KR101291015B1 - Reactor for the hydroformylation of olefin and method for the hydroformylation using the same - Google Patents

Abstract

The present invention is equipped with an injection means for injecting an olefin and synthesis gas (CO / H ₂ ) to the catalyst mixture solution is charged in the reactor; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And a reactor formed between the venturi and the reactor outlet, the reactor having a dispersion plate for switching the flow of olefins and syngas, and a hydroformylation reaction apparatus for olefins and a method for hydroformylation using the same. The densification reactor is characterized in that the gas-liquid contact is smoothed by a dispersion plate provided inside the reactor, and the reaction mixture is circulated to excel in reaction efficiency.

Olefins, syngas, hydroformylation, aldehydes, venturis, dispersion plates, reactor equipment.

Description

Reactor for the hydroformylation of olefin and method for the hydroformylation using the same}

The present invention relates to an apparatus and a method for preparing aldehyde by hydroformylation of olefin, and more particularly, to a catalyst mixture solution mounted on top of a reactor and charged with olefin and synthesis gas (CO / H ₂ ) in the reactor. Spraying means for spraying on; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And a hydroformylation reaction apparatus for olefins including a reactor mounted between the venturi and the reactor outlet and having a dispersion plate for switching the flow of olefins and syngas, and a hydroformylation method using the same.

Hydroformylation reaction, commonly known as OXO reaction, is a linear increase in the number of carbon atoms in the olefin due to the reaction of various olefins and syngas (CO / H ₂ ) in the presence of metal catalysts and ligands. Linear, normal) and branched (iso) aldehydes are produced. The oxo reaction was first discovered by Otto Roelen of Germany in 1938, and as of 2001, around 8.4 million tonnes 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 oxo reaction are converted to aldehyde derivatives, acid and alcohol, through oxidation or reduction processes. In addition, it may be transformed into various acids and alcohols containing long alkyl groups through oxidation or reduction reaction after condensation reaction such as Aldol. These alcohols and acids are used as raw materials for solvents, additives, and various plasticizers.

Currently, the catalysts used in the oxo process are mainly cobalt (Co) and rhodium (Rh) series, and the N / I selectivity of the aldehyde produced according to the type of ligand and the operating conditions applied (iso) of linear (normal) to branched (iso ) isomers) are different. More than 70% of the world's oxo plants employ a low pressure OXO process with rhodium-based catalysts.

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

Ligands include phosphine (Phosphine, PR ₃ , R for C ₆ H ₅ , or nC ₄ H ₉ ), phosphine oxide (Phosphine Oxide, O = P (C ₆ H ₅ ) ₃ ), phosphite, Amines, amides or isonitriles 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 fed to the oxo reactor using the catalyst along with syngas (CO / H ₂ ) to produce normal-butylaldehyde and iso-butylaldehyde. The resulting aldehyde mixture is sent to the separation system together with the catalyst mixture to separate into hydrocarbon and catalyst mixture, then the catalyst mixture is circulated to the reactor and the hydrocarbon component is transferred to the stripper. The hydrocarbons in the stripper are stripped by fresh syngas to recover unreacted propylene and syngas in the oxo reactor and the butylaldehyde is transferred to the fractionation column and separated into normal and iso-butylaldehyde, respectively. The normal-butylaldehyde at the bottom of the fractionation column is introduced into an aldol condensation reactor to produce 2-ethylhexanal by condensation and dehydration, and then transferred to a hydrogenation reactor, whereby octanol (2-ethylhexanol) is produced by hydrogenation. do. The reactants at the outlet of the hydrogenation reactor are transferred to the fractionation column, and the light / heavy end is separated to produce octanol product.

The hydroformylation reaction can be carried out continuously, semicontinuously or batchwise, and a typical hydroformylation reaction process is a gas or liquid recycle system. In hydroformylation reaction, it is important to improve the reaction efficiency by smoothly contacting the starting materials consisting of liquid and gas phase. To this end, conventionally, a continuous stirred tank reactor (CSTR), which stirs the liquid and gaseous components in a reactor, is uniformly used. U.S. Patent No. 5,763,678 also discloses a hydroformylation process that replaces agitation through circulation by applying a series of loop shaped reactors. However, the above methods have limitations in improving the efficiency of the hydroformylation reaction, and since a satisfactory aldehyde product can not be obtained with only a single reactor, generally, a reaction residence time is increased or two or more reactors are connected in series, Products.

