Patent Description:
A hydroformylation reaction of reacting various olefins with carbon monoxide (CO) and hydrogen (H<NUM>) commonly called as a synthetic gas under the presence of a homogeneous organometal catalyst and a ligand to produce a linear (normal) and branched (iso) aldehyde having the number of carbon atoms increased by one was first discovered by Otto Roelen of Germany in <NUM>.

The hydroformylation reaction, generally known as an oxo reaction, is an industrially very important reaction in a homogeneous catalyst reaction, and various aldehydes comprising alcohol derivatives are produced through the oxo process and consumed worldwide.

Various aldehydes synthesized through the oxo reaction are sometimes oxidized or hydrogenated after a condensation reaction such as an aldol, and modified to various acids and alcohols comprising a long alkyl group. Particularly, a hydrogenated alcohol of an aldehyde produced by such an oxo reaction is referred to as an oxo-alcohol, and the oxo-alcohol is widely used industrially as solvents, additives, raw materials of various plasticizers, synthetic lubricants and the like.

Catalysts currently used in the oxo process are mainly cobalt (Co) and rhodium (Rh) series, and normal/iso selectivity (ratio of linear (normal) to branched (iso) isomers) of the produced aldehyde varies depending on the types of ligand used and the operating conditions. Currently, <NUM>% or more of oxo plants around the world are adopting a low pressure oxo process using a rhodium-based catalyst.

As a central metal of the oxo catalyst, iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), nickel (Ni) and the like may be used in addition to cobalt (Co) and rhodium (Rh). However, each of the metals are known to exhibit catalytic activity in the order of Rh>>Co>Ir, Ru>Os>Pt>Pd>Fe>Ni and the like, and accordingly, most processes and studies are focused on rhodium and cobalt.

As the ligand, phosphine (PR<NUM>, R is C<NUM>H<NUM> or n-C<NUM>H<NUM>), phosphine oxide (O=P(C<NUM>H<NUM>)<NUM>), phosphite, amine, amide, isonitrile and the like may be used.

A representative example of hydroformylation comprises preparing octanol (<NUM>-ethylhexanol) from propylene using a rhodium-based catalyst.

Octanol is mainly used as a raw material of a PVC plasticizer such as DOP (dioctyl phthalate), and in addition thereto, is used as an intermediate material of synthetic lubricants, surfactants and the like. Propylene is introduced to an oxo reactor using a catalyst together with a synthetic gas (CO/H<NUM>) to produce normal-butyraldehyde and iso-butyraldehyde. The produced aldehyde mixture is sent to a separation system with a catalyst mixture and separated to a hydrocarbon and a catalyst mixture, and then the catalyst mixture is circulated to the reactor, and the hydrocarbon component is transferred to a stripper. The hydrocarbon of the stripper is stripped by a newly supplied synthetic gas to recover unreacted propylene and synthetic gas to the oxo reactor, and the butyraldehyde is transferred to a fractionating column and separated into normal- and iso-butyraldehyde. The normal-butyraldehyde at the bottom of the fractionating column is introduced to an aldol condensation reactor to produce <NUM>-ethylhexanal using a condensation and dehydration reaction, then transferred to a hydrogenation reactor, and octanol (<NUM>-ethylhexanol) is produced by hydrogenation. The reactants at the outlet of the hydrogenation reactor are transferred to a fractionating column, and after separating soft/hard ends, an octanol product is produced.

The hydroformylation reaction may be conducted continuously, semi-continuously or by the batch, and a typical hydroformylation reaction process is a gas or liquid recirculation system. In the hydroformylation reaction, it is important to increase reaction efficiency by allowing starting materials formed in liquid and gas phases to smoothly contact with each other. For this purpose, a continuous stirred tank reactor (CSTR) stirring components in liquid and gas phases to evenly contact with each other in the reactor has been mainly used in the art.

