KR101251714B1 - Reactor for the hydroformylation of olefin and method for the hydroformylation using the same - Google Patents

Abstract

The present invention relates to a hydroformylation apparatus for olefins and a method for hydroformylation of olefins using the same. More specifically, a synthesis gas including olefins, carbon monoxide, and hydrogen into an oxo reactor through a venturi-coupled nozzle, And a hydroformylation apparatus and method for improving the reactivity of the aldehyde production reaction by injecting and supplying the catalyst composition and promoting the mixing and mass transfer of the olefin, syngas and catalyst composition injected and supplied through the unique expansion structure of the nozzle unit. It is about. The present invention can improve the hydroformylation reactivity to obtain the desired aldehyde in high yield as well as to reduce the circulating flow rate by the external pump, thereby reducing the reactor operating cost and the reaction mixture from the outside of the oxo reactor into the reactor. It also has the advantage of shortening the reaction process by eliminating the process of refeeding.

Olefin, Syngas, Hydroformylation, Venturi, Dispersion Plate, Loop Reactor, Expansion

Description

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

The present invention relates to a hydroformylation apparatus for olefins and a method for hydroformylation of olefins using the same. More specifically, a synthesis gas including olefins, carbon monoxide, and hydrogen into an oxo reactor through a venturi-coupled nozzle, And by injecting and supplying the catalyst composition and promoting the mixing and mass transfer of the olefin, syngas and catalyst composition injected and supplied through the two-stage expansion structure of the venturi to improve the reactivity of the aldehyde manufacturing reaction and react. A hydroformylation apparatus and method for shortening the process are provided.

Hydroformylation reaction, commonly known as OXO, is a linear increase in the number of carbon atoms in an olefin due to the reaction of various olefins and syngas (CO / H ₂ ) in the presence of metal catalysts and ligands. , normal) and branched (iso) aldehydes are produced. This oxo reaction was first discovered by Otto Roelen of Germany in 1938, and as of 2001, around 8.4 million tons of various aldehydes (including alcohol derivatives) are produced and consumed through the oxo process worldwide ( SRI Report). , November 2002 , 682. 700A).

The various aldehydes synthesized by the oxo reaction are transformed into acids and alcohols which are aldehyde derivatives through oxidation or reduction. 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 operating conditions such as the type of ligand applied and the CO partial pressure (ratio of linear (normal) to branched (iso) isomers) is different. More than 70% of the world's oxo plants employ a low pressure OXO process with a rhodium-based catalyst.

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 isonitrile and the like 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 hydrocarbon of the stripper is stripped by freshly supplied syngas so that unreacted propylene and syngas are recovered to the oxo reactor and the butylaldehyde is sent to a fractionation tower to separate normal- and iso-butylaldehyde, respectively. 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, whereby octanol (2-ethylhexanol) is produced by hydrogenation. do. The reactants at the outlet of the hydrogenation reactor are sent to the fractionation tower to produce the octanol product after separating the soft / hard ends.

The hydroformylation reaction can be carried out continuously, semicontinuously or batchwise, and a typical hydroformylation process is a gas or liquid recycle system. The hydroformylation reaction is important to increase the reaction efficiency by the smooth contact between 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 cannot be obtained with a single reactor, it is generally necessary to give a large reaction residence time or to connect two or more reactors in series.

In view of such drawbacks, the present inventors have proposed an apparatus for spraying and supplying through a nozzle and a method using the same through Korean Patent Application No. 10-2008-0050388. However, the above-described prior art is also only a smooth flow of gas and liquid, which was not enough to improve the reactivity, and in order to improve the reaction, some of the reaction mixtures must be charged into the reactor from the outside of the oxo reactor to promote the reaction. There is a disadvantage in that it is cumbersome and requires a running cost such as a process to be performed.

In order to solve the above problems, the present invention is a method for producing an aldehyde by reacting olefins with carbon monoxide and hydrogen, it is possible to obtain the desired aldehyde in high yield by improving the efficiency of the hydroformylation reaction through the expansion structure It is an object of the present invention to provide a hydroformylation apparatus of an olefin having a structure and a method of improving reactivity using the same.

In the present invention, as a means for solving the above problems, in the hydroformylation apparatus of olefin in which a nozzle in which venturi is bonded as an injection means is provided at the upper end inside the oxo reactor,

The nozzle is integrally formed at the lower end of the reactor inlet portion and consists of an expansion portion that is widened toward the reactor outlet side, and has a pipe shape.