The present invention is to solve the problems of the prior art as described above, in the hydroformylation method for producing an aldehyde by reacting olefin with a synthesis gas containing carbon monoxide and hydrogen, it is possible to improve the efficiency of the hydroformylation reaction It is to provide an apparatus for hydroformylation of olefins present and a method for hydroformylation of olefins using the same.

In order to solve the above-mentioned problems, the present invention provides a combustion apparatus comprising: injection means mounted on an upper portion of a reactor for injecting olefin and syngas (CO / H ₂ ) into a catalyst mixture solution charged in a reactor; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And it is provided between the injection means and the reactor outlet, and provides a hydroformylation reaction apparatus of olefin comprising a reactor provided with a dispersion plate for switching the flow of olefin and syngas.

The injection means preferably comprises an ejector equipped with a nozzle, the diameter of the nozzle is preferably 0.1 to 1000mm.

In addition, the injection means preferably comprises a venturi tube coupled to the ejector.

The venturi tube includes an inlet coupled to the ejector and a diffuser directed toward the reactor outlet, wherein the diameter of the inlet is preferably smaller than the diameter of the diffuser and the dispersion plate is one third of the venturi and reactor outlet. It is preferably located between 2 and 2/3, and the dispersion plate is preferably flat in shape, convex with respect to the reactor outlet, or concave.

The hydroformylation reaction apparatus for olefins according to the present invention is connected to the outlet of the reactor and the injection means mounted on the upper part of the reactor, the reaction mixture is recovered from the reactor outlet and supplied to the injection means mounted on the reactor to circulate the reaction mixture. It is preferable to further include a circulation pipe to make.

A separation pipe separating at any one of the circulation pipe to separate the reaction mixture from the circulation flow; A catalyst / aldehyde separation unit connected to the separation line for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And an aldehyde recovery piping connected to the catalyst / aldehyde separator for recovering aldehydes.

The present invention as another means for solving the above problems, the first step of charging a catalyst mixture solution therein; A second step of injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; And it provides a hydroformylation method of the olefin comprising a third step of performing the reaction while switching the injection stream of the olefin and syngas.

It is preferable to further include the step of recovering the reaction mixture after the third step, and supplying the reaction mixture to circulate the reaction mixture.

In the circulating step of the reaction mixture, separating a portion of the circulated reaction mixture to separate the catalyst mixture solution and aldehyde; And supplying the separated catalyst mixture solution to a circulating flow, and recovering the aldehyde.

The hydroformylation apparatus for olefins according to the present invention has a large contact surface area of the olefin and the synthesis gas as a reaction material by a dispersion plate provided inside the reactor, thereby providing a sufficient reaction area, and the reaction material is reacted as the reaction mixture is circulated. It is sufficiently mixed with and the reaction efficiency is excellent.

Hereinafter, the present invention will be described in detail.

Injection means mounted on the reactor and injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And a reactor mounted between the injection means and the reactor outlet and equipped with a dispersion plate for switching the flow of olefins and syngas.

The injection means is not particularly limited as long as it can inject olefins and syngas into the reactor. For example, an ejector equipped with a nozzle may be used, and the nozzle mounted on the ejector serves to increase the speed by reducing the injection cross-sectional area of olefin and synthesis gas supplied into the oxo reactor at high pressure. The diameter of the nozzle may vary depending on the size of the oxo reactor, which is generally preferably 0.1 to 1000 mm.

In addition, it is preferable that the venturi tube is coupled to the ejector. The venturi tube comprises an inlet and a diffuser as is known, wherein the diameter of the inlet is smaller than the diameter of the diffuser and is coupled to the injection means and the diffuser is directed towards the bottom of the reactor. The diameter of the inlet is preferably 1 to 10 times the diameter of the nozzle, and the diameter of the diffusion is preferably 2 to 10 times the diameter of the inlet. In addition, the length of the venturi tube is preferably 0.2 to 0.8 times the total length of the reactor.

