korea Patent Publication No. 10-1150557

An object of the present application is to provide a method for preparing an aldehyde and a method for preparing an alcohol.

An exemplary embodiment of the present application is,

preparing methyl isobutyl ketone (MIBK) using acetone;

preparing a C6 olefin using the methyl isobutyl ketone; and

performing a hydroformylation reaction on the C6 olefin to prepare a C7 aldehyde

It provides a method for producing an aldehyde comprising a.

In addition, another embodiment of the present application is,

preparing C7 aldehyde according to the above method; and

preparing C7 alcohol by performing a hydrogenation reaction on the C7 aldehyde

It provides a method for producing alcohol comprising a.

According to an exemplary embodiment of the present application, it is possible to provide a novel aldehyde production method capable of using acetone as a starting material and finally producing C7 aldehyde, using acetone as a starting material and finally producing C7 alcohol It is possible to provide a novel method for the production of alcohol that can.

1 is a diagram schematically showing a process diagram of a method for producing an aldehyde and a method for producing an alcohol according to an exemplary embodiment of the present application.

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.

In the present application, it is an object of the present application to provide a novel aldehyde preparation method that can use acetone as a starting material and finally produce C7 aldehyde. In addition, in the present application, it is intended to provide a novel method for preparing alcohol using acetone as a starting material and finally producing C7 alcohol.

A method for producing an aldehyde according to an exemplary embodiment of the present application includes preparing methyl isobutyl ketone (MIBK) using acetone; preparing a C6 olefin using the methyl isobutyl ketone; and performing a hydroformylation reaction on the C6 olefin to prepare a C7 aldehyde.

A process diagram of a method for producing an aldehyde according to an exemplary embodiment of the present application is schematically shown in FIG. 1 below.

As shown in FIG. 1 below, a more detailed description of the method for producing an aldehyde according to an exemplary embodiment of the present application is as follows.

In an exemplary embodiment of the present application, the preparing of methyl isobutyl ketone using acetone includes: preparing diacetone alcohol (DAA) by performing a condensation reaction on the acetone; performing a dehydration reaction on the diacetone alcohol to prepare mesityl oxide (MO); and performing a hydrogenation reaction on the mesityl oxide to prepare methyl isobutyl ketone.

In an exemplary embodiment of the present application, the condensation reaction of acetone may be performed using a basic solid catalyst. The basic solid catalyst may include one or more of magnesium hydroxide, calcium hydroxide, strontium hydroxide, valium hydroxide, magnesium oxide, calcium oxide, strontium oxide, valium oxide, and the like, but is not limited thereto. The basic solid catalyst may be used alone, or may be used by being supported on a carrier. The basic solid catalyst may be used by being charged in a reactor in a fixed bed, a fluidized bed, a mobile bed, or the like.

In an exemplary embodiment of the present application, the dehydration reaction of diacetone alcohol may be performed by contacting diacetone alcohol with a catalyst such as sulfuric acid, phosphoric acid, palladium-based, or aluminum-based catalyst.

In an exemplary embodiment of the present application, the hydrogenation reaction of mesityl oxide may use a catalyst for hydrogenation reaction, and the catalyst for hydrogenation reaction is one of ruthenium, palladium, copper, nickel, copper-zinc and platinum. It may include more than one species.

In addition, in an exemplary embodiment of the present application, the step of preparing methyl isobutyl ketone using acetone includes the above-described condensation reaction of acetone, dehydration reaction of diacetone alcohol, and mesityl oxide using a Pd-based catalyst. of hydrogenation reactions can be carried out simultaneously in one reactor.

In an exemplary embodiment of the present application, the preparing of a C6 olefin using the methyl isobutyl ketone includes: preparing a C6 alcohol by performing a hydrogenation reaction on the methyl isobutyl ketone; and performing a dehydration reaction on the C6 alcohol to prepare a C6 olefin.

In an exemplary embodiment of the present application, the hydrogenation reaction of methyl isobutyl ketone may use a catalyst for the hydrogenation reaction, and the catalyst for the hydrogenation reaction is ruthenium, palladium, copper, nickel, copper-zinc and platinum. It may include one or more types.