In this regard, most studies on the catalysts in the art have been conducted in the direction of increasing a ratio of a linear aldehyde derivative (normal-aldehyde) since the linear aldehyde derivative had a higher value among aldehydes produced by an oxo reaction. However, as demands for isoaldehydes have recently increased with the development of compounds using a branched aldehyde derivative (iso-aldehyde), for example, isobutyric acid, neopentyl glycol (NPG), <NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>-pentanediol, isovaleric acid and the like, studies in the direction of increasing selectivity of the branched aldehyde derivative have been continuously conducted.

<CIT> relates to a process of controlling heavies in a recycle catalyst stream, particularly, for use in a continuous hydroformylation process of converting an olefin with synthesis gas in the presence of a hydroformylation catalyst to form an aldehyde product stream with subsequent separation of the catalyst for recycling to the hydroformylation step. Heavies are controlled, and preferably reduced, by means of feeding a recycle gas stream, taken as a portion of an overhead stream from a condenser, back to a vaporizer wherein the aldehyde product stream is separated.

The present application is directed to providing a method for preparing an aldehyde.

The present application provides a method for preparing an aldehyde, the method comprising,.

A method for preparing an aldehyde according to the present application comprises recirculating at least a portion of low-boiling point components separated to an upper part of a vaporizer catch pot to the vaporizer catch pot. Accordingly, a concentration of high-boiling point components present in a section from the vaporizer catch pot to a hydroformylation reactor through a high-boiling point recirculation pipe can be lowered, a temperature of the solution can be lowered, and a residence time taken to reach the hydroformylation reactor can be reduced, and as a result, a content of an aldehyde dimer that can be synthesized in the section reaching the hydroformylation reactor through the high-boiling point recirculation pipe can be reduced.

According to the present application, the amount of produced aldehyde dimer can be reduced, and therefore, a reaction yield of the aldehyde preparation process can be enhanced.

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

In the present specification, a description of a certain member being placed "on" another member comprises not only a case of the certain member being in contact with the another member but a case of still another member being present between the two members.

In the present specification, a description of a certain part "comprising" certain constituents means capable of further comprising other constituents, and does not exclude other constituents unless particularly stated on the contrary.

As shown in <FIG>, butyraldehyde is produced when conducting hydroformylation with propylene, hydrogen and carbon monoxide under a catalyst. The produced butyraldehyde produced herein has a normal form and an iso form, and each of the two butyraldehydes may further go through an aldol reaction with each other to produce an aldehyde dimer. Particularly, aldehyde not discharged through a low-boiling point component pipe of a vaporizer after the hydroformylation reaction may produce an aldehyde dimer through an aldol reaction, and the produced aldehyde dimer causes a problem of reducing a reaction yield of a target aldehyde preparation process.

In addition, in a pipe recirculated from a vaporizer to a hydroformylation reactor, high-boiling point components are concentrated, and accordingly, in order to prevent catalyst precipitation, high-boiling point components are recirculated to the reactor comprising a certain amount of aldehyde under a condition of certain temperature or higher. During this process, an aldehyde dimer content increases causing a problem of a larger amount of aldehyde going through an aldol reaction.

In order to resolve the above-described problems, the present application attempts to reduce the amount of produced aldehyde dimer that may reduce a reaction yield of an aldehyde preparation process.

A method for preparing an aldehyde according to the present application comprises forming a reaction product comprising an aldehyde by reacting an olefin-based compound with a synthetic gas in a hydroformylation reactor (<NUM>) under a catalyst for a hydroformylation reaction; introducing the reaction product comprising an aldehyde to a vaporizer (<NUM>); separating low-boiling point components of the reaction product to an upper part of a vaporizer catch pot (<NUM>) comprised in the vaporizer (<NUM>), and separating high-boiling point components of the reaction product to a lower part of the vaporizer catch pot (<NUM>); and recirculating at least a portion of the low-boiling point components separated to an upper part of the vaporizer catch pot to the vaporizer catch pot, wherein a weight of the low-boiling point components recirculated to the vaporizer catch pot (<NUM>) is from <NUM> times to <NUM> times a weight of the high-boiling point components separated to a lower part of the vaporizer catch pot (<NUM>), wherein the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>) comprise an aldehyde dimer and the catalyst for a hydroformylation reaction, wherein the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>) are recirculated to the hydroformylation reactor (<NUM>), and wherein, based on a total weight of the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>), a content of the aldehyde dimer is <NUM>% by weight or less.