The mixed gas, which is a reaction raw material, is injected into the reactor through the injection means and the venturi tube coupled thereto, and the mixed gas is injected into the catalyst mixed solution charged into the reactor while forming microbubbles. The venturi tube is immersed in the catalyst solution in the reactor, and the catalyst solution and the synthesis gas are mixed at the nozzle portion and descended through the venturi tube to be mixed with the catalyst solution in the reactor.

Due to the high flow rate of the catalyst solution at the nozzle, the synthesis gas becomes microbubbles, and the microbubbles of the mixed gas come into contact with the olefin and the catalyst mixed solution, thereby providing a sufficient reaction area due to the wide contact area of the gas-liquid. .

In addition, the flow of olefin and mixed gas injected by the distribution plate mounted between the venturi tube and the outlet of the reactor is switched. This change in the reaction raw material flow lengthens the residence time of the reaction raw material in the reactor, thereby improving the reaction efficiency. The conversion of the reaction raw material flow is determined according to the position and shape of the dispersion plate, thereby controlling the reaction efficiency.

The dispersion plate is preferably located between 1/3 and 2/3 of the venturi and reactor outlet, more preferably between 1/2.

In addition, depending on the shape of the dispersion plate may be flat, convex or concave with respect to the outlet of the reactor, the concave shape is most preferred. FIG. 2 is a cross-sectional view of the dispersion plate, in which FIG. 2 (a) shows a flat shape, (b) shows a convex shape, and (c) shows a concave shape.

In addition, the dispersion plate is not limited thereto, but may be made of a material such as stainless steel or Teflon. In addition, the size of the dispersion plate may be 0.5 to 0.9 times the diameter of the reactor.

In addition, the hydroformylation reaction apparatus is connected to the outlet of the reactor and the injection means mounted on the reactor top, the reaction mixture is recovered from the reactor outlet and supplied to the injection means mounted on the reactor circulation to circulate the reaction mixture The pipe may further include.

The reaction raw material olefin and syngas are reacted in the presence of a catalyst mixed solution to produce an aldehyde as a reaction product. Accordingly, a reaction mixture including the reaction product, catalyst mixture solution, unconverted olefins, synthesis gas, and other reaction by-products is present in the reactor, and the reaction mixture is recovered from the bottom of the reactor to inject the upper means of the reactor. Supply to circulate. As the circulated reaction mixture is sprayed together with the reaction raw materials, the reaction mixture is sufficiently mixed with the reaction mixture to improve the reaction efficiency. This circulation can be controlled by a circulation pump provided in the circulation pipe.

In addition, the circulation pipe may be provided with a heat exchanger, the position is not limited to a specific position on the circulation pipe. The heat exchanger serves to maintain the reaction mixture circulated to the reactor at a temperature suitable for the hydroformylation reaction conditions.

In addition, the hydroformylation apparatus is separated in any one of the circulation pipe separation pipe for separating the reaction mixture from the circulation flow; A catalyst / aldehyde separation unit connected to the separation line for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And an aldehyde recovery piping connected to the catalyst / aldehyde separator to recover aldehydes.

The reaction mixture discharged from the oxo reactor outlet is sent to a catalyst / aldehyde separator to separate the aldehyde and the catalyst mixture, and then the catalyst mixture solution is circulated to the reactor, and the aldehyde component is recovered through the recovery pipe.

The type of catalyst / aldehyde separator is not limited so long as it is a means for separating the catalyst mixture solution and the aldehyde from the reaction mixture.

Recirculation of the catalyst mixture solution from which the target substance has been separated may be continuously performed, and in some cases, a portion of the recycled reaction mixture may be discharged to regenerate the catalyst, or a fresh catalyst solution or a reactivated catalyst solution may be recycled. Can be added to the flow.

The present invention also

A first step of charging the catalyst mixed solution into the reactor;

A second step of injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; And

It relates to a hydroformylation method of an olefin comprising a third step of performing the reaction while switching the injection stream of the olefin and syngas.

