KR20110128967A - A method for the hydroformylation of olefin having excellent n/i ratio - Google Patents

Abstract

PURPOSE: A method for hydroformylating olefin and an apparatus for the same are provided to easily separate products and a catalyst using a filter and to omit a catalyst separating process of high temperature. CONSTITUTION: An apparatus for hydroformylating olefin includes a loop type reactor(100). The loop type reactor includes a spraying unit(20), a reactor outlet(40), and a venturi pipe(30). The spraying unit is mounted at the upper side of the reactor. The spraying unit sprays olefin and synthesized gas(CO/H_2) into a hetero catalyst mixed solution which is arranged in the reactor. The reactor outlet is arranged at the lower side of the reactor. The reaction mixture of the olefin and the synthesized gas is discharged through the reactor outlet. The venturi pipe is mounted between the spraying unit and the reactor outlet. The flow of the olefin and the synthesized gas circulates through the venturi pipe.

Description

A method for the hydroformylation of olefin having excellent N / I ratio}

The present invention relates to a hydroformylation method of olefins having excellent reaction selectivity. More specifically, as a hydroformylation reaction apparatus, a hydroformylation reaction catalyst is used while using a loop type reactor capable of high pressure reaction and improving reaction efficiency. The present invention relates to a hydroformylation method of an olefin having a freely adjustable CO partial pressure and an N / I selectivity in view of the relatively free activity of the catalyst by using a relatively low activity hetero catalyst.

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 the oxo reaction are transformed into aldehyde derivatives acid and alcohol through oxidation or reduction. In addition, after the condensation reaction such as Aldol (Aldol) may be transformed into various acids and alcohols containing a long alkyl group through oxidation or reduction reaction. Such alcohols and acids are used as solvents, additives, and raw materials for 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 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, Amine, Amide or Isonitrile 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 together with the catalyst mixture to a separation system to separate the hydrocarbon and catalyst mixture, after which the catalyst mixture is circulated to the reactor and the hydrocarbon components are sent 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 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 hydroreactor 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 reaction process is a gas or liquid recycle system. In the 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. 1 is a process chart for performing a hydroformylation process of an olefin using a continuous stirred reactor (CSTR), by connecting a catalyst solution recirculation pipe 18 'between the recirculation pipes 14' and 15 '. An example of introducing the remaining catalyst solution or reactivated catalyst solution after removing aldehyde from 17 'into the reactor system is shown. That is, the olefin (for example, propylene) and the synthesis gas are respectively placed on 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 equipped with a nozzle 20' and an impeller 30 'coupled to the nozzle, and the supplied olefin and syngas are supplied to the nozzle 20'. ) And continuously injected into the oxo reactor 100 '. 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 'by using the circulation pump 50', and then the nozzles provided in the reactor through the recirculation pipes 13 ', 14', 15 ', 16'. 20 '). At this time, a part of the circulating reaction mixture may be introduced into the catalyst / aldehyde separator 70 'from the recirculation pipe through the separation pipe 17' to separate the aldehyde.

The recovered aldehyde is sent to a separation recovery device or the like (not shown) through the aldehyde recovery pipe 19 ', and various aldehydes and condensation products can be separated and recovered by treatment with a conventional distillation device or the like. 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 18 '.

The reaction mixture of the reactor combined with the recycled catalyst mixture is then combined with the olefin and synthesis gas supplied via the heat exchanger 60 'through the olefin feed line 10' and the syngas feed line 11 '. It is injected and supplied into the oxo reactor 100 'through the nozzle 20' provided in the 100 '. In addition, a heat exchanger 60 'may be provided between the recirculation pipes 15' and 16 ', but the position is not limited to a specific position on the circulation cycle. The heat exchanger 60 'serves to maintain the reaction mixture recycled to the oxo reactor 100' at a temperature suitable for the hydroformylation reaction conditions. However, in the case of the above method, a high pressure reaction is difficult due to high activity because of using a low-molecular pressure catalyst such as rhodium / triphenylphosphine for low pressure oxo process, and the CO partial pressure is low due to deactivation of the catalyst. In addition, the N / I selectivity is 89 to 92%, it is difficult to arbitrarily adjust the selectivity in accordance with the market conditions of normal-butyl aldehyde and iso-butyl aldehyde.

