KR101005640B1 - Method and apparatus for preparation of aldehyde - Google Patents

Abstract

The present invention is a method for producing an aldehyde by hydroformylation of a synthesis gas containing carbon monoxide and hydrogen with at least one olefin under a hydroformylation catalyst, and isomerization reaction to the aldehyde produced above. It relates to an aldehyde manufacturing method and apparatus characterized in that by adjusting the ratio of linear aldehyde and branched aldehyde. The aldehyde manufacturing method according to the present invention can adjust the ratio of linear aldehyde or branched aldehyde, it is possible to selectively prepare the aldehyde used as a raw material of various products.

Hydroformylation, olefins, aldehydes, isomerization reactions

Description

Method and apparatus for preparing aldehydes {METHOD AND APPARATUS FOR PREPARATION OF ALDEHYDE}

1 and 2 are diagrams showing a process diagram of an embodiment according to the present invention.

<Explanation of symbols for the main parts of the drawings>

10: olefin and syngas feed line 20: recycle catalyst feed line

30: hydroformylation reactor 40: first reaction product discharge line

50 isomerization reactor 60: second reaction product discharge line

70: catalyst separation device 80: flow control device

90: final product discharge line 100: second reaction product transfer line

The present invention relates to a method and apparatus for producing aldehyde by hydroformylation reaction of at least one olefin with a synthesis gas containing carbon monoxide and hydrogen under a hydroformylation catalyst.

Hydroformylation reactions, commonly known as OXO reactions, react with various olefins and synthetic gases (CO / H ₂ ) in the presence of metal catalysts and ligands, resulting in an increase in the number of carbon atoms in the olefin by one or more. Refers to the process by which linear and branched aldehydes are produced.

The oxo reaction was first discovered by Otto Roelen of Germany in 1938. As of 2001, about 8.9 million tons of various aldehydes (including alcohol derivatives) are produced and consumed through the oxo process worldwide ( SRI report, November). 2002, 682. 700 A). Various aldehydes synthesized by the oxo reaction are transformed into aldehyde derivatives acid and alcohol through oxidation or reduction. In addition, after the condensation reaction of aldol (aldol) and the like through the oxidation or reduction reaction may be transformed into various acids and alcohols containing a long alkyl group. Such alcohols and acids are used as solvents, additives, and raw materials for various plasticizers.

Currently, catalysts used in the oxo process are mainly cobalt (Co) and rhodium (Rh) series, and the linear or branched selectivity of the aldehyde produced varies depending on the type of ligand and the operating conditions. More than 70% of the world's oxo plants employ a low pressure OXO process with rhodium-based catalysts.

According to the present invention, an aldehyde is formed by hydroformylation reaction of at least one olefin with a synthesis gas containing carbon monoxide and hydrogen under a hydroformylation catalyst capable of controlling the ratio of linear aldehyde and branched aldehyde produced through hydroformylation. It is intended to provide a method and apparatus for manufacturing the same.

The present invention to achieve the above object,

Hydroformylation of a synthesis gas comprising carbon monoxide and hydrogen with at least one olefin under a hydroformylation catalyst, and an isomerization reaction to the aldehyde produced to obtain a ratio of linear aldehyde and branched aldehyde. It provides an aldehyde manufacturing method comprising the step of adjusting.

In addition,

1) olefin feed line;

2) a syngas feed line comprising carbon monoxide and hydrogen;

3) catalyst solution supply line;

4) a hydroformylation reactor having a starting material inlet and a first reaction product outlet connected to said 1) olefin feed line, said 2) syngas feed line, and said 3) catalyst solution feed line;

5) a first reaction product discharge line connected to the first reaction product outlet of said hydroformylation reactor;

6) an isomerization reactor having a first reaction product inlet and a second reaction product outlet connected to said 5) first reaction product outlet line; And

7) the second reaction product discharge line connected to the second reaction product outlet of the 6) isomerization reactor

It provides an aldehyde manufacturing apparatus comprising a.

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

In the aldehyde production method according to the present invention, after the aldehyde is prepared through hydroformylation, the ratio of linear aldehyde and branched aldehyde can be adjusted by performing an isomerization reaction.