In an exemplary embodiment of the present application, the dehydration reaction of the C6 alcohol may be performed by contacting the C6 alcohol with a catalyst such as sulfuric acid, phosphoric acid, palladium-based, aluminum-based, Ce-based, Zr-based, or zeolite-based catalyst.

In an exemplary embodiment of the present application, the C6 alcohol may be 4-methyl-2-pentanol.

In an exemplary embodiment of the present application, the C6 olefin is at least one of 4-methyl-1-pentene and 4-methyl-2-pentene. may include In addition, the C6 olefin may include a mixture of 4-methyl-1-pentene and 4-methyl-2-pentene.

In an exemplary embodiment of the present application, the hydroformylation reaction of the C6 olefin is performed by reacting the C6 olefin with a synthesis gas in the presence of a catalyst composition for the hydroformylation reaction, and the catalyst composition for the hydroformylation reaction is phosphorus ligands; A transition metal compound represented by the following formula (1); and solvents.

[Formula 1]

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

In Formula 1,

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 hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) or acetylacetonato (AcAc),

Wherein x, y and z are each independently an integer of 0 to 5, and x, y and z are not 0 at the same time.

In an exemplary embodiment of the present application, the phosphorus-based ligand is a phosphine-based ligand such as triphenylphosphine; phosphite-based ligands such as triphenylphosphite; Xantphos (4,5-bis(diphenylphosphino)); and BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl).

In an exemplary embodiment of the present application, the transition metal compound is cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonylrhodium [Rh(AcAc)(CO) ₂ ], acetylacetonatocarbonyl Triphenylphosphinerhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium [HRh(CO)(TPP) ₃ ], acetylacetonatodicarbonyliridium [Ir (AcAc)(CO) ₂ ], hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP) ₃ ] and chloro(1,5-cyclooctadiene)rhodium[Rh(COD)Cl ₂ ] may include one or more of.

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 an exemplary embodiment of the present application, the step of reacting the C6 olefin with the synthesis gas may be performed under a reaction temperature of 50°C to 130°C, and a pressure of 5bar to 30bar, and a reaction temperature of 70°C to 110°C , and may be carried out under a pressure of 5 bar to 20 bar. If the reaction temperature of the step of reacting the C6 olefin with the synthesis gas 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 be decomposed, Reactivity may be reduced.

In the exemplary embodiment of the present application, in the step of reacting the C6 olefin with the synthesis gas, the molar ratio of the C6 olefin: the synthesis gas may be 95:5 to 5:95.

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

In an exemplary embodiment of the present application, the C7 aldehyde is 5-methylhexanal, 2,4-dimethylpentanal, and 2-isopropylbutanal ) may include one or more of. In particular, the C7 aldehyde may include 5-methylhexanal.

In order to increase the selectivity of 4-methyl-1-pentene more than that of 4-methyl-2-pentene through the dehydration reaction of 4-methyl-2-pentanol, a technique for well controlling the activity of the catalyst is required. In addition, in order to proceed with the hydroformylation reaction in a state in which the two types of pentenes are mixed to obtain high conversion and selectivity, a technique for controlling the types and contents of catalysts and ligands is required. In particular, 1-pentene is a material with relatively high reactivity as a terminal olefin, but 2-pentene has rather low reactivity as an internal olefin and the conditions required for the reaction are different. Controlling skills are important.

In the present application, based on the above description, it is possible to provide a method for producing an aldehyde having high selectivity and conversion rate.

In addition, another exemplary embodiment of the present application includes the steps of preparing a C7 aldehyde according to the manufacturing method; and performing a hydrogenation reaction on the C7 aldehyde to prepare a C7 alcohol.

In an exemplary embodiment of the present application, the hydrogenation reaction of the C7 aldehyde uses a catalyst for the hydrogenation reaction, and the catalyst for the hydrogenation reaction includes at least one of ruthenium, copper, nickel, copper-zinc and platinum. can do.

In addition, the hydrogenation reaction of the C7 aldehyde may be performed in a hydrogenation reactor. The hydrogenation reactor is not particularly limited as long as it can fix the catalyst for the hydrogenation reaction described above. For example, a continuous stirred reactor (CSTR), a venturi-loop reactor, and a trickle-bed reactor, etc. is available.