U. S. Patent No. 5,763, 678 also discloses a hydroformylation method in which a series of loop-type reactors are applied to replace agitation through circulation. However, this still has 90% N / I selectivity, making it difficult to control the selectivity, and there is a limit to improving the efficiency of the hydroformylation reaction, and thus, the reaction residence time is generally not satisfactory with a single reactor alone. It has a disadvantage such as to give a large or to have two or more reactors in series.

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 An apparatus for hydroformylation of olefins present and a method for hydroformylation of olefins having effective reaction selectivity using the same.

The present invention provides a means for solving the above problems, a method for hydroformylating an olefin, comprising the steps of: charging a heterocatalyst mixed solution in a loop reactor equipped with a venturi; Injecting olefin and syngas (CO / H ₂ ) into a heterocatalyst mixed solution charged in the reactor, while controlling a CO partial pressure within a range of 0.5 to 20 mol%; And a third step of carrying out the reaction while switching the injection flow of the olefin and the synthesis gas.

The hydroformylation reaction apparatus for olefins used in the present invention includes: injection means for injecting olefins and syngas (CO / H ₂ ) into a 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 loop type reactor equipped between the injection means and the reactor outlet and having a venturi for circulating a flow of olefins and syngas.

Specifically, the apparatus further includes a circulation pipe connected to the outlet of the reactor bottom and the injection means mounted on the upper part of the reactor, and recovering the reaction mixture from the outlet of the reactor and supplying the reaction mixture to the injection means mounted on the upper part of the reactor to circulate the reaction mixture. desirable.

A separation pipe separating at any one of the circulation pipe to separate the reaction mixture from the circulation flow; A vaporizer connected to the separation pipe for vaporizing the reaction mixture; A heat exchanger connected to the vaporizer to prevent the formation of by-products in the aldehyde product-containing catalyst mixed solution discharged from the vaporizer, and to control the reaction heat of the circulating reaction mixture; A circulation pump connected to the heat exchanger to supply a catalyst mixed solution into the reactor; A catalyst mixed solution supply pipe connected to one of the circulation pipes to supply the catalyst mixed solution to the circulation pipe; And an aldehyde recovery piping connected to the catalyst / aldehyde separator for recovering aldehydes.

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

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.

In addition, the partial pressure of CO inside the reactor 100 may be adjusted relatively freely within a range of 0.5 to 20 mol%.

The present invention is characterized by the use of the above apparatus and the use of a heterocatalyst as a catalyst. That is, a first step of charging a heterocatalyst mixed solution into the venturi-loop 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 carrying out the reaction while circulating the injection stream of the olefin and the syngas. In this case, the partial pressure of CO inside the reactor 100 is controlled to be relatively freely controlled within a range of 0.5 to 20 mol%.

This CO partial pressure control is due to the use of a heterocatalyst as a catalyst in the reactor. Suitable heterocatalysts for use in the present invention include zeolite Y or encapsulated or anchored in a support such as MCM-41, MCM-48 or SBA-15. HRh (CO) (PPh ₃ ) ₃ type catalyst, which has the advantage that there is little Rh leaching of the catalyst Rh falling from the support and relatively high activity compared to other hetero catalysts.

On the other hand, according to the present invention, since the N / I selectivity reaches 75 to 98% as shown in the following examples by using the reactor and the catalyst as described above, an example of the hydroformylation system of the present invention As shown in FIG. 2, in FIG. 1 to which a conventional commercially available continuous stirred reactor (CSTR) is applied, a catalyst separator 70 ′, which is not necessarily required, is provided. Of course, it is preferable to further include the step of recovering the reaction mixture after the third step.

Hereinafter, the present invention will be described in detail with reference to FIG. 2.

First, in the present invention, the injection means 20 is mounted on top of the reactor 100 for injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor 100; A reactor outlet 40 positioned below the reactor 100 through which a reaction mixture of olefin and syngas is discharged; And a loop type reactor 100 mounted between the injection means 20 and the reactor outlet 40 and having a venturi 30 for circulating a flow of olefins and syngas. Provide a device.

