KR101411133B1 - A method for the hydroformylation of olefin having excellent N／I ratio - Google Patents

Abstract

The present invention relates to a process for hydroformylation of olefins which is excellent in reaction selectivity and which uses a loop type reactor capable of high pressure reaction and high reaction efficiency as a hydroformylation reaction apparatus, , It is possible to control the CO partial pressure freely and to control the N / I selectivity. Since the product and the catalyst can be separated by the filter relatively easily, it is possible to perform a complicated catalyst separation process at a high temperature And has an excellent effect that is not necessary.

Description

[0002] A method for hydroformylation of an olefin having excellent reactivity selectivity is known,

The present invention relates to a process for hydroformylation of olefins which is excellent in reaction selectivity and more specifically to a process for the hydroformylation reaction using a loop reactor capable of high pressure reaction and high reaction efficiency, In which the CO partial pressure is freely adjustable and the N / I selectivity can be controlled, in view of the fact that the catalyst is relatively free from deactivation by using a relatively low activity of the hetero catalyst.

A hydroformylation reaction, commonly known as an oxo (OXO) reaction, involves the reaction of various olefins with a synthesis gas (CO / H ₂ ) in the presence of a metal catalyst and a ligand, linear, normal, branched and iso aldehyde are produced. The oxo reaction was first discovered by Otto Roelen in Germany in 1938 and around 8.4 million tons of various aldehydes (including alcohol derivatives) are produced and consumed worldwide through the oxo process in 2001 ( SRI report , November 2002 , 682 , 700A).

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.

The catalysts used in the present oxo process are mainly cobalt (Co) and rhodium (Rh) series, and the ratio of linear (normal) to aldehyde generated by the operating conditions such as the type of ligand and CO partial pressure branched (iso) isomers). Currently, over 70% of the world's oxo plants are adopting the Low Pressure OXO Process, which uses rhodium-based catalysts.

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

Examples of the ligand include phosphine (Phosphine, PR ₃ , R is C ₆ H ₅ or nC ₄ H ₉ ), 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 PVC plasticizer raw material such as DOP (Dioctyl Phathalate), and is also used as an intermediate raw material for synthetic lubricants and surfactants. Propylene is introduced into the oxo reactor using a catalyst together with syngas (CO / H ₂ ) to produce n-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 stripper's hydrocarbons are stripped by the freshly supplied syngas so that unreacted propylene and syngas are recovered in the oxo reactor and the butylaldehyde is transferred to the column and separated into normal and iso-butylaldehyde, respectively. The n-butylaldehyde in the bottom of the column is introduced into the aldol condensation reactor and condensed and dehydrated to produce 2-ethylhexanoic acid, which is then transferred to a hydrogenation reactor and octanol (2-ethylhexanol) is produced by hydrogenation do. The reactants at the outlet of the hydrogenation reactor are transported to the fractionation column and after separating the soft / hard ends, produce the octanol product.

The hydroformylation reaction can be carried out continuously, semicontinuously or batchwise, and a typical hydroformylation process is a gas or liquid recirculation system. It is important that the hydroformylation reaction improves the reaction efficiency by allowing smooth contact of liquid and gaseous starting materials. For this purpose, a continuous stirred tank reactor (CSTR) has been used, which conventionally stirs the liquid and vapor components in the reactor uniformly. FIG. 1 is a flow chart for performing a hydroformylation process of an olefin using a continuous stirred tank reactor (CSTR), in which a catalyst solution recycle line 18 'is connected between recycle lines 14' and 15 ' (17 ') to remove aldehyde and introduce the remaining catalyst solution or reactivated catalyst solution into the reactor system. That is, the olefin (for example, propylene) and the syngas are respectively supplied to the upper portion of the oxo reactor 100 'through which the catalyst solution is loaded through the olefin feed pipe 10' and the synthesis gas feed pipe 11 ' Is supplied to the nozzle 20 'provided.

In order to increase the efficiency of the gas-liquid reaction, a nozzle 20 'and an impeller 30' are provided in the oxo reactor 100 '. The supplied olefin and synthesis gas are supplied to the nozzle 20' ) Into the oxo reactor 100 '. The olefin and synthesis gas 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 and catalyst solutions in addition to the objective aldehydes (e.g., normal- and iso-butylaldehyde).