One or more holes are formed in the upper part of the expansion pipe to provide a hydroformylation apparatus of olefin, characterized in that it promotes mixing and delivery.

The oxo reactor is preferably a venturi-loop reactor.

The diameter of the nozzle is 0.1 to 500 mm, the diameter of the inlet is preferably 1 to 10 times the diameter of the nozzle. In addition, the inlet is preferably a venturi tube is coupled to the ejector. The venturi tube includes an inlet formed in the form of a straight tube and a diffuser formed of a tube extending downward, wherein the inlet is coupled to the ejector and the diameter of the inlet is the same as the diameter of the inlet of the diffuser. Smaller than the diameter of the outlet. At the same time, it is preferable that the outlet direction of the diffusion portion is toward the bottom of the reactor. The diameter of the inlet is preferably 0.2 to 100 mm, and the length of the diffusion inlet is preferably 1/50 to 1/2 of the total length of the reactor. The diameter of the diffusion inlet is equal to the inlet diameter and the diameter of the diffusion outlet is preferably 0.1 to 10 times the diameter of the diffusion inlet. In addition, the length of the diffusion portion is preferably 0.1 to 10 times the length of the inlet portion, and the length of the entire venturi tube combined with the inlet portion and the diffusion portion is preferably 0.01 to 0.95 times the length of the body, and more preferably 0.05 to 0.75 times the length. .

Considering the fact that the injection pressure from the nozzle is significant in order to introduce the catalyst mixture solution in which the olefin and the synthesis gas (CO / H ₂ ), which are already placed into the reactor through the nozzle and the venturi, is circulated back into the venturi by circulation. Thus, the hole is preferably made to include an upper inclined surface and a lower inclined surface formed inclined to the lower side of the oxo reactor. At this time, the upper inclination is more than 45 °, the lower inclination is less than 15 ° is preferable in view of the effective inlet side.

A dispersion plate is provided between the injection means and the oxo reactor outlet to switch the flow of olefins and syngas, the dispersion plate being 0.5 to 0.9 times the diameter of the reactor and 1/3 to 2 / of the venturi and reactor outlet. It is preferably located between three and is flat, convex or concave with respect to the reactor outlet.

In another aspect of the present invention, in the hydroformylation method using a hydroformylation reaction apparatus of an olefin, the hydroformylation reaction apparatus of an olefin is used as a catalyst in the reactor using the above-described apparatus. A first step of charging a mixed solution; A second step of injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; And a third step of carrying out the reaction while promoting the mixing and mass transfer of the injected olefin and the synthesis gas to produce a reaction mixture.

The catalyst mixture solution is composed of a metal-carbonyl complex catalyst, a ligand and a solvent. The concentration of the metal-carbonyl complex catalyst is 10 to 2000 ppm based on the solvent content, and the concentration of the ligand is 1 to 30 wt% based on the solvent content. It is preferable that it is%.

The molar ratio of the injected olefin and syngas is 95: 5 to 5:95, and the mixed molar ratio of syngas CO to H ₂ is 5:95 to 70:30.

The olefin and syngas are preferably injected and supplied into the oxo reactor through a nozzle at a spray linear velocity of 5 to 40 m / s under a pressure of 5 to 200 bar, respectively.

In the third step, it is preferable to supply the reaction mixture to the nozzle at the upper end of the reactor at 0.01 to 10 times the reactor charging capacity per minute to promote the mixing and mass transfer of the reaction mixture.

It is preferable to further include a fourth step of producing a reaction mixture by performing the reaction while switching the injection, mixing, or delivery flow of olefins and syngas simultaneously or sequentially with the third step. The reaction of the third and fourth steps is preferably carried out at a temperature of 50 to 200 ℃ and a pressure of 5 to 100 bar, respectively.

Furthermore, separating a portion of the reaction mixture of the fourth step catalyst mixture solution and aldehyde; And supplying the separated catalyst mixture solution to a circulating stream and recovering aldehydes. It is preferable to further include.

Hereinafter, the present invention will be described in detail.

Examples of olefins which are preferably used in the present invention include 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, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl acetate, allylbutyrate , Methyl methacrylate, vinyl methyl ether, vinyl ethyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, 4-methylstyrene, 4-isopropylstyrene, etc. have.

Typical processes according to the present invention include the reaction of propylene with normal- and iso-butylaldehyde hydroformylation using a rhodium catalyst.

