KR20230115562A - Method for producing aldehyde - Google Patents

Abstract

A method for producing aldehyde according to an exemplary embodiment of the present application includes C6 aldehyde, unreacted raw-C5, and a catalyst solution by reacting raw-C5 feed with synthesis gas in the presence of a catalyst solution for hydroformylation reaction. Preparing a first reaction product to; preparing a second reaction product including C6 aldehyde and unreacted raw-C5 by separating a catalyst solution from the first reaction product at a temperature of 80° C. to 130° C. and a pressure of 3 bar or less; and separating C6 aldehyde from the second reaction product at a temperature of 30° C. to 130° C. and a pressure of 0.1 bar or more.

Description

Method for producing aldehyde {METHOD FOR PRODUCING ALDEHYDE}

This application relates to a method for preparing aldehydes.

Various olefins are reacted with carbon monoxide (CO), commonly referred to as a synthesis gas, and hydrogen (H ₂ ) in the presence of a homogeneous organometallic catalyst and a ligand to produce linear, normal, and branched, iso ) The hydroformylation reaction that produces aldehydes was first discovered by Otto Roelen in Germany in 1938.

A hydroformylation reaction, generally known as an 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 sometimes transformed into various acids and alcohols containing long alkyl groups by oxidation or hydrogenation after a condensation reaction such as aldol. In particular, hydrogenated alcohol of aldehyde by the oxo reaction is called oxoalcohol, and oxoalcohol is widely used industrially for 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 ( iso) isomers) are different. Currently, more than 70% of OXO factories around the world adopt the Low Pressure OXO Process with a rhodium-based catalyst.

In addition to cobalt (Co) and rhodium (Rh), the central metals of the oxo catalyst include iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), and nickel (Ni). ), etc. can be applied. However, since each metal is known to show 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.

As the ligand, phosphine (PR ₃ , R is C ₆ H ₅ , or nC ₄ H ₉ ), phosphine oxide (O=P(C ₆ H ₅ ) ₃ ), phosphite, Amine, amide, isonitrile, etc. are applicable.

A representative example of hydroformylation is the production of 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 introduced into the oxo reactor using a catalyst together with synthesis gas (CO/H ₂ ) to produce normal-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, and then the catalyst mixture is circulated to the reactor and the hydrocarbon component is transferred to the stripper. The hydrocarbons of the stripper are stripped by the newly supplied synthesis gas, and unreacted propylene and synthesis gas are recovered to the oxo reactor, and butyraldehyde is transferred to the fractionation column and separated into normal- and iso-butylaldehyde, respectively. Normal-butylaldehyde at the bottom of the fractionation column is introduced into the aldol condensation reactor to produce 2-ethylhexanal through condensation and dehydration, and then transferred to the hydrogenation reactor, where octanol (2-ethylhexanol) is produced by hydrogenation. do. The reactants at the outlet of the hydrogenation reactor are transferred to a fractionation tower, and octanol products are produced after separating the soft/hard ends.

The octanol process accounts for a large portion of plasticizer alcohol production, but has the following two limitations.

The first drawback of the octanol process is the continued rise in raw material costs. Propylene, a raw material of the octanol process, is also in high demand as a raw material for other polymers such as polypropylene, and its price continues to rise. The second disadvantage of the octanol process is that the process is complex and the investment cost is high. The octanol process consists of three steps: hydroformylation, dimer formation, and hydrogenation, and the hydroformylation is carried out in a continuous manner requiring two or more pressure reactors rather than a simple batch process. Since the existing octanol process cannot exclude these factors, it is necessary to develop a process for producing a new high-performance alcohol other than octanol at low cost.

Republic of Korea Patent Registration No. 10-1150557

This application is intended to provide a method for preparing aldehydes.

An exemplary embodiment of the present application,

preparing a first reaction product including C6 aldehyde, unreacted raw-C5, and a catalyst solution by reacting raw-C5 feed with synthesis gas in the presence of a catalyst solution for hydroformylation reaction;

preparing a second reaction product including C6 aldehyde and unreacted raw-C5 by separating a catalyst solution from the first reaction product at a temperature of 80° C. to 130° C. and a pressure of 3 bar or less; and

Separating C6 aldehyde from the second reaction product at a temperature of 30 ° C to 130 ° C and a pressure of 0.1 bar or more

It provides a method for producing an aldehyde comprising a.