In addition, the aldehyde production method according to the present invention further comprises the step of measuring the ratio of linear aldehyde and branched aldehyde in the reaction product between the hydroformylation step and the isomerization step and / or after the isomerization step. can do.

In general, aldehydes prepared through hydroformylation reactions are prepared as a mixture of linear aldehydes and branched aldehydes. The linear aldehydes and branched aldehydes are separated into individual isomers by an isomer separation process, and then used as raw materials for various products.

The method for producing aldehyde according to the present invention can perform an isomerization reaction on a mixture of linear aldehydes and branched aldehydes, thereby controlling the ratio of the linear aldehydes and branched aldehydes. Branched aldehyde can be prepared.

Catalysts that can be used in the isomerization reaction include [C ₅ Me ₅ Rh (C ₂ H ₃ R ₁ ) ₂ ] complex alone or the [C ₅ Me ₅ Rh (C ₂ H ₃ R ₁ ) ₂ ] complex Compounds such as pens are mixed, but are not limited thereto. R ₁ is _{one selected} from C ₁ to C ₂₀ alkyl group, phenyl group, and silyl group (-R ₂ Si, R ₂ is C ₁ to C ₂₀ alkyl group).

In the method for producing aldehyde according to the present invention, the ratio of linear aldehyde / branched aldehyde before the isomerization reaction is usually a ratio of 8 to 11/1, and when increasing the ratio of linear aldehyde through isomerization, linear aldehyde / branch The ratio of the type aldehyde is preferably 30/1 or more, and when the ratio of the branched aldehyde is increased, the ratio of the linear aldehyde / branched aldehyde is preferably 3/1 or less.

In the aldehyde production method according to the present invention, the reactor in which the isomerization reaction proceeds may be a continuous stirred reactor (CSTR) or a batch reactor (bacth reactor) equipped with a stirrer which is commonly used. In the isomerization reaction, the reaction temperature is 30 to 150 ° C., preferably 50 to 90 ° C., and the reaction pressure is atmospheric pressure to 20 kgf / cm ² , preferably atmospheric pressure to 5 kgf / cm ² . The residence time is 1 to 5 hrs, preferably 1 to 2 hrs.

In the hydroformylation reaction, the hydroformylation catalyst may be used without particular limitation as long as it is known in the art. For example, transition metal catalysts, specifically cobalt (Co), rhodium (Rh) iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), nickel (Ni A catalyst comprising a metal such as) may be used, with a catalyst comprising cobalt, rhodium or iridium being preferred. More specifically, acetylacetonatodicarbonyldium (Rh (AcAc) (CO) ₂ ), acetylacetonatocarbonyltriphenylphosphinedium (Rh (AcAc) (CO) (TPP)), hydridocarbonyl Li (triphenylphosphine) rhodium (HRh (CO) (TPP) ₃ ), rhodium / typtiphyses (Rh / TPPTS), acetylacetonatodicarbonyliridium (Ir (AcAc) (CO) ₂ ), hidolido Carbonyltri (triphenylphosphine) iridium (Hir (CO) (TPP) ₃ ), tetra (carbonyl) cobalt sodium (NaCo (CO) ₄ ), hydridotricarbonyltributylphosphine cobalt (HCo (CO ) ₃ PBu ₃ ) and the like, but is not limited to these examples.

In the hydroformylation step, the olefin may be an olefin having 2 to 30 carbon atoms. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene , 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpropene (isobutylene), 2-methylbutene , 2-pentene, 2-hexene, 3-hexene, 2-heptene, cyclohexene, 2-ethyl-1hexene, 2-octene, styrene, and the like, but are not limited thereto.

In the hydroformylation reaction, the composition of the carbon monoxide and hydrogen may vary in a wide range. The molar ratio of carbon monoxide and hydrogen is usually in the range of 5:95 to 95: 5, preferably 80:20 to 20:80, and it is particularly preferable to use those in which the molar ratio of carbon monoxide and hydrogen is about 1: 1.

In the hydroformylation reaction, the composition of the olefin and syngas may vary in a wide range. Typically, the molar ratio of olefins and syngas can range from 5:95 to 95: 5.