The aldehydes prepared according to the invention can be hydrogenated and converted into the corresponding alcohols which can be used for the production of solvents and plasticizers and the like.

To the hydroformylation reaction, a rhodium (Rh), cobalt (Co), iridium (Ir) VIII group transition may be used is a homogeneous catalyst composed mainly of metal, a ligand such as an olefin is hydride (H ^-), carboxylic Carbonyl (CO), triphenylphosphine (TPP) and the like can be used, but is not limited to these may be used in the art. Although rhodium catalysts are expensive, they provide more stable reaction conditions for hydroformylation processes than cobalt or iridium catalysts, and most commercialized processes employ them with good catalytic activity and high selectivity.

The olefins used as starting materials are injected and supplied through a nozzle provided in an oxo reactor together with a synthesis gas containing carbon monoxide and hydrogen. The nozzle is preferably provided at the upper end inside the oxo reactor.

The preferred diameter of the nozzle provided in the oxo reactor may vary depending on the size of the reactor, and may be 0.1 mm to 100 cm, preferably 1 mm to 50 cm. The nozzle may be composed of two or more pieces.

Olefin and syngas are each injected and supplied to the oxo reactor through a nozzle at a feed pressure of 1 to 200 bar. The molar ratio of olefin: synthetic gas supplied to the oxo reactor is about 95: 5 to 5:95, preferably 75:25 to 25:75. The hydroformylation reaction is carried out at a temperature of 50 to 200 ℃, preferably 50 to 150 ℃, pressure is 5 to 100 bar, preferably 5 to 50 bar.

Unlike the conventional hydroformylation process using a continuous stirred reactor (CSTR), the present invention using a continuous reactor equipped with a nozzle and a venturi can increase the reaction efficiency by smoothing the gas-liquid contact in the hydroformylation reaction. .

In particular, when using a continuous reactor (venturi-loop reactor) equipped with a nozzle and a venturi, the starting material olefin and syngas (CO + H ₂ ) are injected into the venturi to facilitate gas-liquid contact through the nozzle. can do.

In addition, it is possible to maximize the reactivity of the aldehyde production reaction by promoting the mixing and mass transfer of the olefin, syngas and catalyst composition injected and supplied through the unique aspiration structure of the nozzle unit.

Specifically, the expansion structure of the nozzle unit is as follows:

<1st expansion structure >

An inlet coupled to the nozzle and a diffuser directed towards the outlet of the bottom of the reactor, the diameter of the inlet being smaller than the diameter of the diffuser. The inlet is coupled to the ejector and has a constant length, a tube of constant diameter, the outlet diameter of the inlet is the same as the inlet diameter of the diffuser and is smaller than the outlet diameter of the diffuser.

<2nd Expansion  Structure

At least one hole is provided in an upper part of the diffusion part leading from the inlet part outlet of the primary expansion pipe structure. In particular, the hole includes an upwardly inclined surface and a downwardly inclined surface formed to be inclined toward the lower portion of the oxo reactor. At this time, the upper inclined surface is 45 ° or more on the horizontal basis, the lower inclined surface is preferable because it can prevent the flow back to the hole from the nozzle when less than 15 °.

That is, by using the expansion structure, the reaction mixture can be circulated into the nozzle unit at 0.01 to 10 times the reactor charging capacity per minute to promote the mixing and mass transfer of the reaction mixture, so that the reaction gas phase does not participate in the reaction in the conventional reactor. It is supplied to the mixed gas supply pipe through the circulation pipe has the advantage that it does not need to be injected into the reactor through the nozzle.

Meanwhile, in the hydroformylation reaction of the present invention, a part of the product (reaction mixture) can be reused as a reactant (starting material) using a circulating reactor. The reaction mixture recovered from the bottom of the oxo reactor contains aldehydes, unconverted olefins and catalyst solutions. From the reaction mixture, an aldehyde, which is a target substance, can be separated using a separator. The separated aldehyde is recovered, and the catalyst mixture from which the aldehyde is separated from the reaction mixture is injected and supplied back into the oxo reactor through a nozzle provided in the oxo reactor.

BRIEF DESCRIPTION OF THE DRAWINGS In order that the present invention may be clearly understood and easily carried out, preferred forms of processes using the method of the present invention will be described by the accompanying schematic drawings. In FIG. 1, various standard items actually used in a factory, such as a valve, a temperature measuring device, and a pressure regulating device, which can be easily recognized by those skilled in the art, are omitted.