The reaction mixture containing the aldehyde is recovered through the recycle line 12 'using the circulation pump 50' and then passed through the recycle line 13 ', 14', 15 ', 16' 20 '). At this time, a part of the circulating reaction mixture may be led to the catalyst / aldehyde separation unit 70 'from the recycle line through the separation line 17' to separate the aldehyde.

The recovered aldehyde is sent to a separation and recovery device (not shown) through an aldehyde recovery pipe 19 ', and can be separated and recovered by treating with various kinds of aldehydes and condensation products by a conventional distillation apparatus or the like. The aldehyde as the target material is recovered from the reaction mixture, and the remaining catalyst mixture is supplied to the recycle pipe 15 'of the oxo reactor 100' through the catalyst solution recycle line 18 '.

The reaction mixture of the reactor thus combined with the recycled catalyst mixture is passed through the heat exchanger 60 'and the olefin and synthesis gas fed through the olefin feed line 10' and the synthesis gas feed line 11 ' Is injected and supplied into the oxo reactor 100 'through the nozzle 20' provided in the reactor 100 '. In addition, a heat exchanger 60 'may be provided between the recycle lines 15' and 16 ', but the location thereof 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, since a homogeneous catalyst for low-pressure oxo processing such as rhodium / triphenylphosphine is used as a reaction catalyst, high-pressure reaction is difficult due to its high activity, and difficulty in the reaction process such as low CO partial pressure due to inactivation of the catalyst , N / I selectivity is 89 to 92%, and it is difficult to arbitrarily control the selectivity in accordance with the market conditions of n-butylaldehyde and iso-butylaldehyde.

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, it still has a N / I selectivity of about 90%, which makes it difficult to control the selectivity and has limitations in improving the efficiency of the hydroformylation reaction. As a single reactor can not obtain a satisfactory aldehyde product, Or two or more reactors must be connected in series.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a process for producing aldehydes by reacting olefins with a synthesis gas containing carbon monoxide and hydrogen to improve the efficiency of the hydroformylation reaction And a process for the hydroformylation of an olefin having an effective reaction selectivity using the same.

As a means for solving the above problems, the present invention provides a method for hydroformylating an olefin, comprising the steps of: charging a heterogeneous catalyst mixture solution into a loop reactor equipped with a venturi; A second step of injecting olefin and syngas (CO / H ₂ ) into the heterogeneous catalyst mixed solution charged in the reactor and adjusting the CO partial pressure to within a range of 0.5 to 20 mol%; And a third step of performing a reaction while changing the injection flow of the olefin and the syngas. The present invention also relates to a process for hydroformylation of an olefin having excellent reaction selectivity.

The apparatus for hydroformylation of olefins used in the present invention comprises injection means for injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor, A reactor outlet located downstream of the reactor and through which a reaction mixture of olefin and synthesis gas is discharged; And a loop type reactor mounted between the injection means and the reactor outlet and equipped with a venturi circulating a flow of olefin and synthesis gas.

More specifically, the apparatus further comprises a circulation pipe connected to the outlet of the lower portion of the reactor and the injection means mounted on the upper portion of the reactor, for collecting the reaction mixture from the reactor outlet and supplying the same to the injection means mounted on the upper portion of the reactor to circulate the reaction mixture desirable.

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

Preferably, the injection means includes an ejector having a nozzle, and the diameter of the nozzle is preferably 0.1 to 1000 mm.

It is also preferable that the injection means includes a venturi tube coupled to the ejector. The venturi tube preferably includes an inlet coupled to the ejector and a diffuser facing the reactor outlet, wherein the diameter of the inlet is preferably less than the diameter of the diffuser, and the diffuser has a venturi and a 1/3 To 2/3, and it is preferable that the dispersion plate has a flat shape, a convex shape with respect to the reactor outlet, or a concave shape.