The injection means 20 is not particularly limited as long as it can inject olefin 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, the ejector tube 30 is preferably coupled to the ejector. The venturi tube 30 includes an inlet portion 30a and a diffusion portion 30b as is known, and the diameter of the inlet portion 30a is smaller than the diameter of the diffusion portion 30b (0.1 to 10000 mm). ), It is preferably coupled to the injection means 20, and the diffusion portion 30b is directed toward the bottom of the reactor 100. The diameter of the inlet portion 30a is preferably 1 to 10 times the diameter of the nozzle, and the diameter of the diffusion portion 30b is preferably 2 to 10 times the diameter of the inlet portion 30a. In addition, the length of the venturi tube 30 is preferably 0.2 times to 0.8 times the total length of the reactor 100.

The mixed gas, which is a reaction raw material, is injected into the reactor 100 through the injection means 20 and the venturi tube 30 coupled thereto, and the mixed gas is injected into the reactor 100 while forming micro bubbles. It is injected into the catalyst mixture solution charged in. The venturi tube 30 is immersed in the catalyst solution in the reactor 100, the catalyst solution and the synthesis gas is mixed at the nozzle portion is descended through the venturi tube 30 and mixed with the catalyst solution in the reactor 100.

Due to the high flow rate of the catalyst solution at the nozzle area, 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, it is more preferable that the flow of the olefin and the mixed gas injected by the distribution plate (not shown) mounted between the venturi tube 30 and the reactor outlet 40 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 30 and the reactor outlet 40, even more preferably between 1/2.

In addition, the shape of the dispersion plate may be flat or convex or concave with respect to the outlet of the reactor, the size may be 0.5 to 0.9 times the diameter of the reactor (100).

In addition, the hydroformylation reactor is connected to the outlet 40 of the reactor bottom and the injection means 20 mounted on the reactor top, and the injection means mounted on the reactor by recovering the reaction mixture from the reactor outlet 40 And circulating piping (12, 13, 14, 16) to supply to (20) to circulate the reaction mixture.

The reaction raw material olefin and syngas are reacted in the presence of a heterocatalyst mixed solution to produce an aldehyde as a reaction product. Accordingly, a reaction mixture including the reaction product, heterocatalyst mixed solution, unconverted olefin, synthesis gas, and other reaction by-products is present in the reactor, and the reaction mixture is recovered from the reactor bottom 40 to It is supplied to the upper injection means 20 and circulated. 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 may be controlled by the circulation pump 50 provided in the circulation pipe 12.

In addition, in the conventional continuous stirred reactor (CSTR) shown in Figure 1, while 0.5 to 3 mol%, the partial pressure of CO inside the reactor 100 can be controlled relatively freely within the range of 0.5 to 20 mol% N / I It is easy to adjust the selectivity.

In addition, the circulation pipe may be provided with a heat exchanger 60, the position is not limited to a specific position on the circulation pipe. The heat exchanger 60 serves to maintain the reaction mixture circulated to the reactor 100 at a temperature suitable for the hydroformylation reaction conditions. Recirculation of the catalyst mixture solution may be carried out continuously, and in some cases, a portion of the recycled reaction mixture may be discharged to regenerate the catalyst, or fresh catalyst solution or reactivated catalyst solution may be added to the recycle stream of the reaction mixture. have.

The present invention also provides a first step of charging a heterocatalyst mixed solution in the reactor described above; Injecting olefin and synthesis gas (CO / H ₂ ) into a heterocatalyst mixed solution charged in the reactor, while controlling a CO partial pressure within a range of 0.5 to 20 mol%; And a third step of performing the reaction while switching the injection flow of the olefin and syngas. It relates to a hydroformylation method of an olefin comprising a.

The first step is to charge a heterocatalyst mixed solution in the reactor, the heterocatalyst mixed solution loaded in the reactor is generally used in the hydroformylation reaction, the metal-carbonyl complex catalyst and ligand It may include.

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 ] are encapsulated in a support such as Zeolite Y or MCM-41, MCM-48, SBA-15, etc. Or anchoring 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, when the hydridocarbonyltri (triphenylphosphine) rhodium [HRh (CO) (TPP) ₃ ] complex, which is an active form of the catalyst, is encapsulated or anchored to the support, it is generally used to stabilize the Rh catalyst in a homogeneous catalyst. The use of TPP entering an excess of 100 mol or more of the catalyst is unnecessary, thus avoiding additional cost loss.