According to an exemplary embodiment of the present application, raw-C5 feed is directly subjected to the hydroformylation reaction process without separating specific olefins from the raw-C5 feed, which has no special use as a by-product of the Naphtha Cracking Center (NCC) process can be applied Accordingly, in one embodiment of the present application, there is an effect of creating high added value by using a low-cost feed compared to the prior art during the manufacturing process of aldehyde.

In addition, according to an exemplary embodiment of the present application, the purity of C6 aldehyde produced can be improved, and unreacted raw-C5 can be recycled or vaporized in a separate chemical process to be used as a fuel.

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

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 the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

As a method of utilizing raw-C5, a product of the Naphtha Cracking Center (NCC) process, conventionally, it is limited to separating/purifying components such as CPD (cyclopentadiene) and DCPD (dicyclopentadiene) from raw-C5. There is, and the remaining raw-C5 component from which the active ingredient is separated was not suitable for use.

Accordingly, the present application intends to provide a technology for generating and separating C6 aldehyde through hydroformylation of olefins present in raw-C5.

A method for producing aldehyde according to an exemplary embodiment of the present application includes C6 aldehyde, unreacted raw-C5, and a catalyst solution by reacting raw-C5 feed with synthesis gas in the presence of a catalyst solution for hydroformylation reaction. Preparing a first reaction product to; preparing a second reaction product including C6 aldehyde and unreacted raw-C5 by separating a catalyst solution from the first reaction product at a temperature of 80° C. to 130° C. and a pressure of 3 bar or less; and separating C6 aldehyde from the second reaction product at a temperature of 30° C. to 130° C. and a pressure of 0.1 bar or more.

In one embodiment of the present application, the raw-C5 feed is a product of a Naphtha Cracking Center (NCC) process, and the raw-C5 feed is terminal monoene, internal monoene ) and mixtures of dienes.

In one embodiment of the present application, specific components of the raw-C5 feed are shown in Table 1 below.

[Table 1]

In an exemplary embodiment of the present application, the C5 terminal monoene is 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene (3 -methyl-1-butene), cyclopentene, and the like. In addition, the C5 internal monoene may include 2-pentene, 2-methyl-2-butene, and the like. In addition, the C5 diene is isoprene, 1,3-pentadiene (1,3-pentadiene), 1,4-pentadiene (1,4-pentadiene), 2-methyl-1-butene-3-in (2-methyl-1-buten-3-yne) and the like.

In one embodiment of the present application, based on the total weight of the mixture of the terminal monoene, internal monoene, and diene, the content of the diene may be 30% by weight or more, , It may be 40% by weight to 80% by weight, and may be 45% by weight to 75% by weight. Internal monoene with relatively low reactivity when the content of the diene is less than 30% by weight based on the total weight of the mixture of the terminal monoene, internal monoene and diene It is not preferable because the olefin conversion rate in the raw-C5 feed may be lowered because the content of

In one embodiment of the present application, the catalyst solution for the hydroformylation reaction includes a phosphorus-based ligand; transition metal compounds; and a solvent.

In one embodiment of the present application, the transition metal compound may be represented by Formula 1 below.

[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 (acetylacetonato, AcAc),

The 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 transition metal compound is cobaltcarbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonylodium [Rh(AcAc)(CO) ₂ ], acetylacetonatocarbonyl Triphenylphosphine rhodium [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 them.

In an exemplary embodiment of the present application, the solvent is tetraethylene glycol dimethyl ether, propane aldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, It may include one or more of pentanol, octanol, tensanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride, and heptane.