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

The present invention is characterized by using the above apparatus and using a hetero catalyst as a catalyst. That is, the first step of charging the heterotrophic catalyst mixed solution into the venturi-loop reactor; A second step of injecting olefin and synthesis gas (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 synthesis gas. The present invention also provides a method for hydroformylation of olefins. At this time, the partial pressure of CO in the reactor 100 is relatively freely adjusted within a range of 0.5 to 20 mol%.

Such control of the CO partial pressure is due to the use of a heterogeneous catalyst as a catalyst in the reactor. Suitable hetero-catalysts suitable for use in the present invention are encapsulated or anchored in a support such as Zeolite Y or MCM-41, MCM-48 or SBA-15 HRh (CO) (PPh ₃ ) ₃ type catalysts because there is almost no Rh leaching in which the catalyst Rh is released from the support, and it is relatively active compared to other hetero catalysts.

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

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

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

The injection means 20 is not particularly limited as long as it can inject the olefin and the synthesis gas into the reactor. For example, an ejector equipped with a nozzle can be used, and the nozzle mounted on the ejector serves to increase the speed by reducing the injection cross-sectional area of the olefin and the syngas fed into the oxo reactor at high pressure. The diameter of the nozzle may vary depending on the size of the oxo reactor, and it is generally preferably 0.1 to 1000 mm.

Further, it is preferable that the venturi pipe 30 is coupled to the ejector. The venturi tube 30 includes an inlet portion 30a and a diffusion portion 30b as known in the art and the diameter of the inlet portion 30a is smaller than the diameter of the diffusion portion 30b , And the diffusion unit 30b is connected to the injection unit 20, and the diffusion unit 30b is directed to the lower part of the reactor 100. [ The diameter of the inflow 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 inflow portion 30a. The length of the venturi tube 30 is preferably 0.2 to 0.8 times the entire length of the reactor 100.

The mixed gas as the reaction raw material is injected into the reactor 100 through the injection means 20 and the venturi pipe 30 connected to the injector 20. The mixed gas injected in this manner is injected into the reactor 100 Is injected into the catalyst mixture solution. The venturi tube 30 is submerged in the catalyst solution in the reactor 100 and the catalyst solution and the syngas are mixed at the nozzle portion through the venturi tube 30 and mixed into the catalyst solution in the reactor 100.

The syngas becomes a microcapsule due to the rapid flow rate of the catalyst solution at the nozzle site, and the minute bubbles of the gas mixture come into contact with the olefin and the catalyst mixture solution, thereby providing a sufficient contact area of the gas- .

Further, it is more preferable that the flow of the olefin and the mixed gas injected by the dispersing plate (not shown) mounted between the venturi pipe 30 and the reactor outlet 40 is switched. By the change of the flow of the reaction raw material, the residence time of the reaction raw material in the reactor becomes longer, thereby improving the reaction efficiency. The conversion of the reaction raw material stream is determined according to the position and shape of the dispersing plate, and thus the reaction efficiency can be controlled. At this time, it is preferable that the dispersion plate is located between 1/3 and 2/3 of the venturi 30 and the reactor outlet 40, and more preferably, it is located between 1/2.

The shape of the dispersing plate may be flat or convex or concave with respect to the outlet of the reactor, and the size may be 0.5 to 0.9 times the diameter of the reactor 100.

The hydroformylation reactor is connected to an outlet 40 at the lower portion of the reactor and the injection means 20 mounted at the upper portion of the reactor. The reaction mixture is recovered from the reactor outlet 40, (12, 13, 14, 16) for circulating the reaction mixture through the circulation pipe (20).

The olefin and the synthesis gas, which are the raw materials for the reaction, react in the presence of the heterogeneous catalyst mixture solution to produce aldehyde as a reaction product. Accordingly, a reaction mixture including the reaction product, the hetero- catalyzed mixed solution, the unconverted olefin, the synthesis gas, and other reaction by-products is present in the reactor, and the reaction mixture is recovered in the lower part of the reactor 40, To the upper injection means 20 and circulated. The circulating reaction mixture is injected with the reaction raw material and sufficiently mixed with the reaction mixture to improve the reaction efficiency. This circulation can be controlled by the circulation pump 50 provided in the circulation pipe 12.