The first step is to charge the catalyst mixture solution in the reactor, the catalyst mixture solution charged in the reactor is generally used in the hydroformylation reaction, and will include a metal-carbonyl complex catalyst and ligand Can be.

Metal-carbonyl complex catalysts can be used without limitation as long as they are generally used in the art, for example, cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os), platinum A catalyst using a transition metal such as (Pt), palladium (Pd), iron (Fe), or nickel (Ni) as a center metal can be used. Specifically, cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonyldium [Rh (AcAc) (CO) ₂ ], acetylacetonatocarbonyltriphenylphosphinedium [Rh (AcAc) ( CO) (TPP)], hydridocarbonyltri (triphenylphosphine) rhodium [HRh (CO) (TPP) ₃ ], acetylacetonatodicarbonyliridium [Ir (AcAc) (CO) ₂ ] and hydrido One or more complex catalysts selected from the group consisting of carbonyltri (triphenylphosphine) iridium [HIr (CO) (TPP) ₃ ] can be used.

In addition, the ligand may be a trisubstituted phosphine (Phosphine), phosphine oxide (Phosphine Oxide), amines (Amine), amides (Amide), or isonitrile (Isonitrile) and the like, tri-substituted phosphine is used It is desirable to. The tri-substituted phosphines include, but are not limited to, triaryl phosphine, triaryl phosphite, alkyldiaryl phosphine, and more specifically triphenyl phosphine, tritolyl phosphine, triphenyl phosphite, and n -Butyldiphenylphosphine and the like can be used.

Although rhodium catalysts are expensive, they provide more stable reaction conditions for hydroformylation processes than cobalt or iridium catalysts and are used in most commercialized processes due to the advantages of excellent catalytic activity and high selectivity. It is more preferable to use. In addition, it is more preferable to include triphenylphosphine (TPP) as a ligand in view of activity, stability and price of the catalyst.

Examples of the solvent used in the catalyst mixture solution include, but are not limited to, aldehydes such as propanaldehyde, butylaldehyde, pentylaldehyde, and valeraldehyde; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or cyclohexanone; Alcohols such as ethanol, pentanol, octanol, and pentanol; Aromatic compounds such as benzene, toluene and xylene; Ethers such as tetrahydrofuran, dimethoxyethane and dioxane; And paraffin hydrocarbons such as heptane. Preferably, the aldehyde produced through the hydroformylation reaction from the olefin used as the raw material is used as the raw material. For example, butylaldehyde is used when propylene is a raw material, and pentylaldehyde is used when butylen is a raw material.

In addition, the concentration of the catalyst mixture solution is preferably 10 to 2000 ppm for the metal carbonyl complex catalyst and 1 to 30% by weight for the ligand.

The second step is to supply the olefin and the synthesis gas as the reaction raw material into the reactor, the mixed gas as the reaction raw material is injected into the catalyst mixture solution by the injection means. The injected mixed gas forms micro bubbles, and the micro bubbles of the mixed gas come into contact with the olefin and catalyst mixed solution, thereby providing a sufficient reaction area due to the wide gas-liquid contact surface area.

Injection of olefins and syngas may be performed using an ejector equipped with a nozzle and a venturi tube coupled thereto.

The olefins usable in the present invention are not limited thereto, but olefins having 2 to 20 carbon atoms may be used, more specifically ethylene, propylene, butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2 -Methylpropene, 2-pentene, 2-hexene, 2-heptene, 2-ethylhexene, 2-octene, styrene, 3-phenyl-1-propene or 4-isopropylstyrene, and the like, and ethylene, propylene, It is more preferable that it is 1-butene or 1-octene.

Syngas, another starting material of the hydroformylation reaction, is a mixed gas of carbon monoxide and hydrogen, and the mixing molar ratio of CO: H ₂ is not limited thereto, but is preferably 5:95 to 70:30, and 40: It is more preferable that it is 60-60: 40, and it is most preferable that it is 50: 50-40: 60.