In one embodiment of the present application, the phosphorus ligand is 1,2-bis (diphenylphosphino) ethane, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, triphenylphosphine , tris(2,4-di-tert-butylphenyl)phosphite, cyclohexyldiphenylphosphine, triphenylphosphite and 6,6'-[(3,3'-di-tert-butyl-5,5 At least one of '-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine) can include

In one embodiment of the present application, the step of preparing the first reaction product may be carried out at a reaction temperature of 90 ° C or higher and a reaction pressure of 15 bar or higher, a reaction temperature of 90 ° C to 130 ° C, and a reaction of 15 bar to 75 bar can be performed under pressure.

When the reaction temperature is less than 90° C., conversion of olefin molecules having low reactivity such as internal monoene or diene may occur slowly or hardly occur because sufficient energy required for the reaction is not supplied. In addition, even for terminal monoene, the reaction time required for conversion is too long, and thus the production efficiency may decrease. In addition, when the reaction temperature exceeds 130° C., the ligand molecule is thermally decomposed and the catalyst may not function normally, which is undesirable.

When the reaction pressure is 15 bar or more, the equilibrium of the syngas is sufficiently large compared to the olefin, so that conditions favorable to the hydroformylation reaction equilibrium can be created. In addition, C5 olefin molecules having a low boiling point exist in a liquid phase even at high temperatures, which may be advantageous for contact with the catalyst in the reaction solution. In addition, when the reaction pressure is less than 15 bar, conversion of olefin molecules having low reactivity such as internal monoene or diene may occur slowly or hardly occur. In addition, when the reaction pressure exceeds 75 bar, additional investment costs such as strengthening the reactor for the high-pressure process may occur, and the risk of the high-pressure process may increase, which is not preferable.

In one embodiment of the present application, the step of preparing a second reaction product including C6 aldehyde and unreacted raw-C5 by separating the catalyst solution from the first reaction product is at a temperature of 80 ° C to 130 ° C, and It may be performed under a pressure condition of 3 bar or less, and may be performed at a temperature of 100 ° C to 125 ° C and a pressure condition of 0 to 1.5 bar. When the temperature exceeds 130° C., a structural change of the catalytic component such as rhodium in the catalytic solution may occur due to heat, and thus reactivity may be reduced, which is not preferable. In addition, when the temperature is lower than 80° C., separation of C6 aldehyde and raw-C5 components by vaporization may not occur sufficiently, which is not preferable.

In one embodiment of the present application, the catalyst solution separated in the step of preparing the second reaction product may be recycled to the step of preparing the first reaction product.

In one embodiment of the present application, the step of separating C6 aldehyde from the second reaction product may be performed at a temperature of 30 ° C to 130 ° C and a pressure of 0.1 bar or more, and at a temperature of 30 ° C to 130 ° C, And it may be performed under pressure conditions of 0.3 bar to atmospheric pressure.

More specifically, the step of separating the C6 aldehyde from the second reaction product may be performed in a multi-stage distillation column, wherein the temperature of the top of the multi-stage distillation column may be 30 ° C to 70 ° C, and the multi-stage distillation column The temperature of the lower end (bottom) of may be 90 ℃ to 130 ℃. When the temperature of the upper part of the multi-stage distillation column exceeds 70° C., C6 aldehyde may reach the upper part and thus loss of production may occur, which is undesirable. In addition, when the temperature at the upper end of the multi-stage distillation column is less than 30° C., unreacted raw-C5 may exist at the lower end of the multi-stage distillation column, which is undesirable because the purity of C6 aldehyde may be lowered. In addition, when the temperature at the lower end of the multi-stage distillation column exceeds 130° C., there is a possibility that C6 aldehyde may be dimerized, which is not preferable. In addition, when the temperature at the lower end of the multi-stage distillation column is less than 90° C., unreacted raw-C5 components may not sufficiently vaporize, which is not preferable.

The number of theoretical stages of the multi-stage distillation column is not particularly limited, but if the number of theoretical stages is increased, the recovery rate and resolution can be further increased, and those skilled in the art can appropriately select them.

In the step of separating C6 aldehyde from the second reaction product, C6 aldehyde and unreacted raw-C5 may be separated from each other from the second reaction product, and the separated C6 aldehyde and unreacted raw-C5 are used respectively. Depending on the product, it can be applied to the product or recycled for other chemical processes.