1 schematically shows the hydroformylation process of an olefin according to one embodiment of the invention. The olefin (for example, propylene) and the synthesis gas (carbon monoxide + hydrogen) are respectively formed in the upper portion 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. It is supplied to the nozzle 20 provided.

In order to increase the efficiency of the gas-liquid reaction, the inside of the oxo reactor 100 is provided with a nozzle 20 and a venturi 30 coupled to the nozzle, and the supplied olefin and syngas are supplied through the nozzle 20. It is continuously injected and supplied into the venturi 30. As such, the oxo reactor 100 may be a reactor equipped with a nozzle or a nozzle and a venturi for the purpose of increasing the efficiency of the gas-liquid reaction therein, and preferably the venturi-loop reactor. have.

The venturi tube comprises an inlet pointing to the top of the reactor and a diffusion pointing towards the bottom of the reactor as is known, wherein the diameter of the inlet is smaller than the diameter of the diffusion and is coupled to the injection means, and the expansion pipe located in the inlet. It is preferable to have one or more holes 60 in the upper portion. The hole 60 includes an upwardly inclined surface 61 and a downwardly inclined surface 62 each having an angle sufficient to prevent backflow from the nozzle.

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 0.01 to 0.95 times the length of the reactor body.

The mixed gas, which is a reaction raw material, is injected into the reactor while passing through the nozzle unit. The mixed gas is injected into the catalyst mixed solution charged into the reactor while forming micro bubbles. The high velocity of the catalyst solution at the nozzle makes the synthesis gas microbubbles, and the microbubbles of the mixed gas come into contact with the olefin and the catalyst mixed solution, thus providing a sufficient reaction area due to the large contact area of the gas-liquid. do. 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, and the hole is formed as a primary expansion structure and a secondary expansion structure. To facilitate mixing and mass transfer.

In addition, the flow of olefin and mixed gas injected by a dispersion plate mounted between the venturi tube and the outlet of the reactor may be 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, 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.

The olefin and syngas injected into the oxo reactor 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-butylaldehydes).

The reaction mixture containing the aldehyde is recovered through the recirculation pipe 12 using the circulation pump 40, and then circulated through the recirculation pipe 13 to the nozzle 20 provided in the reactor, a part of the reaction mixture circulated May be led to the catalyst / aldehyde separation device 50 through a separation pipe 17 branching from the recycle pipe 13 to separate the aldehyde.

The catalyst / aldehyde separator 50 for separating aldehydes is not limited as long as it is a means capable of separating aldehydes from the reaction mixture. The recovered aldehyde is sent to a separate recovery apparatus (not shown) through the aldehyde recovery pipe 18, and can be separated and recovered by various aldehydes and condensation products by treatment with a conventional distillation apparatus.

For example, in a hydroformylation process that produces butylaldehyde from propylene, the butylaldehyde recovered from the oxo reactor is sent to a fractionation tower to separate normal- and iso-butylaldehyde, respectively. The n-butylaldehyde in the fractionation column is hydrogenated with an aldol condensation reactor to produce octanol (2-ethylhexanol).

The target aldehyde 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 19.

The reaction mixture of the reactor mixed with the recycled catalyst mixture is passed through the heat exchanger 70 to the oxo reactor 100 together with the olefin and the synthesis gas supplied through the olefin supply pipe 10 and the synthesis gas supply pipe 11. It is injected and supplied into the oxo reactor 100 through the nozzle 20 provided. Recycling of the catalyst mixture from which the target material has been separated may be performed continuously.

In some cases, a portion of the recycled reaction mixture may be withdrawn to regenerate the catalyst, or fresh catalyst solution or reactivated catalyst solution may be added to the recycle stream of the reaction mixture. A heat exchanger 70 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 70 serves to maintain the reaction mixture recycled to the oxo reactor 100 at a temperature suitable for the hydroformylation reaction conditions.

The present invention also provides a first step of charging the catalyst mixture solution in the reactor; A second step of injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; And a third step of promoting mixing and mass transfer of the injected olefin and synthesis gas.

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), A catalyst using a transition metal such as platinum (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.

The ligand may be a tri-substituted phosphine, a phosphine oxide, an amine, an amide, or an isonitrile, or may be a tri-substituted phosphine, . 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; Aromatics 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, propylene is used when propylene is a raw material, and pentyl aldehyde is used when butylene 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 wt% 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, ethylene, propylene, 1 It is more preferable that it is -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 40:60. It is more preferable that it is to 60:40, and it is most preferable that it is 50: 50-40: 60.

