KR20220015126A - Hydroformylation process - Google Patents

Abstract

A hydroformylation method according to an exemplary embodiment of the present application includes a hydroformylation step of manufacturing an aldehyde by reacting a raw-C5 feed with a synthesis gas in the presence of a catalyst composition for a hydroformylation reaction. The hydroformylation method can reduce operating costs and investment costs.

Description

Hydroformylation method {HYDROFORMYLATION PROCESS}

This application relates to a hydroformylation process.

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 by Otto Roelen in Germany in 1938.

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

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

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, and the soft/hard ends are separated to produce an octanol product.

Although the octanol process accounts for a large proportion of alcohol production for plasticizers, it has two limitations as follows.

The first disadvantage of the octanol process is the continuous increase in raw material cost. Propylene, a raw material for the octanol process, is 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 complicated and thus the investment cost is high. The octanol process consists of three steps of 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 method. Since the existing octanol process cannot exclude these factors, it is necessary to develop a process for producing a new high-performance alcohol inexpensively, not octanol.

Republic of Korea Patent Publication No. 10-1150557

The present application provides a method for hydroformylation.

An exemplary embodiment of the present application is,

In the presence of a catalyst composition for hydroformylation reaction, a hydroformylation step of reacting a raw-C5 feed with a synthesis gas to produce an aldehyde,

The catalyst composition for the hydroformylation reaction includes a phosphine-based ligand represented by the following formula (1), a transition metal compound represented by the following formula (2), and a solvent,

The hydroformylation step is performed at a reaction temperature of 90 ° C. or higher and a reaction pressure of 15 bar or higher,

The raw-C5 feed is a product of a naphtha cracking center (NCC, Naphtha Cracking Center) process, and the raw-C5 feed is a mixture of terminal monoene, internal monoene and diene. It provides a hydroformylation method comprising the.

[Formula 1]

In Formula 1,

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

a to b are each independently an integer of 0 to 5;

[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 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.

According to an exemplary embodiment of the present application, the raw-C5 feed, which is a product of the Naphtha Cracking Center (NCC) process, may be directly applied to the hydroformylation reaction process. Accordingly, in the exemplary embodiment of the present application, there is an effect that can reduce the operating cost and investment cost compared to the prior art.

In addition, according to an exemplary embodiment of the present application, in the hydroformylation step, a catalyst composition including the phosphine-based ligand represented by Formula 1 is used, and the olefin in the raw-C5 feed is carried out at a specific reaction temperature and reaction pressure. There are features that can increase the conversion rate of

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

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

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

As described above, the octanol process occupies a large proportion of the production of alcohol for plasticizers, but there is a problem that the raw material cost is continuously rising and the investment cost is high due to the complexity of the process. Therefore, since the existing octanol process cannot exclude these factors, it is necessary to develop a process for inexpensively producing a new high-performance alcohol other than octanol.

Aldehydes used to make various alcohol and amine substances are mainly synthesized through the hydroformylation process of olefins, and the development of an economical hydroformylation process is very important for the commercialization of aldehyde production. Raw-C5, one of the products of the Naphtha Cracking Center (NCC) process, is traded cheaply at the price of naphtha, and has a high olefin content of 40% to 50% by weight, so it is converted to aldehyde through the hydroformylation process It is a raw material with high economic effect. However, when several types of olefins with different reaction characteristics (such as internal monoene, terminal monoene, diene, etc.) are mixed, such as raw-C5, it is difficult to aldehyde effectively under a single catalyst system, and analysis of reaction results is difficult. Because it is difficult, there is no related research.

Accordingly, in the present application, it is intended to provide a hydroformylation method capable of reducing operating costs and investment costs compared to the prior art while using a raw-C5 feed, and improving the conversion rate of olefins.

The hydroformylation method according to an exemplary embodiment of the present application includes a hydroformylation step of preparing an aldehyde by reacting a raw-C5 feed with a synthesis gas in the presence of a catalyst composition for the hydroformylation reaction, The catalyst composition for the hydroformylation reaction includes a phosphine-based ligand represented by the following formula (1), a transition metal compound represented by the following formula (2), and a solvent, and the hydroformylation step is performed at a reaction temperature of 90° C. or higher and a reaction pressure of 15 bar or higher. 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 diene. ) and a mixture of

[Formula 1]

In Formula 1,

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

a to b are each independently an integer of 0 to 5;

[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 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, 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 (1-pentene), 2-methyl-1-butene (2-methyl-1-butene), 3-methyl-1-butene (3 -methyl-1-butene), cyclopentene, etc. may be included. In addition, the C5 internal monoene may include 2-pentene, 2-methyl-2-butene, and the like. In addition, the C5 diene is isoprene (isoprene), 1,3-pentadiene (1,3-pentadiene), 1,4-pentadiene (1,4-pentadiene), 2-methyl-1-butene-3-yne (2-methyl-1-buten-3-yne) and the like.