It is preferable that it is 95: 5-5: 95, and, as for the molar ratio of the said olefin and syngas, it is more preferable that it is 75: 25-25: 75.

In addition, the olefin and the synthesis gas is preferably injected at a pressure of 5 to 200 bar, respectively. In addition, the linear velocity of the olefin and the synthesis gas is preferably 5 m / s to 40 m / s.

The third step is to perform the reaction while switching the injection flow of the olefin and synthesis gas, the residence time of the reaction raw material in the reactor is increased by the conversion of the reaction raw material flow, thereby improving the reaction efficiency . Olefin and syngas can be achieved by mounting a dispersion plate between the outlet of the venturi and the reactor when the nozzle is injected through the ejector equipped with the nozzle and the venturi tube coupled thereto.

The reaction is preferably carried out at a temperature of 50 to 200 ℃, more preferably carried out at a temperature of 50 to 150 ℃. In addition, the reaction is preferably carried out at a pressure of 5 to 100bar, more preferably carried out at a pressure of 5 to 50bar.

In the hydroformylation method of the olefin according to the present invention, it is preferable to further include the step of recovering the reaction mixture after the third step and feeding the reaction mixture to circulate the reaction mixture.

The reaction mixture discharged through the reactor outlet is recovered, and the reaction raw material is sufficiently mixed with the reaction mixture by a circulation system supplied into the reactor, thereby improving the reaction efficiency. The reaction mixture contains unconverted olefins, reaction by-products, and catalyst mixed solution in addition to the target aldehydes (normal- and iso-butylaldehyde).

Such a circulation system can be achieved by circulation piping coupled to the reactor outlet and injection means of the reactor and a circulation pump coupled thereto. The flow rate of the circulating reaction mixture may vary depending on the amount of reactor charged catalyst solution, and the flow rate of the circulated reaction mixture per minute is preferably 0.01 to 20 times the reactor charge capacity. For example, when the reactor charge catalyst amount is 10 liters, the flow rate of the reaction mixture circulated per minute is preferably 0.1 to 200 L / min.

In addition, in the circulating step of the reactant, separating a portion of the circulated reaction mixture to separate the catalyst mixture solution and aldehyde; And

The separated catalyst mixture solution may be supplied to a circulating flow, and the aldehyde may further include recovering the aldehyde.

A portion of the circulating reaction mixture is separated to separate the catalyst mixture solution and the aldehyde, and the catalyst mixture solution is resupplied to the circulation stream.

Specifically, when the olefin which is a starting material of the hydroformylation method is propylene, the reaction mixture contains butylaldehyde, more specifically, normal-butylaldehyde and iso-butylaldehyde, and the reaction mixture is a catalyst / aldehyde separation device. And then separated into aldehyde and catalyst mixture, the catalyst mixture is circulated to the reactor and the aldehyde component is sent to the fractionation tower to separate normal- and iso-butylaldehyde, respectively.

At this time, the normal-butylaldehyde at the bottom of the fractionation column is introduced into the aldol condensation reactor to produce 2-ethylhexanal by condensation and dehydration, and then transferred to a hydrogenation reactor. Octanol (2-ethylhexanol) is added by hydrogenation. Can be generated.

Hereinafter, in order to clearly understand and easily carry out the present invention, it will be described by the accompanying schematic drawings.

1 schematically shows the hydroformylation process of an olefin according to one embodiment of the invention. In FIG. 1, various standard items actually used in a factory, such as a valve, a temperature measuring device, a pressure regulator, etc., which can be easily recognized by those skilled in the art, are omitted.

The olefin (for example, propylene) and the synthesis gas are ejectors 20 provided on the upper part of the oxo reactor 100 in which the catalyst solution is charged through the olefin supply pipe 10 and the synthesis gas supply pipe 11, respectively. Is supplied to the nozzle.

In order to increase the efficiency of the gas-liquid reaction, the inside of the oxo reactor 100 is provided with a nozzle in the ejector 20 and a venturi 30 coupled to the nozzle, and the supplied olefin and syngas are supplied to the ejector 20. It is continuously injected and supplied into the venturi 30 through the inner nozzle. The olefin and syngas injected into the oxo reactor 100 undergo a hydroformylation reaction in the presence of a catalyst to produce a reaction mixture. The reaction mixture includes unconverted olefins, reaction by-products, catalyst solutions, and the like, in addition to the target aldehydes (eg, normal- and iso-butylaldehyde).