The molar ratio of the olefin to the synthesis gas is preferably 95: 5 to 5:95, and more preferably 75:25 to 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 to 40 m / s.

The third step is to promote the mixing and mass transfer of the injected olefin and synthesis gas, and to promote the mixing and mass transfer of the injected olefin and synthesis gas by the two-stage expansion structure shown in FIG. This improves the reaction efficiency. That is, by using the expansion structure described above, the reaction mixture may be re-supplied into the nozzle unit at 0.01 to 10 times the reactor charging capacity per minute to promote mixing and mass transfer of the reaction mixture.

In the hydroformylation method of an olefin according to the present invention, it is preferable to add a step (fourth step) of carrying out the reaction while switching injection, mixing or delivery flow of the olefin and syngas simultaneously or sequentially with the third step. However, the conversion of the reaction raw material flow lengthens the residence time of the reaction raw material in the reactor, thereby maximizing 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 100 bar, more preferably carried out at a pressure of 5 to 50 bar.

It is then preferred to further include the step of recovering the reaction mixture and feeding it into the reactor 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 reactor charge catalyst capacity, and the flow rate of the reaction mixture circulated per minute is preferably 0.01 to 10 times the reactor charge capacity. For example, when the reactor charge catalyst capacity is 10 liters, the flow rate of the reaction mixture circulated per minute is preferably 0.1 to 100 L / min.

In the circulating step of the reactant, the method may further include separating a part of the circulated reaction mixture to separate the catalyst mixture solution and the aldehyde, and supplying the separated catalyst mixture solution to the circulation flow, and recovering the aldehyde. can do.

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 includes butyl aldehyde, more specifically, normal-butylaldehyde and iso-butylaldehyde, and the reaction mixture is a catalyst / aldehyde separation device. After being sent to separate the 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 in the fractionation column is introduced into the aldol condensation reactor to produce 2-ethylhexanal by condensation and dehydration, and then transferred to the hydrogenation reactor.

The present invention can improve the hydroformylation reactivity to obtain the desired aldehyde in a high yield, as well as to reduce the circulation flow rate by the external pump to reduce the reactor operating cost, and the economical effect of reducing the reactor operating nozzle in the reactor It also has the advantage that there is no need to refeed through the reactor.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are intended to help a specific understanding of the present invention, and the scope of the present invention is not limited to the Examples.

< Example  One: Comparative example  1 and circulating flow rate equal (2.0 liters per minute)>

1 and 2, a venturi-loop reactor 100 having a 3-liter capacity was manufactured and installed. The reactor 100 was able to maintain a constant temperature inside the reactor by flowing the heat medium oil in the jacket instead of the external heat exchanger (70).

The diameter of the nozzle 20 mounted in the venturi-loop reactor 100 was 1.7 mm, the diameter of the inlet was 8.0 mm, the length was 50 mm, the diameter of the diffusion was 25 mm, the length was 200 mm. Three holes 60 at the mm position were disposed on the same plane at 120 ° intervals. The inclination angle of the upper inclined surface 61 was 45 degrees, and the inclination angle of the lower inclined surface 62 was 15 degrees.

To 800 g of purified n-butylaldehyde, 48 g of triphenylphosphine (TPP) (corresponding to 6 wt% of solvent content), 0.8 g of rhodium triphenylphosphine acetylacetonate carbonyl (ROPAC) weight (based on solvent content) 1000 ppm) was dissolved to prepare an n-butylaldehyde catalyst solution.

The catalyst solution thus prepared was introduced into the reactor 100 and the external circulation pump 40 was operated to slowly circulate the catalyst solution at a rate of 1.5 liters per minute while purifying nitrogen gas through the nozzle 20 above the reactor 100. The whole system was purged three times.

The external circulation pump 40 was continuously maintained at a rate of 2.0 liters per minute, and the heat medium oil was flowed into the jacket outside the venturi-loop reactor 100 to maintain the temperature of the reactor 100 at 90 ° C. When the temperature was stabilized to 90 ℃ propylene was supplied at a flow rate of 12 g / min until the internal pressure of the reactor 100 is 16.2 bar.