The solvent used in the catalyst mixed solution is not limited thereto, for example, aldehydes such as propane aldehyde, butyl aldehyde, pentyl aldehyde, or baler aldehyde; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or cyclohexanone; Alcohols such as ethanol, pentanol, octanol and tensanol; 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 aldehyde 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 wt% or less 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 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.

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 100 bar, more preferably carried out at a pressure of 5 to 50 bar.

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 content of the catalyst solution charged into the reactor, and the flow rate of the reaction mixture circulated per minute is preferably 0.01 to 20 times the reactor charging capacity. For example, when the amount of the reactor charged catalyst is 10 liters, the flow rate of the reaction mixture circulated per minute is preferably 0.1 to 200 L / min.

Specifically, when the olefin which is the starting material of the hydroformylation method is propylene, the reaction mixture contains butylaldehyde, more specifically, up to 99% of normal-butylaldehyde and at least 1% of iso-butylaldehyde, and most of them The normal-butylaldehyde is introduced into the aldol condensation reactor to produce 2-ethylhexanal by condensation and dehydration, and then transferred to a hydrogenation reactor, whereby hydrogenated to produce octanol (2-ethylhexanol). have.

2 schematically shows the hydroformylation process of an olefin according to one embodiment of the invention. In FIG. 2, various standard items actually used in a factory, such as a valve, a temperature measuring device, a pressure regulating device, etc., which can be easily recognized by those skilled in the art, are omitted.

The olefin (for example, propylene) and the syngas are nozzles 20 provided 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. Is supplied.

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. Continuously sprayed and supplied into the venturi 30. 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 50, and then circulated to the nozzle 20 provided in the reactor through the recirculation pipes 13, 14, 15, and 16. The recovered aldehyde may be treated with a conventional distillation apparatus or the like to separate and recover various aldehydes and condensation products. 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 60. It is injected and supplied into the oxo reactor 100 through the nozzle 20 provided. Given that the catalyst used in the present invention is of the slurry type, a catalyst type catalyst separator 80 is provided, such as a simple membrane filter that separates the product from the top of the reactor nozzle or from the circulation line.

In addition, a heat exchanger 60 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 60 serves to maintain the reaction mixture recycled to the oxo reactor 100 at a temperature suitable for the hydroformylation reaction conditions.

According to the present invention, the CO partial pressure can be freely used because the reactor is relatively free of deactivation of the catalyst by using a loop type reactor capable of high pressure reaction and increasing the reaction efficiency and a hetero catalyst having relatively low activity as the reaction catalyst. N / I selectivity is adjustable because it can be controlled, and the product and catalyst can be separated relatively easily by a filter, thereby having an excellent effect of not having to undergo a high temperature complex catalyst separation process.

1 is a schematic diagram showing a reactor used in the hydroformylation process of an olefin when using a continuous stirred reactor (CSTR) and a homo catalyst according to the prior art.
Figure 2 is a schematic diagram showing the reactor used in the hydroformylation process of the olefin when the venturi-loop type apparatus of the present invention and a hetero catalyst are used.

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.

In Comparative Examples 1 and 1-3, the CO partial pressure conditions and the N / I selectivity results of the examples using the venturi-loop reactor + hetero catalyst according to the present invention and the example using the conventional CSTR reactor + homo catalyst were respectively tested. Observe.

< Comparative example  1-3>

As shown in FIG. 1, a CSTR 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. A catalyst solution was prepared by dissolving 48 g of triphenylphosphine (TPP) and 0.8 g of rhodium triphenylphosphine acetylacetonate carbonyl (ROPAC) in 800 g of purified toluene. The reason why toluene is used as the solvent is to facilitate N / I selectivity analysis of the generated aldehyde. 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 flowed into the jacket outside the 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 was confirmed that the internal temperature of the reactor was maintained at 90 ℃, the reaction was started by injecting a synthesis gas preset at a supply pressure of 18.8 bar so that the CO partial pressure is 2.5 mol%.