In an exemplary embodiment of the present application, based on the total weight of the mixture of terminal monoene, internal monoene, and diene, the content of the diene may be 30% by weight or more, and , may be 40 wt% to 80 wt%.

In the exemplary embodiment of the present application, 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, 1-ethylbutyl group and the like, but is not limited thereto.

In an exemplary embodiment of the present application, Chemical Formula 1 may be represented by Chemical Formula 3 below.

[Formula 3]

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 tetraethylene glycol dimethyl ether, propane aldehyde, butyl aldehyde, pentyl aldehyde, valer aldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, thesanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane.

In an exemplary embodiment of the present application, the hydroformylation step may be performed at a reaction temperature of 90°C or higher, and may be performed at a reaction temperature of 90°C to 120°C. When the reaction temperature of the hydroformylation step is less than 90° C., the energy required for the reaction is not sufficiently supplied, so that the conversion of olefin molecules with low reactivity, such as internal monoene or diene, may occur slowly or hardly occur. In addition, even for terminal monoene, the reaction time required for conversion becomes too long, and production efficiency may decrease. In addition, when the reaction temperature of the hydroformylation step exceeds 120° C., thermal decomposition of the ligand molecule is performed, which is not preferable because the catalyst may not function normally.

In an exemplary embodiment of the present application, the hydroformylation step may be performed at a reaction pressure of 15 bar or more, and may be performed at a reaction pressure of 20 bar to 40 bar. When the reaction pressure of the hydroformylation step is 15 bar or more, the equivalent of the synthesis gas is sufficiently large compared to the olefin, so that the hydroformylation reaction equilibrium is favorable for the forward reaction. In addition, C5 olefin molecules having a low boiling point exist in a liquid phase even at a high temperature, which may be advantageous for contact with the catalyst in the reaction solution. In addition, when the reaction pressure of the hydroformylation step is less than 15 bar, conversion of olefin molecules with low reactivity such as internal monoene or diene may occur slowly or hardly occur. In addition, if the reaction pressure of the hydroformylation step exceeds 40 bar, there is no problem in the reaction, but 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, so it is not preferable .

In an exemplary embodiment of the present application, in the hydroformylation step, the molar ratio of the raw-C5 feed:syngas 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 5:95 to 70:30, and 40:60 to 60:40.

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>

The C5 stream solution collected from the Daesan NCC plant of LG Chem and the catalyst precursor, ligand, and solvent were mixed in a predetermined ratio and put into a pressure reactor (capacity: 500 mL). Rhacac(CO) ₂ as a catalyst precursor, 1,2-bis(diphenylphosphino)ethane (DPPE) as a ligand, and tetraethylene glycol dimethyl ether ( Tetraethylene glycol dimethyl ether, TEGDME) was used, respectively. C5 stream solution : catalyst precursor : ligand : solvent = 10 g : 0.1 g : 2 g : 100 g was added. The composition of the C5 stream solution is the same as in Table 1 above.

The reaction solution was stirred at 1,000 rpm and the inside of the reactor was purged with nitrogen atmosphere. When the purging was completed, the temperature inside the reactor was heated to 100°C. After reaching the reaction temperature, synthesis gas (CO/H ₂ = 1/1) was introduced 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 the gas inside the reactor.

<Examples 2 to 3 and Comparative Examples 1 to 5>

Except for applying the ligand, reaction temperature, and reaction pressure described in Table 2 below, the same procedure as in Example 1 was carried out.

[Table 2]

DPPE: 1,2-bis(diphenylphosphino)ethane

Xantphos: 4,5-bis(diphenylphosphino)

BIPHEPHOS: 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]dioxaphosphepin)

TPP: Triphenylphosphine

<Experimental example>

After completion of the reaction according to Examples and Comparative Examples, the reaction solution was collected and the olefin conversion rate and aldehyde selectivity were calculated through gas chromatography (GC). The results are shown in Table 3 below.