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

In one embodiment of the present application, the molar ratio of the raw-C5 feed: 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 carbon monoxide:hydrogen molar ratio may be 5:95 to 70:30 or 40:60 to 60:40. When the molar ratio of carbon monoxide: hydrogen is satisfied, the olefin conversion rate in the raw-C5 feed can be further improved.

Hereinafter, examples will be described in detail in order to specifically describe the present application. However, embodiments according to the present application may be modified in many different forms, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present application to those skilled in the art.

<Example>

<Example 1>

A C5 stream solution collected from LG Chem's Daesan NCC plant, a catalyst precursor, a ligand, and a solvent were mixed at a predetermined ratio and put into a pressure reactor (capacity: 500 mL). Rhacac(CO) ₂ was used as a catalyst precursor, 1,2-bis(diphenylphosphino)ethane (DPPE) was used as a ligand, and C6 aldehyde was used as a solvent. . The C5 stream solution: catalyst precursor: ligand: solvent = 10 g: 0.1 g: 2 g: 100 g was introduced. Components of the C5 stream solution are the same as those in Table 1 above.

While stirring the reaction solution at 700 rpm, the inside of the reactor was purged with a nitrogen atmosphere. When purging was completed, the temperature inside the reactor was heated to 120°C. After reaching the reaction temperature, synthesis gas (CO/H ₂ = 1/1) was injected into the reactor at 40 bar to initiate the hydroformylation reaction. After maintaining the hydroformylation reaction conditions for 12 hours, the reactor was cooled to room temperature and the reaction was terminated by removing gas inside the reactor.

<Experimental Example 1>

After completion of the reaction according to Example 1, the final reaction solution was collected and olefin conversion and aldehyde selectivity were calculated through gas chromatography (GC). The results are shown in Table 2 below.

The C5-olefin conversion rate was calculated through the total consumption ratio of C5 olefins present in the raw-C5 feed before and after the reaction. In addition, the aldehyde selectivity was calculated as the amount of total C6 aldehydes produced after the reaction compared to the consumption of all C5 olefins present in the raw-C5 feed.

Olefin conversion (%) = [(number of moles of C5 olefins reacted) / (number of moles of C5 olefins present in the raw-C5 feed fed)] × 100

Aldehyde selectivity (%) = [(Number of moles of C6 aldehydes produced)/(Number of moles of C5 olefins reacted)] x 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: 34.46psi, Total flow: 32.8ml/min, Split flow: 28.4ml/min, spill ratio: 20:1

④ Column flow: 1.4ml/min

⑤ Oven temp.: 35℃, 20min(hold) / 170℃, 2℃/min / 300℃, 10℃/min 20min(hold) (Total 120min)

⑥ Detector temp.: 250℃, H2: 30ml/min, Air: 300ml/min, He: 25ml/min

⑦ GC Model: Agilent 7890B

[Table 2]

<Experimental Example 2>

The composition of the first reaction product of the hydroformylation reaction obtained from the reaction result of Example 1 was confirmed, and the results in Tables 3 and 4 were obtained by simulation using this. In Table 3 below, the feed is the sum of syngas and catalyst recycle in the process, and pure raw-C5 is the result of simulation based on 10g input. The catalyst recycle stream contains C6 aldehyde and joins the feed stream. The first reaction product is a value after exhausting a part of the syngas, and aldehyde appears as a major component. Here, the second reaction product is obtained by separating the C6 aldehyde and the unreacted raw-C5 component. At this time, the simulation conditions were set to a temperature of 80 ℃ to 130 ℃, and a pressure condition of 0 to 1.5 bar.

ASPEN plus (a process simulation program) was used for the simulation.