In one embodiment of the present application, the low-boiling point components separated to an upper part of the vaporizer catch pot may comprise an aldehyde, an unreacted olefin-based compound and a synthetic gas. Herein, at least a portion of the low-boiling point components separated to an upper part of the vaporizer catch pot is recirculated to the vaporizer catch pot. By recirculating at least a portion of the low-boiling point components separated to an upper part of the vaporizer catch pot to the vaporizer catch pot as above, the recirculated low-boiling point components are mixed with the high-boiling point components present in the vaporizer catch pot, which may reduce a concentration of the highboiling point components. Accordingly, the concentration of the high-boiling point components present in a section from the vaporizer catch pot to the hydroformylation reactor through the high-boiling point recirculation pipe may be reduced, a temperature of the solution may be lowered, and a residence time taken to reach the hydroformylation reactor may be reduced, and as a result, a content of an aldehyde dimer that may be synthesized in the section reaching the hydroformylation reactor through the high-boiling point recirculation pipe may be reduced.

In the present application, the weight of the low-boiling point components recirculated to the vaporizer catch pot may be <NUM> times to <NUM> times, and may be <NUM> time to <NUM> times the weight of the high-boiling point components separated to a lower part of the vaporizer catch pot. When satisfying the weight range of the low-boiling point components recirculated to the vaporizer catch pot, a content of an aldehyde dimer that may be synthesized in the section reaching the hydroformylation reactor through the high-boiling point recirculation pipe may be reduced.

In addition, when the weight of the low-boiling point components recirculated to the vaporizer catch pot is less than <NUM> times the weight of the high-boiling point components separated to a lower part of the vaporizer catch pot, an effect of reducing the amount of produced aldehyde dimer described above is insignificant, and the reaction yield may decrease by consuming an aldehyde that is a product of the hydroformylation reaction. In addition, when the weight of the low-boiling point components recirculated to the vaporizer catch pot is greater than <NUM> times the weight of the high-boiling point components separated to a lower part of the vaporizer catch pot, a concentration of the catalyst component introduced to the hydroformylation reactor through the high-boiling point recirculation pipe becomes too low reducing hydroformylation reactivity.

In the present application, the high-boiling point components separated to a lower part of the vaporizer catch pot comprise an aldehyde dimer and a catalyst for a hydroformylation reaction. Herein, the high-boiling point components separated to a lower part of the vaporizer catch pot are recirculated to the hydroformylation reactor. As described in <FIG>, the aldehyde dimer is produced by two aldehydes going through an aldol reaction with each other.

In the present application, by recirculating at least a portion of the low-boiling point components separated to an upper part of the vaporizer catch pot to the vaporizer catch pot, the recirculated low-boiling point components are mixed with the high-boiling point components present in the vaporizer catch pot, which may reduce a concentration of the highboiling point components.

In the present application, the aldehyde dimer content is <NUM>% by weight or less, may be <NUM>% by weight or less, and may be <NUM>% by weight or greater based on a total weight of the high-boiling point components separated to a lower part of the vaporizer catch pot. The aldehyde dimer content being greater than <NUM>% by weight based on a total weight of the highboiling point components separated to a lower part of the vaporizer catch pot is not preferred since the amount of produced aldehyde increases in the high-boiling point recirculation pipe, which may increase the aldehyde dimer content in the hydroformylation reactor.