The reaction mixture containing the aldehyde is recovered through the recirculation pipe 12 using the circulation pump 60, and then circulated to the nozzle in the ejector 20 provided in the reactor through the recirculation pipes (13, 14, 15, 16). do.

At this time, a portion of the circulating reaction mixture may be led to the catalyst / aldehyde separation device 70 from the recirculation pipe through the separation pipe 17 to separate the aldehyde.

The recovered aldehyde is sent to a separation recovery apparatus or the like (not shown) through the aldehyde recovery pipe 19, and can be separated and recovered by various aldehydes and condensation products by treating with a conventional distillation apparatus.

The aldehyde, which is a target substance, is recovered from the reaction mixture, and the remaining catalyst mixture is supplied to the recirculation pipe 15 of the oxo reactor 100 via the catalyst solution recirculation pipe 18.

The reaction mixture of the reactor combined with the recycled catalyst mixture is passed to the oxo reactor 100 together with the olefin and the synthesis gas supplied through the olefin feed pipe 10 and the syngas feed pipe 11 via a heat exchanger 80. It is injected and supplied into the oxo reactor 100 through the nozzle in the ejector 20 provided.

FIG. 1 shows an example in which a catalyst solution recirculation pipe 18 is connected between recirculation pipes 14 and 15 to remove aldehydes and introduce remaining catalyst solution or reactivated catalyst solution into the reactor system.

A heat exchanger 80 may be provided between the recirculation piping 15 and 16, but the position is not limited to a specific position on the circulation cycle. The heat exchanger 80 serves to maintain the reaction mixture recycled to the oxo reactor 100 at a temperature suitable for the hydroformylation reaction conditions.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by the examples in order to facilitate a specific understanding of the invention.

[Comparative Example]

Comparative Example 1 (without dispersion plate)

As in FIG. 1, a venturi-loop reactor having a 3 liter capacity was manufactured and installed. The reactor flowed the heat medium oil to the jacket instead of the external heat exchanger to maintain a constant temperature inside the reactor. The diameter of the nozzle mounted in the venturi-loop reactor was 1.7 mm, the diameter of the expansion pipe was 8.0 mm, and the length was 200 mm.

800 g of triphenylphosphine (TPP) and 0.8 g of rhodium triphenylphosphine acetylacetonate carbonyl (ROPAC) were dissolved in 800 g of purified normal-butylaldehyde to prepare a normal-butylaldehyde catalyst solution.

The catalyst solution thus prepared was introduced into the reactor and the circulation pump was operated to purge the whole system three times with purified nitrogen gas through the nozzle at the top of the reactor while circulating the catalyst solution slowly at a rate of 2 liters per minute.

While maintaining the external circulation pump at a rate of 2 liters per minute, the heat medium oil was poured into the jacket outside the venturi-loop reactor to maintain the temperature inside the reactor at 90 ° C. When the temperature stabilized at 90 ° C., propylene was fed at a flow rate of 12 g / min until the internal pressure of the reactor was 16.2 bar. 5 minutes after the supply, confirm that the internal temperature of the venturi-loop reactor was maintained at 90 ° C, and the synthesis gas (mixed gas having a molar ratio of carbon monoxide and hydrogen of 50:50) at a supply pressure of 18.8 bar was injected into the nozzle of the reactor. The reaction was started simultaneously with feeding to the neck (10 in FIG. 1).

The flow rate of the syngas supplied to the reactor was measured over time while maintaining the internal temperature of the venturi-loop reactor at 90 ° C. through an automatic temperature control device to be connected to the reactor. After reacting for 2 hours, the mixed gas was shut off, the operation of the circulating pump was immediately stopped, the reactor temperature was lowered to room temperature, the pressure was released, and the mixture of the total catalyst solution and the product was recovered in a separate pipe and weighed. It was found that the total weight of the reaction solution was 1.265 g, and thus the weight of butylaldehyde produced by the reaction was 456 g. In addition, when the total amount of mixed gas consumed was measured through an integrated flow meter installed in the mixed gas supply pipe, the maximum consumption rate of the syngas during the reaction was 5.4 liters per minute. The results are shown in Table 1 below.