In an exemplary embodiment of the present application, the C7 alcohol may be 5-methylhexanol.

A process diagram of a method for producing alcohol according to an exemplary embodiment of the present application is schematically shown in FIG. 1 below. As shown in FIG. 1 below, in an exemplary embodiment of the present application, C7 aldehyde may be prepared according to the method for preparing the aldehyde of the present application, and then C7 alcohol may be prepared by performing a hydrogenation reaction on the C7 aldehyde.

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>

1) Preparation of MIBK using acetone

After putting 190 g of acetone in the batch reactor, 10 g of a Pd-based catalyst (Pd content of 0.5 wt %) and 10 g of an ITSD material were added to the reactor. Then, methyl isobutyl ketone (MIBK) was prepared by performing a reaction for 3 to 6 hours under conditions of 120° C. and hydrogen (H ₂ ) 30 bar.

The conversion rate of acetone was 47%, and the selectivity of MIBK was more than 99%. The reaction result was obtained by using Agilent's 7890B equipment and analyzing it by gas chromatography (GC).

For each reaction step, an internal standard (ITSD) method was used to accurately calculate the reaction result. In each reaction step, n-heptane or n-decane was used as an ITSD material.

Conversion of starting material (%) = [(number of moles of reacted starting material)/(number of moles of supplied starting material)] × 100

Selectivity of target material (%) = [(number of moles of generated target material)/(number of moles of reacted starting material)] × 100

<GC analysis conditions>

① Column: HP-1 (L:100m, ID:0.25mm, film:0.5㎛)

② Injection volume: 1 μl

③ Inlet Temp.: 250℃, Pressure: 33.848psi, Total flow: 25.72ml/min, Split flow: 21.3ml/min, spilt ratio: 15:1

④ Column flow: 1.42ml/min

⑤ Oven temp.: 30℃/20min hold-20℃/min-300℃/20min hold (Total 53.5min)

⑥ Detector temp.: 300℃, H ₂ : 35ml/min, Air: 300ml/min, He: 20ml/min

⑦ GC Model: Agilent 7890B

2) Preparation of 4-methyl-2-pentanol

After separating acetone and the catalyst from MIBK from the solution prepared in 1) above, 100 g of MIBK, 1.5 g of Ru-based catalyst (Ru content 5 wt%), and 10 g of ITSD material (n-heptane) were mixed and put into a batch reactor. did. Thereafter, the reaction was carried out for 4 hours under conditions of 120° C. and 30 bar of hydrogen (H ₂ ) to prepare 4-methyl-2-pentanol.

The conversion rate of MIBK was 99.6%, and the selectivity of 4-methyl-2-pentanol was 99% or more.

3) Preparation of C6 Olefins

A trace amount of MIBK and the catalyst are separated from the solution prepared in 2) above, and 4-methyl-2-pentanol is injected at a flow rate of 0.062 ml/min using a pump and vaporized in a vaporizer heated to 160° C., a fixed bed The reactor was injected with 122 ml/min of N ₂ and 10 g of ITSD material (n-heptane). The fixed bed reactor had an inner diameter of 1 inch, was charged with 3 g of γ-alumina used as a catalyst, and was heated to a temperature of 200°C. The weight hourly space velocity (WHSV) of the reaction was about 1.0 h ⁻¹ . Through the above reaction, a mixture of 4-methyl-1-pentene and 4-methyl-2-pentene was prepared.

The conversion rate of 4-methyl-2-pentanol is 94%, the selectivity of 4-methyl-1-pentene is 42%, and the 4-methyl-2-pentene (4-methyl-2) -pentene) showed a selectivity of 58%.

4) Preparation of C7 aldehyde

4-methyl-1-pentene from the mixture of 4-methyl-1-pentene and 4-methyl-2-pentene prepared in 3) above separated and subjected to an oxo reaction of 4-methyl-1-pentene.