Confirm that the internal temperature of the venturi-loop reactor 100 was maintained at 90 ° C. for 5 minutes after the supply, and then the synthesis gas (mixed gas having a molar ratio of carbon monoxide and hydrogen of 50:50) was set at a supply pressure of 18.8 bar. The reaction was started at the same time as feeding to the nozzle neck portion 20 of.

The flow rate of the syngas supplied to the reactor 100 was measured over time while maintaining the internal temperature of the venturi-loop reactor 100 at 90 ° C. through an automatic temperature control device (not shown) connected to the reactor 100. . After the reaction for 2 hours, the mixed gas was shut off, the external circulating pump 40 was immediately stopped, the reactor 100 was cooled to room temperature, the pressure was released, and the mixture of the total catalyst solution and the product was separated. The weight of the entire solution after the reaction was 1,302 g, and the butyl aldehyde produced by the reaction was 482 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 synthesis gas during the reaction was 5.7 liters per minute.

< Example  2: Comparative example  2 and circulating flow rate equal (1.5 liters per minute)>

Other conditions and methods were performed in the same manner as in Example 1 except that only the circulation flow rate was reduced to 1.5 liters per minute.

The total weight of the mixture of the catalyst solution and the product obtained after the reaction for 2 hours was 1,271 g and the weight of the butylaldehyde produced by the reaction was 469 g. The maximum consumption rate of the synthesis gas during the reaction was 5.5 liters per minute.

< Comparative example  1>

As shown in FIG. 3, the flow rate of the external circulation pump 40 was increased to 2.0 liters per minute and the venturi-loop reactor 100 ′ having no hole 60 at the top of the expansion pipe was used. The method was carried out in the same manner as in Example 1.

The total weight of the mixture of catalyst solution and product obtained after 2 hours of reaction was 1,265 g and the weight of butylaldehyde produced by the reaction was 465 g. The maximum consumption rate of the synthesis gas during the reaction was 5.4 liters per minute.

< Comparative example  2>

Other conditions and methods were repeated in the same experiment as in Comparative Example 1 except that the circulation flow rate was lowered to 1.5 liters per minute.

The total weight of the mixture of catalyst solution and product obtained after 2 hours of reaction was 1,207 g, the weight of butylaldehyde produced after the reaction was 405 g, and the maximum consumption rate of the synthesis gas during the reaction was 3.9 liters per minute.

< Comparative example  3>

2 hours while maintaining 1000 rpm in a stirring apparatus while supplying syngas with the same method and procedure as Example 1, except that a 3 liter autoclave reactor having the same capacity was used instead of the Venturi-loop reactor of Example 1. Reaction was carried out.

The total weight of the mixture of the catalyst solution and the product obtained after the reaction for 2 hours was 1,201 g, the weight of butylaldehyde produced after the reaction was 403 g, and the maximum consumption rate of the syngas during the reaction was 3.9 liters per minute.

The configuration and measurement results of Example 1-2 and Comparative Example 1-3 are summarized as Table 1 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reactor type Venturi-Loop Venturi-Loop Venturi-Loop Venturi-Loop Autoclave Hall presence Three
(70 mm position from the top of the nozzle) Three
(70 mm position from the top of the nozzle) - - Circulating flow rate of circulation pump (L / min) 2.0 1.5 2.0 1.5 - Total weight of mixture of catalyst solution and product (g) 1,302 1,271 1,265 1,207 1,201 Butylaldehyde
Production amount (g) 482 469 465 405 403 Syngas consumption rate (L / min) 5.7 5.5 5.5 3.9 3.9

As shown in Table 1, the Venturi-loop reactor having a hole in the upper part of the expansion pipe than Comparative Example 1, 2 or the comparative example 3 using the autoclave reactor having no separate hole in the upper part of the expansion pipe was used. In the case of Example 1, in which the circulation flow rate of the circulation pump was reduced by 1/4 compared to Comparative Example 1, the reaction rate was measured in all measurement items such as the total weight of the mixture of the catalyst solution and the product, the butylaldehyde weight, and the maximum consumption rate of the synthesis gas. Was high and the efficiency was high. Particularly, in the case of Example 2 in which the circulation flow rate was reduced by 1/4, it was confirmed that the reaction efficiency was equal to or higher than that of Comparative Example 1 in which the circulation flow rate was not reduced.

While the invention has been described in detail above 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 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 an enlarged cross-sectional view of a nozzle unit showing expansion phenomenon in a hydroformylation apparatus of an olefin of the present invention. FIG.