The 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 reacted C5 olefins)/(number of moles of C5 olefins present in the feed raw-C5 feed)] × 100

Aldehyde selectivity (%) = [(number of moles of produced C6 aldehydes)/(number of moles of reacted C5 olefins)] × 100

<GC analysis conditions>

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

② Injection volume: 1 μl

③ Inlet Temp.: 250 ℃, Pressure: 6.92psi, Total flow: 64.2ml/min, Split flow: 60ml/min, spilt ratio: 50:1

④ Column flow: 1.2ml/min

⑤ Oven temp.: 50℃/3min-10℃/min-280℃/41min (Total 67min)

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

⑦ GC Model: Agilent 6890

[Table 3]

As shown in Table 3 above, Examples 1 to 3 using DPPE as a ligand according to an exemplary embodiment of the present application are olefin conversion and aldehyde selectivity compared to Comparative Examples 1 to 3 using Xantphos, BIPEPHOS and TPP as ligands, respectively It can be seen that is excellent.

In particular, as shown in the results of Examples 1 to 3, at the same time as using DPPE as a ligand, at a reaction temperature of 100 ° C to 120 ° C and a reaction pressure of 20 bar to 40 bar, 75% or more of olefin conversion and 60% or more of aldehyde selectivity. can be checked However, as in Comparative Examples 4 and 5, it can be confirmed that even when DPPE is used as a ligand, the hydroformylation reaction does not proceed well at a reaction temperature of less than 90° C. or a reaction pressure of less than 15 bar.

Therefore, according to an exemplary embodiment of the present application, the raw-C5 feed, a product of the naphtha cracking center (NCC, Naphtha Cracking Center) process, can be directly applied to the hydroformylation reaction process. Accordingly, in the exemplary embodiment of the present application, there is an effect that can reduce the operating cost and investment cost compared to the prior art.

In addition, according to an exemplary embodiment of the present application, in the hydroformylation step, a catalyst composition including the phosphine-based ligand represented by Formula 1 is used, and the olefin in the raw-C5 feed is carried out at a specific reaction temperature and reaction pressure. There are features that can increase the conversion rate of

Claims (8)

In the presence of a catalyst composition for hydroformylation reaction, a hydroformylation step of reacting a raw-C5 feed with a synthesis gas to produce an aldehyde,
The catalyst composition for the hydroformylation reaction includes a phosphine-based ligand represented by the following formula (1), a transition metal compound represented by the following formula (2), and a solvent,
The hydroformylation step is performed at a reaction temperature of 90 ° C. or higher and a reaction pressure of 15 bar or higher,
The raw-C5 feed is a product of a naphtha cracking center (NCC, Naphtha Cracking Center) process, and the raw-C5 feed is a mixture of terminal monoene, internal monoene, and diene. A method for hydroformylation comprising:
[Formula 1]

In Formula 1,
R1 to R4 are the same as or different from each other, and are each independently hydrogen or an alkyl group;
a to b are each independently an integer of 0 to 5;
[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 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, based on the total weight of the mixture of terminal monoene (terminal monoene), internal monoene (internal monoene) and diene (diene), the content of the diene is 30% by weight or more hydroformylation method . The method according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 3: Hydroformylation method:
[Formula 3]

The method according to claim 1, wherein the transition metal compound is cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonylrhodium [Rh(AcAc)(CO) ₂ ], acetylacetonatocarbonyltriphenylphosphine Rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium[HRh(CO)(TPP) ₃ ], acetylacetonatodicarbonyliridium[Ir(AcAc)( CO) ₂ ], one of hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP) ₃ ] and chloro(1,5-cyclooctadiene)rhodium [Rh(COD)Cl ₂ ] A hydroformylation method comprising the above. The method according to claim 1, wherein the hydroformylation step is performed at a reaction temperature of 100 ℃ to 120 ℃ hydroformylation method. The method according to claim 1, wherein the hydroformylation step is carried out at a reaction pressure of 20 bar to 40 bar hydroformylation method. The method according to claim 1, wherein the raw-C5 feed: the molar ratio of the syngas is 95: 5 to 5: 95 will be the hydroformylation method. The method according to claim 1, wherein the synthesis gas comprises carbon monoxide and hydrogen,
The molar ratio of carbon monoxide: hydrogen is 5: 95 to 70: 30 of the hydroformylation method.