In one embodiment of the present application, the vaporizer catch pot may have a temperature of <NUM> to <NUM>, and <NUM> to <NUM>. In addition, the vaporizer catch pot may have a pressure of atmospheric pressure to <NUM> bar, and atmospheric pressure to <NUM> bar. Herein, the atmospheric pressure means normal pressure, and means a pressure when not particularly increased or decreased. When satisfying the temperature range and the pressure range of the vaporizer catch pot, the aldehyde dimer content may be reduced.

In one embodiment of the present application, the catalyst for a hydroformylation reaction may comprise a phosphite ligand represented by the following Chemical Formula <NUM> and a transition metal compound represented by the following Chemical Formula <NUM>.

[Chemical Formula <NUM>]     M(L1)x(L2)y(L3)z.

In one embodiment of the present application, a content of the transition metal compound represented by Chemical Formula <NUM> may be from <NUM> moles to <NUM> moles, may be from <NUM> moles to <NUM> moles, and may be from <NUM> moles to <NUM> moles, based on <NUM> mole of the phosphite ligand represented by Chemical Formula <NUM>. When the content of the transition metal compound represented by Chemical Formula <NUM> satisfies <NUM> moles to <NUM> moles based on <NUM> mole of the phosphite ligand represented by Chemical Formula <NUM>, activity of the catalyst for the hydroformylation reaction may be superior, and the content being outside the above-mentioned range may cause a problem of reducing catalyst activity and stability.

The transition metal compound represented by Chemical Formula <NUM> may be one or more types selected from the group consisting of cobalt carbonyl (Co<NUM>(CO)<NUM>), rhodium acetylacetonato dicarbonyl (Rh(AcAc)(CO)<NUM>), rhodium acetylacetonato carbonyl triphenylphosphine (Rh(AcAc)(CO)(TPP)), hydridocarbonyl tri(triphenylphosphine)rhodium [HRh(CO)(TPP)<NUM>], iridium acetylacetonato dicarbonyl (Ir(AcAc)(CO)<NUM>) and hydridocarbonyl tri(triphenylphosphine)iridium (HIr(CO)(TPP)<NUM>).

In one embodiment of the present application, the olefin-based compound may be represented by the following Chemical Formula <NUM>.

In Chemical Formula <NUM>,
R<NUM> and R<NUM> are the same as or different from each other, and each independently hydrogen, an alkyl group, fluorine (F), chlorine (Cl), bromine (Br), trifluoromethyl (-CF<NUM>), or a substituted or unsubstituted aryl group.

The aryl group may be unsubstituted or substituted with one or more types of substituents of nitro (-NO<NUM>), fluorine (F), chlorine (Cl), bromine (Br), methyl, ethyl, propyl and butyl.

More specifically, the olefin-based compound may be one or more types selected from the group consisting of ethylene, propylene, <NUM>-butene, <NUM>-pentene, <NUM>-hexene, <NUM>-octene and styrene.

In one embodiment of the present application, the olefin-based compound may be propylene, and the aldehyde may be butyraldehyde.

In one embodiment of the present application, the hydroformylation reaction may be conducted using a method of dissolving the transition metal compound represented by Chemical Formula <NUM> and the phosphite ligand represented by Chemical Formula <NUM> in a solvent to prepare a mixed solution of the transition metal compound and the phosphite ligand, that is, a catalyst composition, injecting the olefin-based compound represented by Chemical Formula <NUM> and a synthetic gas together with the catalyst composition, and stirring the result while raising a temperature and applying a pressure.

The solvent may be one or more types selected from the group consisting of propane aldehyde, butyraldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, texanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane.