Comparative Example 2 (Scatter Plate Installed at Reactor Outlet)

In the same reactor as Comparative Example 1, the dispersion plate of FIG. 2 (a) was installed to be located at a point just above the outlet of the reactor, and then, the same process as in Comparative Example 1 was performed.

[Example]

Examples 1 to 2 (Example according to the change of position of the dispersion plate)

Example 1

In the same reactor as that of Comparative Example 1, the dispersion plate of FIG. 2 (a) was installed to be positioned at a point 1/3 of the distance from the reactor outlet to the expansion pipe, and the same method as in Comparative Example 1 was performed. Shown in

Example 2

In the same reactor as that of Comparative Example 1, the dispersion plate of FIG. Shown in

 [Table 1]

Distribution location Comparative Example 1
(Without distribution board) Comparative Example 2
(Reactor outlet) Example 1
(1/3 point from reactor outlet) Example 2
(1/2 point from reactor outlet) Butylaldehyde
Production amount (g) 456 474 478 487 Syngas consumption rate (L / min) 5.4 5.5 5.6 5.8

As shown in Table 1, it can be seen that the reaction rate is higher and the reaction efficiency is higher in the case of the embodiment according to the present invention than when the dispersion plate is not installed or when the dispersion plate is located at the reactor outlet side (Comparative Examples 1 and 2). .

In addition, it can be seen that the dispersion plate is located at the intermediate point between the reactor outlet and the expansion (Example 2) rather than located at 1/3 point from the reactor outlet (Example 1), showing a higher reaction rate.

Examples 3 to 5 (change in shape of the dispersion plate)

Example 3

In the same reactor as that of Comparative Example 1, a dispersion plate (a) of FIG. 2 was installed to be located at a half point of the distance from the outlet of the reactor to the expansion pipe, and the same method as in Comparative Example 1 was performed. The results are shown in Table 2 below.

Example 4

In the same reactor as in Comparative Example 1, the dispersion plate (b) of FIG. The results are shown in Table 2 below.

Example 5

In the same reactor as in Comparative Example 1, the dispersion plate (c) of FIG. 2 (downward convex shape) was installed to be located at a half point of the distance from the reactor outlet to the expansion pipe, and the same method as in Comparative Example 1 was performed. The results are shown in Table 2 below.

[Table 2]

Dispersion Form Example 3 Example 4 Example 5 Butylaldehyde production amount (g) 487 486 508 Syngas consumption rate (L / min) 5.8 5.7 6.1

As shown in Table 2, it can be seen that in the case of Examples 3 to 5 all exhibit a high reaction rate and high reaction efficiency, of which the case of installing a convex semicircular dispersion plate down (Example 5) It can be seen that it shows a high reaction rate and reaction efficiency.

While the invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

1 is a schematic process diagram showing a hydroformylation process of an olefin according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view of the dispersion plate provided in the hydroformylation apparatus of the olefin of the present invention, which shows (a) a flat plate shape, (b) a semicircular shape convex upward, and (c) a semicircular shape dispersion plate downward.

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

10: olefin supply piping 11: syngas supply piping

12, 13, 14, 15, 16: Circulation piping 17: Separation piping

18: catalyst solution supply piping 19: aldehyde recovery piping

20: ejector 30: venturi tube

40: reactor outlet 50: dispersion plate

60: circulating pump 70: catalyst / aldehyde separation device

80: heat exchanger 100: oxo reactor

Claims (24)