[Table 3]

The second reaction product undergoes syngas degassing, and is transferred to a multi-stage distillation tower to be separated. C6 aldehyde may be recovered from the bottom of the multi-stage distillation column. The multi-stage distillation column was set to 7 theoretical stages, and the recovery rate was set to 77.5%. In addition, the temperature of the top of the multi-stage distillation column was set to 30 ° C to 70 ° C, the temperature of the bottom of the multi-stage distillation column was set to 90 ° C to 130 ° C, and the pressure was set to 0.3 bar to atmospheric pressure. did

[Table 4]

As a result, according to an exemplary embodiment of the present application, the raw-C5 feed is directly hydrous without separating a specific olefin from the raw-C5 feed, which has no special use as a by-product of the Naphtha Cracking Center (NCC) process. It can be applied to the formylation reaction process. Accordingly, in one embodiment of the present application, there is an effect of creating high added value by using a low-cost feed compared to the prior art during the manufacturing process of aldehyde.

In addition, according to an exemplary embodiment of the present application, the purity of C6 aldehyde produced can be improved, and unreacted raw-C5 can be recycled or vaporized in a separate chemical process to be used as a fuel.

Claims (13)

preparing a first reaction product including C6 aldehyde, unreacted raw-C5, and a catalyst solution by reacting raw-C5 feed with synthesis gas in the presence of a catalyst solution for hydroformylation reaction;
preparing a second reaction product including C6 aldehyde and unreacted raw-C5 by separating a catalyst solution from the first reaction product at a temperature of 80° C. to 130° C. and a pressure of 3 bar or less; and
Separating C6 aldehyde from the second reaction product at a temperature of 30 ° C to 130 ° C and a pressure of 0.1 bar or more
Method for producing an aldehyde comprising a. The method according to claim 1, wherein the raw-C5 feed is a product of a Naphtha Cracking Center (NCC) process,
The raw-C5 feed is a method for producing an aldehyde comprising a mixture of terminal monoene, internal monoene and diene. The method according to claim 2, wherein the content of the diene is 30% by weight or more based on the total weight of the mixture of the terminal monoene, the internal monoene, and the diene. . The method of claim 1, wherein the catalyst solution for the hydroformylation reaction includes a phosphorus ligand, a transition metal compound, and a solvent. The method according to claim 4, wherein the transition metal compound is cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonato dicarbonyl rhodium [Rh (AcAc) (CO) ₂ ], acetylacetonatocarbonyltriphenylphosphine Rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium[HRh(CO)(TPP) ₃ ], acetylacetonatedicarbonyliridium[Ir(AcAc)( CO) ₂ ], one of hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP) ₃ ] and chloro(1,5-cyclooctadiene)rhodium [Rh(COD)Cl ₂ ] A method for producing an aldehyde comprising the above. The method according to claim 4, wherein the phosphorus ligand is 1,2-bis (diphenylphosphino) ethane, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, triphenylphosphine, tris (2 ,4-di-tert-butylphenyl)phosphite, cyclohexyldiphenylphosphine, triphenylphosphite and 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy -1,1'-biphenyl-2,2'-diyl) bis (oxy)] bis (dibenzo [d, f] [1,3,2] dioxaphosphepine) containing at least one kind Method for producing phosphorus aldehyde. The method of claim 1, wherein the step of preparing the first reaction product is performed at a reaction temperature of 90° C. or higher and a reaction pressure of 15 bar or higher. The method of claim 1, wherein the pressure in the step of preparing the second reaction product is 0 to 1.5 bar. The method of claim 1, wherein the catalyst solution separated in the step of preparing the second reaction product is recycled to the step of preparing the first reaction product. The method according to claim 1, wherein the step of separating the C6 aldehyde from the second reaction product is performed in a multi-stage distillation column,
The temperature of the top of the multi-stage distillation column is 30 ° C to 70 ° C,
Method for producing aldehyde, wherein the temperature of the bottom of the multi-stage distillation column is 90 ° C to 130 ° C. The method of claim 1, wherein the pressure in the step of separating the C6 aldehyde from the second reaction product is 0.3 bar to atmospheric pressure. The method according to claim 1, wherein the raw-C5 feed: syngas molar ratio is 95:5 to 5:95. The method according to claim 1, wherein the synthetic gas includes carbon monoxide and hydrogen,
The carbon monoxide:hydrogen molar ratio is 5:95 to 70:30.