In one embodiment of the present application, the step of reacting the olefin-based compound with a synthetic gas in the hydroformylation reactor may be conducted at a temperature of <NUM> to <NUM> and a pressure of <NUM> bar to <NUM> bar, and may be conducted at a temperature of <NUM> to <NUM> and a pressure of <NUM> bar to <NUM> bar. When the temperature in the hydroformylation reaction step is lower than <NUM>, reactivity may significantly decrease, and when the temperature is higher than <NUM>, the content of heavies increases resulting in a decreased yield. In addition, when the pressure in the hydroformylation reaction step is less than <NUM> bar, reactivity may significantly decrease, and the pressure being greater than <NUM> bar has disadvantages in terms of cost and design of the apparatus.

In one embodiment of the present application, the olefin-based compound:the synthetic gas may have a molar ratio of <NUM>:<NUM> to <NUM>:<NUM>, and <NUM>:<NUM> to <NUM>:<NUM> in the hydroformylation reaction step. When the olefin-based compound:the synthetic gas have a molar ratio of <NUM>:<NUM> to <NUM>:<NUM> in the hydroformylation reaction step, activity of the catalyst for the hydroformylation reaction may be superior, and the molar ratio being outside the above-mentioned range may cause a problem of reducing catalyst activity and stability.

In addition, an apparatus for preparing an aldehyde suitable for the present invention comprises a hydroformylation reactor provided with a reactant supply pipe and a reaction product moving pipe; a vaporizer connected to the reaction product moving pipe of the hydroformylation reactor and provided with a vaporizer catch pot; a low-boiling point component pipe provided at an upper part of the vaporizer catch pot, and a high-boiling point component pipe provided at a lower part of the vaporizer catch pot; and a low-boiling point recirculation pipe connecting the low-boiling point component pipe and the vaporizer catch pot.

In one embodiment, a high-boiling point recirculation pipe connecting the high-boiling point component pipe and the hydroformylation reactor may be further comprised.

<FIG> schematically illustrates an apparatus for preparing an aldehyde suitable for the present invention, and <FIG> schematically illustrates an existing apparatus for preparing an aldehyde.

As illustrated in <FIG>, the apparatus for preparing an aldehyde suitable for the present invention comprises a hydroformylation reactor (<NUM>) provided with a reactant supply pipe (<NUM>) and a reaction product moving pipe (<NUM>); a vaporizer (<NUM>) connected to the reaction product moving pipe (<NUM>) of the hydroformylation reactor (<NUM>) and provided with a vaporizer catch pot (<NUM>); a low-boiling point component pipe (<NUM>) provided at an upper part of the vaporizer catch pot (<NUM>), and a high-boiling point component pipe (<NUM>) provided at a lower part of the vaporizer catch pot (<NUM>); and a low-boiling point recirculation pipe (<NUM>) connecting the low-boiling point component pipe (<NUM>) and the vaporizer catch pot (<NUM>). Herein, the apparatus for preparing an aldehyde may further comprise a high-boiling point recirculation pipe (<NUM>) connecting the high-boiling point component pipe (<NUM>) and the hydroformylation reactor (<NUM>). The vaporizer (<NUM>) and the vaporizer catch pot (<NUM>) may be directly connected to each other. For example, an outlet of the vaporizer (<NUM>) may become an inlet of the vaporizer catch pot (<NUM>).

Hereinafter, the present application will be described in detail with reference to examples in order to specifically describe the present application. Examples of the present application are provided in order to more fully describe the present application to those having average knowledge in the art.

As a catalyst, rhodium acetylacetonato carbonyl triphenylphosphine (Rh(AcAc)(COXTPP), ROPAC) and tris(<NUM>-tert-butyl-<NUM>-methylphenyl)phosphite (TTBMPP) were used.

A high-boiling point component solution comprising ROPAC and TTBMPP was dissolved in a butyraldehyde solution, a low-boiling point component, to prepare an aldehyde solution (<NUM>) having a concentration as in the following Table <NUM>, and the aldehyde solution was introduced to a <NUM> autoclave reactor. After introducing the aldehyde solution, inside the autoclave reactor was pressurized to <NUM> bar using nitrogen, and the reaction was conducted for <NUM> hours at <NUM> at a stirring rate of <NUM>,<NUM> rpm. The reaction solution was sampled every <NUM> minutes, and each content of the organic matters was analyzed by gas chromatography (GC).