While maintaining the internal temperature of the reactor at 90 ℃ to maintain the rpm of the stirring apparatus to 1000 to measure the flow rate of the synthesis gas supplied to the reactor over time. Maximum flow rate was 3.9 liters per minute. After reacting for 1.5 hours, the mixed gas was shut off, and 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. The total weight of the reaction solution was 1.210 g, so the butylaldehyde produced by the reaction was 361 g. The N / I selectivity of the aldehydes produced by gas chromatography was 89.7%.

The experiments were conducted according to the same procedure except that the CO partial pressure was injected by adjusting the ratio of the synthesis gas to 0.5 mol% and 3.5 mol%, and the results are summarized together in Table 1.

division Comparative Example 1 Comparative Example 2 Comparative Example 4 CO concentration (%) 2.5 0.5 3.5 Butylaldehyde production amount (g) 361 340 375 Syngas consumption rate (L / min) 3.7 3.5 3.8 N / I selectivity (%) 89.7 91.3 88.1

<Aging test>

The same catalyst as the above reaction was injected into the CSTR reactor to inject carbon monoxide and nitrogen such that the gaseous molar ratio of carbon monoxide was as shown in Table 2 below, maintaining the pressure in the reactor to be 18.8 bar and at 120 ° C. at the time shown in Table 2 below. According to the aging experiment after the temperature was lowered to room temperature and the internal gas was removed and the catalytic activity experiment was carried out in the same manner as the above method and the results are shown in Table 2.

At this time, the catalytic activity of each condition was expressed as a relative value with the catalyst activity of the fresh catalyst solution not subjected to the aging experiment as 100, and the catalytic activity was based on the weight of the butylaldehyde produced during the reaction for 2 hours. It was measured by.

division CO gas partial pressure, Mol% Catalytic activity (%) Fresh 50 hr 200 hr 350 hr 500 hr Comparative Example 1 2.5 100 95 91 90 88 Comparative Example 2 0.5 100 99 98 99 97 Comparative Example 3 3.5 100 86 78 73 67

< Example  1-4>

A venturi-loop reactor with a 3 liter capacity was constructed and installed as in FIG. 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.

A catalyst solution was prepared by adding 4.0 g of a heterogeneous catalyst (catalyst content 0.5% w / w) anchored with phosphotungstic acid catalyst HRh (CO) (PPh ₃ ) ₃ to a zeolite-Y support prepared in advance in 800 g of purified toluene. It was. 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 flowed into the jacket outside the 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 33 bar. 5 minutes after the supply, confirm that the internal temperature of the venturi-loop reactor is maintained at 90 ° C., and the pre-set synthesis gas is injected at a supply pressure of 40 bar so that the CO partial pressure is 2.5 mol%. The reaction was started simultaneously with feeding 10).

The flow rate of the syngas supplied to the reactor was measured over time while maintaining the internal temperature of the venturi-loop reactor through a thermostat connected to the reactor at 90 ° C. Maximum flow rate was 2.8 liters per minute. After reacting for 2 hours, the mixed gas was shut off, the circulating pump was stopped immediately, 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. The total weight of the reaction solution was 1.168 g, and thus the weight of butylaldehyde produced by the reaction was 364 g. The N / I selectivity of the resulting butylaldehyde was 92.1%.

The experiment was carried out according to the same procedure except that the CO partial pressure was injected to adjust the ratio of the synthesis gas to 0.5 mol%, 10 mol%, 20 mol%, the results obtained are summarized together in Table 3 below.

division Example 1 Example 2 Example 3 Example 4 CO concentration (%) 2.5 0.5 10 20 Butylaldehyde production amount (g) 364 347 418 443 Syngas consumption rate (L / min) 2.8 2.5 3.1 3.4 N / I selectivity (%) 92.3 95.1 87.0 82.5

Aging Experiment

The same catalyst as the above reaction was introduced into a venturi-loop reactor to inject carbon monoxide and nitrogen such that the gaseous molar ratio of carbon monoxide was as shown in Table 4 below, maintaining the pressure in the reactor at 40 bar and After the aging experiment was performed over time, the catalytic activity experiment was performed in the same manner as the above method, and the results are shown in Table 4 below.