The oxo reaction of 4-methyl-1-pentene uses 200 g of tetraethylene glycol dimethyl ether (TEGDME) as a solvent, 10 g of 4-methyl-1-pentene, 0.05 g of Rh(acac)(CO) ₂ as a catalyst, and triphenyl as a ligand 2.4 g of triphenyl phosphite and 0.85 g of ITSD material (n-decane) were mixed. This mixed solution was put into a 0.5L buchi batch reactor and the temperature was raised to 90° C., and then synthesis gas in a molar ratio of CO/H ₂ =1:1 was added, and the reaction was carried out for 2 hours while maintaining the internal pressure at 10 bar. . The reaction was carried out to prepare 5-methylhexanal (5-methylhexanal).

As a result of the oxo reaction of 4-methyl-1-pentene, the conversion rate of 4-methyl-1-pentene was 99.7%, the selectivity of 5-methylhexanal was 88.5%, and the side reaction product (isomer 2.9%, 4-methyl-1 -pentane 8.6%) was 11.5%.

C7 alcohol can be prepared by performing a hydrogenation reaction on the C7 aldehyde (5-methylhexanal) prepared in the above Example. The hydrogenation reaction of the C7 aldehyde may use a method known in the art. More specifically, the hydrogenation reaction of the C7 aldehyde uses a catalyst for the hydrogenation reaction, and the catalyst for the hydrogenation reaction may include at least one of copper, nickel, copper-zinc and platinum.

As described above, according to an exemplary embodiment of the present application, it is possible to provide a novel aldehyde preparation method capable of using acetone as a starting material and finally preparing C7 aldehyde, using acetone as a starting material, and finally It is possible to provide a novel method for producing an alcohol capable of producing C7 alcohol.

Claims (11)

preparing methyl isobutyl ketone (MIBK) using acetone;
preparing a C6 olefin using the methyl isobutyl ketone; and
performing a hydroformylation reaction on the C6 olefin to prepare a C7 aldehyde
A method for producing an aldehyde comprising a. The method according to claim 1, wherein the step of preparing methyl isobutyl ketone using acetone,
performing a condensation reaction on the acetone to prepare diacetone alcohol (DAA);
performing a dehydration reaction on the diacetone alcohol to prepare mesityl oxide (MO); and
A method for producing an aldehyde comprising the step of preparing methyl isobutyl ketone by performing a hydrogenation reaction on the mesityl oxide. The method according to claim 2, wherein in the step of preparing methyl isobutyl ketone using acetone, the condensation reaction of acetone, the dehydration reaction of diacetone alcohol, and the hydrogenation reaction of mesityl oxide using a Pd-based catalyst are performed in one reactor A method for producing an aldehyde, which is carried out simultaneously in The method according to claim 1, wherein the step of preparing a C6 olefin using methyl isobutyl ketone,
performing a hydrogenation reaction on the methyl isobutyl ketone to prepare a C6 alcohol; and
A method for producing an aldehyde comprising the step of performing a dehydration reaction on the C6 alcohol to produce a C6 olefin. The method of claim 4, wherein the C6 alcohol is 4-methyl-2-pentanol. The method according to claim 1, wherein the C6 olefin comprises at least one of 4-methyl-1-pentene and 4-methyl-2-pentene. A method for the production of phosphorus aldehyde. The method according to claim 1, wherein the hydroformylation reaction of the C6 olefin is carried out by reacting the C6 olefin with synthesis gas in the presence of a catalyst composition for the hydroformylation reaction,
The catalyst composition for the hydroformylation reaction includes a phosphorus-based ligand; a transition metal compound represented by the following formula (1); And a method for producing an aldehyde comprising a solvent:
[Formula 1]
M(L1)x(L2)y(L3)z
In Formula 1,
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 hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) or acetylacetonato (AcAc),
Wherein x, y and z are each independently an integer of 0 to 5, and x, y and z are not 0 at the same time. The method according to claim 1, wherein the C7 aldehyde is 5-methylhexanal. Preparing a C7 aldehyde according to any one of claims 1 to 8; and
preparing C7 alcohol by performing a hydrogenation reaction on the C7 aldehyde
A method for producing alcohol comprising a. The method according to claim 9, wherein the hydrogenation reaction of the C7 aldehyde uses a catalyst for hydrogenation reaction,
The catalyst for the hydrogenation reaction is a method for producing an alcohol comprising at least one of ruthenium, copper, nickel, copper-zinc and platinum. The method of claim 9, wherein the C7 alcohol is 5-methylhexanol.

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