Example <NUM> sets a condition of a vaporizer catch pot and a high-boiling point recirculation pipe. In other words, Example <NUM> sets a process condition in which at least a portion of the low-boiling point components separated to an upper part of a vaporizer catch pot is recirculated to the vaporizer catch pot. Herein, a weight of the low-boiling point components recirculated to the vaporizer catch pot was set to <NUM> times a weight of the high-boiling point components separated to a lower part of the vaporizer catch pot.

Preparation was made in the same manner as in Example <NUM> except that the weight of the low-boiling point components recirculated to the vaporizer catch pot was adjusted as in the following Table <NUM>.

Each of the reaction solutions according to the examples and the comparative example was sampled every <NUM> minutes, and each content of the organic matters was analyzed by gas chromatography. The content of the aldehyde dimer is shown in the following Table <NUM>, and the increased amount of the aldehyde dimer before and after the reaction is shown in <FIG>.

<NUM>) Column: HP-<NUM> (L: <NUM>, ID: <NUM>, film: <NUM>)
<NUM>) Injection volume: <NUM>µl
<NUM>) Inlet temp. : <NUM>, pressure: <NUM> kPa (<NUM> psi), total flow: <NUM>/min, split flow: <NUM>/min, split ratio: <NUM>:<NUM>
<NUM>) Column flow: <NUM>/min
<NUM>) Oven temp. : <NUM>/<NUM>-<NUM>/min-<NUM>/<NUM>
<NUM>) Detector temp. : <NUM>, H2: <NUM>/min, air: <NUM>/min, He: <NUM>/min
<NUM>) GC model: Agilent <NUM>.

From the results shown above, it was identified that, as the content of the aldehyde dimer is lower before the reaction, the content of the aldehyde dimer produced under the same condition decreased.

The method for preparing an aldehyde according to the present application comprises recirculating at least a portion of low-boiling point components separated to an upper part of a vaporizer catch pot to the vaporizer catch pot. Accordingly, a concentration of high-boiling point components present in a section from the vaporizer catch pot to a hydroformylation reactor through a high-boiling point recirculation pipe may be lowered, a temperature of the solution may be lowered, and a residence time taken to reach the hydroformylation reactor may be reduced, and as a result, a content of an aldehyde dimer that may be synthesized in the section reaching the hydroformylation reactor through the high-boiling point recirculation pipe may be reduced.

Claim 1:
A method for preparing an aldehyde, the method comprising:
forming a reaction product comprising an aldehyde by reacting an olefin-based compound with a synthetic gas in a hydroformylation reactor (<NUM>) under a catalyst for a hydroformylation reaction;
introducing the reaction product comprising the aldehyde to a vaporizer (<NUM>);
separating low-boiling point components of the reaction product to an upper part of a vaporizer catch pot (<NUM>) comprised in the vaporizer (<NUM>), and separating highboiling point components of the reaction product to a lower part of the vaporizer catch pot (<NUM>); and
recirculating at least a portion of the low-boiling point components separated to the upper part of the vaporizer catch pot (<NUM>) to the vaporizer catch pot (<NUM>),
wherein a weight of the low-boiling point components recirculated to the vaporizer catch pot (<NUM>) is from <NUM> times to <NUM> times a weight of the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>),
wherein the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>) comprises an aldehyde dimer and the catalyst for a hydroformylation reaction,
wherein the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>) is recirculated to the hydroformylation reactor (<NUM>), and
wherein, based on a total weight of the high-boiling point components separated to the lower part of the vaporizer catch pot (<NUM>), a content of the aldehyde dimer is <NUM>% by weight or less.