In the hydroformylation reaction, the temperature of the hydroformylation reaction is usually in the range of 25 to 300 ° C, preferably 50 to 150 ° C. In addition, the reaction pressure is in the range of 1 to 700 bar, preferably 1 to 300 bar, more preferably 1 to 100 bar.

In the hydroformylation step, after the hydroformylation reaction, the catalyst can be separated from the product and recycled to continue use.

By the step of the hydroformylation reaction, linear aldehydes and branched aldehydes having one or more carbon atoms increased in the olefin compound used as a reactant can be prepared.

In the hydroformylation step, the olefin is propylene, and the aldehyde produced is preferably butylaldehyde.

In the present invention, following the hydroformylation reaction, the linear aldehyde and the branched aldehyde can be separated through an isomer separation process.

The linear aldehyde may be subjected to an aldol condensation process to produce acrolein, and the acrolein may be subjected to a hydrogenation process to prepare alcohol. The aldol condensation process and the hydrogenation process may be performed by a general process method known in the art.

In addition, the branched aldehyde may be used for the preparation of glycols such as NPG (Neo Pentyl Glycol).

In addition, the aldehyde manufacturing apparatus according to the present invention comprises: 1) an olefin supply line; 2) syngas feed line comprising carbon monoxide and hydrogen; 3) catalyst solution supply line; 4) a hydroformylation reactor having a starting material inlet and a first reaction product outlet connected to said 1) olefin feed line, said 2) syngas feed line, and said 3) catalyst solution feed line; 5) a first reaction product discharge line connected to the first reaction product outlet of said hydroformylation reactor; 6) an isomerization reactor having a first reaction product inlet and a second reaction product outlet connected to said 5) first reaction product outlet line; And 7) a second reaction product discharge line connected to the second reaction product outlet of the 6) isomerization reactor.

In the aldehyde production apparatus according to the present invention, the isomerization reactor of 6) performs an isomerization reaction on a mixture of linear aldehyde and branched aldehyde which is a first reaction product, thereby controlling the ratio of the linear aldehyde and branched aldehyde. Do it. Thus, as the second reaction product, selective aldehydes, ie high content of linear aldehydes or high content of branched aldehydes, can be prepared.

In addition, the aldehyde manufacturing apparatus according to the present invention is provided on the 5) the first reaction product discharge line is separated from the catalyst of the first reaction product passing through the 5) the first reaction product discharge line 5) the hydro of 4). A catalyst separation device for recirculating to a formylation reactor, a flow rate adjusting device for measuring a ratio of linear aldehyde and branched aldehyde in the first reaction product from which the catalyst is separated, and discharging the first reaction product when the ratio is greater than or equal to a predetermined ratio; And a final product discharge line through which the first reaction product is discharged from the flow control device.

In addition, in the aldehyde manufacturing apparatus according to the present invention, the final product discharge line may be connected to the second reaction product discharge line of the 7).

In addition, the aldehyde manufacturing apparatus according to the present invention, 5) is provided on the first reaction product discharge line is separated from the catalyst in the first reaction product passing through the first reaction product discharge line 5) the first reaction product of 4) hydro A catalyst separation device for recycling to a formylation reactor, the ratio of linear aldehyde and branched aldehyde in the second reaction product which is provided on the second reaction product discharge line of 7) and passes through the second reaction product discharge line A flow rate control device for measuring and for transferring the second reaction product to the first reaction product discharge line when the ratio is less than a predetermined amount; And a second reaction product transfer line through which the second reaction product is transferred from the flow rate control device to the 5) first reactant discharge line.

Hereinafter, the present invention will be described in detail with reference to FIGS. 1 and 2.

Aldehyde manufacturing apparatus according to the present invention comprises: 1) an olefin feed line; 2) a syngas feed line comprising carbon monoxide and hydrogen; 3) catalyst solution supply line; 4) a hydroformylation reactor 30 having a starting material inlet and a first reaction product outlet connected to said 1) olefin feed line, said 2) syngas feed line, and said 3) catalyst solution feed line; 5) the first reaction product discharge line 40 connected to the first reaction product outlet of 4) the hydroformylation reactor 30; 6) an isomerization reactor 50 having a first reaction product inlet and a second reaction product outlet connected to said 5) first reaction product outlet line 40; And 7) a second reaction product discharge line 60 connected to the second reaction product outlet of 6) isomerization reactor 50.