division CO gas partial pressure, Mol% Catalytic activity (%) Fresh 50 hr 200 hr 350 hr 500 hr Example 1 2.5 100 98 97 96 97 Example 3 10 100 94 92 90 91 Example 4 20 100 89 89 87 87

As shown in Tables 1 to 4 above, a hetero catalyst having a relatively low activity as a hydroformylation reaction catalyst is used as a hydroformylation reaction apparatus, and a loop type reactor capable of high pressure reaction and improving reaction efficiency according to the present invention. In the case of Examples 1 to 4 using the catalyst, the CO partial pressure can be freely adjusted because it is relatively free of deactivation of the catalyst, and thus the N / I selectivity can be adjusted compared to Comparative Examples 1 to 3, and the product and the catalyst can be easily separated by a filter. Since it was possible to confirm that it has an excellent effect that does not need to go through a high temperature complex catalyst separation process.

10,10 ': Olefin supply piping 11,11': Syngas supply piping
12,12 ', 13,13', 14,14 ', 15,15', 16,16 ': circulation pipe
17,17 ': Separation pipe 18': Catalyst solution supply pipe
19 ': Aldehyde recovery piping
20,20 ': Ejector 20a, 20a': Nozzle
30: Venturi tube 30 ': impeller
30a: inlet 30b: diffusion
40, 40 ': reactor outlet 50, 50': circulation pump
60,60 ': Heat exchanger 70': Catalyst / aldehyde separator
80: membrane filter 100, 100 ': oxo reactor

Claims (16)

Injection means mounted on the reactor to inject olefin and syngas (CO / H ₂ ) into the heterocatalyst mixed 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 venturi tube mounted between the injection means and the reactor outlet for circulating a flow of olefins and syngas; It consists of a loop reactor equipped with
Hydroformylation reactor of olefins. The method of claim 1,
The injection means is characterized in that it comprises an ejector equipped with a nozzle having a diameter in the range of 0.1 to 1000mm
Hydroformylation reactor of olefins. The method of claim 1,
The venturi tube consists of an inlet from the top and a diffuser directed toward the reactor outlet, the diameter of the inlet being smaller than the diameter of the diffuser.
Hydroformylation reactor of olefins. The method of claim 3, wherein
Inlet diameter of the venturi tube is characterized in that in the range of 0.1 to 10000 mm
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,
Between the venturi and 1/3 to 2/3 of the reactor outlet is characterized in that the dispersion plate of 0.5 to 0.9 times the size of the reactor is further located
Hydroformylation reactor of olefins. The method of claim 2,
A filter type catalyst separator for separating the product and the catalyst in the nozzle top or the circulation line is further provided.
Hydroformylation reactor of olefins. A first step of charging a heterocatalyst mixed solution in a loop reactor equipped with the venturi of any one of claims 1 to 7;
Injecting olefin and synthesis gas (CO / H ₂ ) into a heterocatalyst mixed solution charged in the reactor, while controlling a CO partial pressure within a range of 0.5 to 20 mol%; And
And a third step of performing the reaction while switching the injection flow of the olefin and syngas.
Hydroformylation of Olefin. The method of claim 8,
The heterocatalyst solution is a metal-carbonyl complex catalyst And a ligand and a support thereof.
Hydroformylation of Olefin. The method of claim 9,
The concentration of the catalyst mixture solution is characterized in that the metal carbonyl complex catalyst 10 to 2000 ppm, ligand 1 wt% or less
Hydroformylation of Olefin. The method of claim 8,
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. The method of claim 8,
The mixed gas (CO: H ₂ ) is characterized in that the mixing ratio of CO: H ₂ is 5:95 to 70:30
Hydroformylation of Olefin. The method of claim 8,
The molar ratio of the olefin and the synthesis gas is injected is characterized in that 95: 5 to 5:95
Hydroformylation of Olefin. The method of claim 8,
The olefin and the synthesis gas are respectively injected and supplied into the oxo reactor at a pressure of 5 to 200 bar
Hydroformylation of Olefin. The method of claim 8,
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. The method of claim 8,
The reaction of the third step is characterized in that it is carried out at a temperature of 50 to 200 ℃ and a pressure of 5 to 100 bar
Hydroformylation of Olefin.

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