3 is a schematic contrast process diagram illustrating the hydroformylation process of olefins according to the prior art.

<Explanation of symbols for main parts of the drawings>

10,10 ': olefin feed piping

11,11 ': Syngas supply piping

12, 13, 14, 15, 16, 12 ', 13', 14 ', 15', 16 ': recirculation piping

17, 17 ': Separate piping

18, 18 ': aldehyde recovery piping

19, 19 ': catalyst solution supply pipe

20, 20 ': nozzle

30, 30 ': Venturi

40, 40 ': External circulation pump

50, 50 ': catalyst / aldehyde separator

60: hole

61: upward slope

62: downward slope

70, 70 ': heat exchanger

100, 100 ': oxo reactor

Claims (14)

In the hydroformylation apparatus of the olefin is provided with a nozzle in which the venturi is coupled to the upper end inside the oxo reactor, The nozzle is integrally formed at the lower end of the reactor inlet portion and consists of a diffusion portion that is widened toward the reactor outlet side to have an expanded pipe shape. At least one hole is formed in the upper part of the expansion pipe (hydroformylation apparatus of olefin), characterized in that inducing the promotion of mixing and delivery. The method of claim 1, The oxo reactor is a venturi-loop reactor, hydroformylation reactor of olefins. The method of claim 1, The diameter of the nozzle is 0.1 to 500 mm, Inlet diameter of the inlet and the diffusion is 1 to 10 times the diameter of the nozzle, respectively. The reactor outlet side diameter of the diffusion portion is 0.1 to 10 times the diameter of the inlet side of the diffusion portion hydroformylation reactor of the olefin. The method of claim 3, wherein The total length of the diffusion portion is 0.1 to 10 times the length of the inlet portion hydroformylation reactor of the olefin. The method of claim 1, The length of the venturi is hydroformylation reactor of olefin is 0.01 to 0.95 times the length of the reactor body. The method of claim 1, The hole includes an upper inclined surface and a lower inclined surface formed to be inclined toward the bottom of the oxo reactor, The upper inclined surface is 45 degrees or more on a horizontal basis, The lower inclined surface is hydroformylation reaction apparatus of olefin is less than 15 ° on the horizontal basis. In the hydroformylation method using a hydroformylation reactor of olefins, The olefin hydroformylation reaction apparatus may include a first step of charging a catalyst mixture solution into a reactor using the apparatus of any one of claims 1 to 6; A second step of injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; And A third step of carrying out the reaction while promoting the mixing and mass transfer of the injected olefin and synthesis gas to produce a reaction mixture; Hydroformylation method of the olefin comprising a. The method of claim 7, wherein The catalyst mixed solution is composed of a metal-carbonyl complex catalyst, a ligand and a solvent, the metal-carbonyl complex catalyst is 10 to 2000 ppm based on the solvent content, and the ligand is 1 to 30 wt% based on the solvent content. Method for hydroformylation of olefins, characterized in that. The method of claim 7, wherein The molar ratio of the injected olefin and the synthesis gas is 95: 5 to 5:95, the molar ratio of the synthesis gas CO: H ₂ is 5:95 to 70:30. The method of claim 7, wherein The olefin and syngas are each injected and supplied into the oxo reactor through a nozzle at a spray linear velocity of 5 to 40 m / s under a pressure of 5 to 200 bar, respectively. The method of claim 7, wherein The third step is a method for hydroformylation of olefins characterized in that to promote the mixing and mass transfer of the reaction mixture by re-feeding the reaction mixture to the nozzle at the top of the reactor at 0.01 to 10 times the reactor charge capacity per minute. The method of claim 7, wherein A fourth step of performing the reaction at a temperature of 50 to 200 ° C. and a pressure of 5 to 100 bar while switching injection, mixing or delivery flows of olefins and syngas simultaneously or sequentially with the reaction of the third step. step; Hydroformylation method of the olefin, characterized in that it further comprises. 13. The method of claim 12, Separating a portion of the reaction mixture of the fourth step to separate the catalyst mixture solution and the aldehyde; And Supplying the separated catalyst mixture solution to a circulating flow and recovering aldehydes; Hydroformylation method of the olefin, characterized in that it further comprises sequentially. The method of claim 7, wherein The reaction of the third step is a hydroformylation method of olefin, characterized in that carried out at a temperature of 50 to 200 ℃ and a pressure of 5 to 100 bar.

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