The 1) olefin feed line and 2) syngas feed line may consist of one integrated starting material feed line 10.

The 3) catalyst solution supply line is provided with a catalyst separation device 70 on the 5) first reaction product discharge line 40, the catalyst in the first reaction product to separate the catalyst 4) hydroformylation reactor (30) May be a recycle catalyst feed line 20 for recycling.

The olefin, syngas, and catalyst solution are supplied to the hydroformylation reactor 30 through the 1) olefin supply line, 2) syngas supply line, and 3) catalyst solution supply line to perform hydroformylation reaction. Afterwards, the resulting linear aldehyde and branched aldehyde are fed to the 6) isomerization reactor 50.

The flow control device 80 is provided on the 4) first reaction product discharge line 40 for supplying the first reaction product from the hydroformylation reactor 30 to 6) the isomerization reactor 60. The ratio of linear aldehyde to branched aldehyde in the separated first reaction product can be measured and 6) the amount of the mixture of linear aldehyde and branched aldehyde fed to the isomerization reactor 60 can be adjusted.

In addition, the flow control device 80 is installed on the 6) second reaction product discharge line 60 for discharging the second reaction product from the isomerization reactor (60) and linear aldehyde and branched in the second reaction product It is also possible to measure the ratio of aldehydes and 6) recycle the mixture of linear aldehydes and branched aldehydes to the isomerization reactor 60.

Hereinafter, the present invention will be described in detail by the following examples and comparative examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

< Example >

< Comparative example  1>

To prepare a catalyst for use in the hydroformylation reaction, 0.29 g of acetylacetonatocarbonyltriphenylphosphinedium (Rh (AcAc) (CO) (TPP)) and 12 g of triphenylphosphine (TPP) were stirred in 187 g of toluene. And completely dissolved. 100 g of the prepared catalyst solution was placed in a 600 cc jacketed reactor, heated to 90 ° C., and then reacted with propylene, hydrogen, and carbon monoxide in a molar ratio of 1: 1: 1, and reacted at 8 bar for 2 hours. After the reaction, the amount of produced butylaldehyde and the ratio of linear aldehyde / branched aldehyde were measured and shown in Table 1 below.

< Example  1>

After distilling the product produced in the same manner as in Comparative Example 1 at 120 ℃ to separate linear aldehyde / branched aldehyde and toluene with the catalyst, the separated solution C ₂ MeRh (C ₂ H ₃ Me 0.67 g of ₅ Rh (C ₂ H ₃ Me) was added to a solution containing the isomerization catalyst added to a 600 cc jacketed reactor, pressurized to 2 bar with propylene, and then the temperature was raised to 80 ° C. and stirred for 2 hours. The amount of butyl aldehyde and the ratio of linear aldehyde / branched aldehyde after isomerization was measured and shown in Table 1 below.

In Comparative Example 1, which does not undergo isomerization, the ratio of linear aldehyde / branched aldehyde is 10/1, whereas in Example 1, which undergoes isomerization, the ratio of linear aldehyde / branched aldehyde is changed to 2/1. The reaction shows that linear aldehyde / branched aldehyde ratio control is effective.

In the method for preparing aldehyde according to the present invention, the ratio of linear aldehyde or branched aldehyde can be adjusted by performing isomerization reaction on a mixture of linear aldehyde and branched aldehyde prepared through hydroformylation reaction, and the raw materials of different products The linear aldehyde or branched aldehyde which is widely used can be selectively prepared.

Claims (18)