It is equipped with a nozzle as an injection means which is mounted on the venturi-loop oxo reactor to inject the olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged inside the reactor, and the venturi tube is integrally attached to the nozzle. An ejector coupled, wherein the venturi tube is configured to be submerged in the catalyst mixture solution; A reactor outlet positioned below the reactor to discharge a reaction mixture of olefin and syngas; A venturi-loop oxo reactor mounted between the injection means and the reactor outlet and equipped with a dispersion plate for switching the flow of olefins and syngas; A circulation pipe connected to the outlet at the bottom of the reactor and the injection means mounted at the top of the reactor, and collecting the reaction mixture from the reactor outlet and supplying the reaction mixture to the injection means mounted at the top of the reactor to circulate the reaction mixture; A separation pipe separating at any one of the circulation pipe to separate the reaction mixture from the circulation flow; A catalyst / aldehyde separation unit connected to the separation line for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And An aldehyde recovery piping connected to the catalyst / aldehyde separator to recover aldehydes; Hydroformylation reactor of olefins. delete The method of claim 1, The diameter of the nozzle is characterized in that 0.1 to 1000mm Hydroformylation reactor of olefins. delete The method of claim 1, The venturi tube comprises an inlet coupled to the ejector and a diffuser directed toward the reactor outlet, wherein the diameter of the inlet is smaller than the diameter of the diffuser. 6. The method of claim 5, The diameter of the inlet is characterized in that 1 to 10 times the diameter of the nozzle Hydroformylation reactor of olefins. The method of claim 1, The length of the venturi tube is characterized in that 0.2 to 0.8 times the total length of the reactor Hydroformylation reactor of olefins. The method of claim 1, The dispersion plate is located between 1/3 and 2/3 of the venturi and the reactor outlet Hydroformylation reactor of olefins. The method of claim 1, The dispersion plate is characterized in that the flat shape, the convex shape with respect to the reactor outlet, or concave shape. Hydroformylation reactor of olefins. The method of claim 1, The size of the dispersion plate is characterized in that 0.5 to 0.9 times the diameter of the reactor Hydroformylation reactor of olefins. delete delete A first step of charging a catalyst mixture solution in a venturi-loop oxo reactor of the hydroformylation reactor of claim 1; A second step of injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; A third step of carrying out the reaction while switching the injection flow of the olefin and syngas; Recovering the reaction mixture after the third step, and feeding the reaction mixture into a reactor to circulate the reaction mixture; Separating a part of the circulated reaction mixture to separate a catalyst mixture solution and an aldehyde; And Supplying the separated catalyst mixture solution to a circulating flow and recovering aldehydes; Containing Hydroformylation of Olefin. 14. The method of claim 13, The catalyst mixed solution comprises a metal-carbonyl complex catalyst and a ligand Hydroformylation of Olefin. 15. The method of claim 14, The concentration of the catalyst mixture solution is characterized in that the metal carbonyl complex catalyst 10 to 2000 ppm, the ligand is 1 to 30% by weight Hydroformylation of Olefin. 14. The method of claim 13, The olefin is ethylene, propylene, butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpropene, 2-pentene, 2-hexene, 2-heptene, 2-ethylhexene, 2-octene , Styrene, 3-phenyl-1-propene or 4-isopropylstyrene Hydroformylation of Olefin. 14. The method of claim 13, The mixed gas (CO: H ₂ ) is characterized in that the mixing mole ratio of CO: H ₂ is 5:95 to 70:30 Hydroformylation of Olefin. 14. The method of claim 13, The molar ratio of the olefin and the synthesis gas is injected is characterized in that 95: 5 to 5:95 Hydroformylation of Olefin. 14. The method of claim 13, The olefin and syngas are each injected and supplied into the oxo reactor through a nozzle at a pressure of 5 to 200 bar, respectively. Hydroformylation of Olefin. 14. The method of claim 13, The linear velocity injected of the olefin and the synthesis gas is characterized in that 5 m / s to 40 m / s Hydroformylation of Olefin. 14. The method of claim 13, The reaction of the third step is characterized in that carried out at a temperature of 50 to 200 ℃ and a pressure of 5 to 100 bar Hydroformylation of Olefin. delete 14. The method of claim 13, The flow rate of the circulating reaction mixture is characterized in that 0.01 to 20 times the reactor charge capacity per minute Hydroformylation of Olefin. delete

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