Hydroformylation of a synthesis gas comprising carbon monoxide and hydrogen with at least one olefin under a hydroformylation catalyst, and an isomerization reaction to the aldehyde produced to obtain a ratio of linear aldehyde and branched aldehyde. Aldehyde manufacturing method comprising the step of adjusting. The aldehyde of claim 1, further comprising measuring a ratio of linear aldehyde and branched aldehyde in the reaction product between the hydroformylation reaction step and the isomerization step, or after the isomerization step. Manufacturing method. The method according to claim 1, wherein the catalyst used in the isomerization reaction is a [C ₅ Me ₅ Rh (C ₂ H ₃ R ₁ ) ₂ ] complex alone, or the [C ₅ Me ₅ Rh (C ₂ H ₃ R ₁ ) ₂ ] Aldehyde manufacturing method characterized in that the compound is a mixture of propene to the complex: R ₁ is _{one selected} from C ₁ to C ₂₀ alkyl group, phenyl group, and silyl group (-R ₂ Si, R ₂ is C ₁ to C ₂₀ alkyl group). The ratio of linear aldehyde / branched aldehyde before the isomerization reaction is 8 to 11/1, and the ratio of linear aldehyde / branched aldehyde after isomerization is 30/1 or more or 3/1 or less. Aldehyde manufacturing method. The method of claim 1, wherein the reaction temperature is 30 to 150 ° C., the reaction pressure is normal pressure to 20 kgf / cm ² , and the residence time in the reactor is 1 to 5 hr. The method of claim 1, wherein the hydroformylation catalyst of the hydroformylation step is cobalt (Co), rhodium (Rh) iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd ), Iron (Fe), or nickel (Ni) comprising a catalyst containing a aldehyde manufacturing method. The method of claim 1, wherein the olefin of the hydroformylation step is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dode Cene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpro Pen (isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, cyclohexene, 2-ethyl-1hexene, 2-octene, and styrene An aldehyde manufacturing method, characterized in that. The method of claim 1, wherein the molar ratio of carbon monoxide and hydrogen in the hydroformylation step is in the range of 5: 95 to 95: 5. The method of claim 1, wherein the molar ratio of olefin and syngas in the hydroformylation step is in the range of 5: 95 to 95: 5. The method of claim 1, wherein the hydroformylation of the hydroformylation step of the temperature is 25 to 300 ℃ range, the pressure is 1 to 700 bar range aldehyde production method characterized in that. The method of claim 1, wherein the olefin of the hydroformylation step is propylene, the aldehyde produced is butyl aldehyde characterized in that the butyl aldehyde. A method for separating linear aldehydes and branched aldehydes comprising the step of producing a compound comprising linear aldehydes and branched aldehydes from the method for preparing aldehydes, and performing an isomer separation process for the compounds. Separating the linear aldehyde and the branched aldehyde by the method of claim 12, and performing the aldol condensation process for the linear aldehyde to produce acrolein. A process for producing an acrolein according to the method of claim 13, and performing a hydrogenation process for the acrolein. 1) olefin feed line; 2) a syngas feed line comprising carbon monoxide and hydrogen; 3) catalyst solution supply line; 4) a hydroformylation reactor having a starting material inlet and a first reaction product outlet connected to said 1) olefin feed line, said 2) syngas feed line, and said 3) catalyst solution feed line; 5) a first reaction product discharge line connected to the first reaction product outlet of said hydroformylation reactor; 6) an isomerization reactor having a first reaction product inlet and a second reaction product outlet connected to said 5) first reaction product outlet line; And 7) the second reaction product discharge line connected to the second reaction product outlet of the 6) isomerization reactor Aldehyde manufacturing apparatus comprising a. The method according to claim 15, wherein 5) is provided on the first reaction product discharge line 5) separating the catalyst in the first reaction product passing through the first reaction product discharge line and recycled to the hydroformylation reactor of 4) A catalyst separation device, a flow rate adjusting device for measuring a ratio of linear aldehyde and branched aldehyde in the first reaction product from which the catalyst is separated, and discharging the first reaction product if the ratio is greater than or equal to a predetermined ratio; And a final product discharge line through which the first reaction product is discharged from the flow control device. The apparatus of claim 16, wherein the second reaction product discharge line of 7) is connected to the final product discharge line. The method according to claim 15, wherein 5) is provided on the first reaction product discharge line 5) separating the catalyst in the first reaction product passing through the first reaction product discharge line and recycled to the hydroformylation reactor of 4) A catalyst separation device, which is provided on the second reaction product discharge line of the 7) and measures the ratio of linear aldehyde and branched aldehyde in the second reaction product passing through the second reaction product discharge line, 7). A flow rate adjusting device for transferring the second reaction product to the first reaction product discharge line when the ratio is 5; And a second reaction product conveying line from which the second reaction product is transferred from the flow rate adjusting device to the 5) first reactant discharge line.

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