In addition, since the CO partial pressure in the reactor 100 is relatively freely adjustable within the range of 0.5 to 20 mol%, while the conventional CSTR (CSTR) shown in FIG. 1 is 0.5 to 3 mol% It is easy to control selectivity.

Further, the circulation pipe may be provided with a heat exchanger (60), and its 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 hydroformylation reaction conditions. Recirculation of the catalyst mixture solution can be continuously carried out and the catalyst can be regenerated by discharging a part of the reaction mixture which is recycled in some cases or a new catalyst solution or reactivated catalyst solution can be added to the recycle stream of the reaction mixture have.

The present invention also provides a process for producing a heterogeneous catalyst, comprising: a first step of charging a hetero- A second step of injecting olefin and syngas (CO / H ₂ ) into the heterogeneous catalyst mixed solution charged in the reactor and controlling the partial pressure of CO within the range of 0.5 to 20 mol%; And a third step of performing a reaction while switching the injection flow of the olefin and the synthesis gas; ≪ / RTI > to a process for the hydroformylation of olefins.

The first step is a step of charging the hetero-catalyst mixed solution into the inside of the reactor. The hetero- catalytic mixed solution charged in the reactor is generally used for the hydroformylation reaction. The metal-carbonyl complex catalyst and the ligand .

The metal-carbonyl complex catalyst can be used without limitation as long as it is commonly used in the art. Examples of the catalyst include cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os) A catalyst containing a transition metal such as palladium (Pt), palladium (Pd), iron (Fe), or nickel (Ni) as a central metal may be used. Specifically, there may be mentioned cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonato dicarbonyl rhodium [Rh (AcAc) (CO) ₂ ], acetylacetonato carbonyl triphenylphosphine rhodium [Rh (CO) (TPP) ₃ ], acetylacetonatedicarbonyl iridium [Ir (AcAc) (CO) ₂ ], and hydrido At least one complex catalyst selected from the group consisting of carbonyl tri (triphenylphosphine) iridium [HIr (CO) (TPP) ₃ ] is encapsulated in a support such as Zeolite Y or MCM-41, MCM-48, SBA-15 Or anchoring.

The rhodium catalyst is used in most commercialized processes because it provides stable reaction conditions for the hydroformylation process rather than cobalt or iridium catalyst and provides excellent catalytic activity and high selectivity. Is more preferable. In addition, encapsulating or anchoring the hydridocarbonyltri (triphenylphosphine) rhodium [HRh (CO) (TPP) ₃ ] complex, which is an active form of the catalyst, on the support can be used to stabilize the Rh catalyst generally in a homogeneous catalyst The use of TPP in excess of 100 mol of the catalyst is unnecessary, thus avoiding additional cost loss.

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 a raw material. For example, butylaldehyde is used when propylene is a raw material, and pentylaldehyde is used when butylen is a raw material.

The concentration of the catalyst mixture solution is preferably 10 to 2000 ppm in the case of the metal carbonyl complex catalyst and 1 wt% or less in the case of the ligand.

The second step is a step of supplying an olefin and a synthesis gas as reaction materials into the reactor, and the mixed gas as a reaction raw material is injected into the catalyst mixture solution by the injection means. The injected mixed gas forms fine bubbles, and the minute bubbles of the mixed gas are brought into contact with the olefin and the catalyst mixed solution, so that the gas-liquid contact surface area is wide, thereby providing a sufficient reaction area.

The step of injecting the olefin and the syngas can be carried out 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 can be used. More specifically, olefins having 1 to 20 carbon atoms such as ethylene, propylene, butene, 1-hexene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-pentadecene, 2-hexene, 2-hexene, 2-octene, styrene, 3-phenyl-1-propene or 4-isopropylstyrene, and ethylene, propylene, 1 -Butene, or 1-octene.

The synthesis gas, which is another starting material of the hydroformylation reaction, is a mixed gas of carbon monoxide and hydrogen. The mixing ratio of CO: H ₂ is not limited thereto, but it is preferably 5:95 to 70:30, More preferably 60:40 to 50:50, and most preferably 50:50 to 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. The olefin and the synthesis gas are preferably injected at a pressure of 5 to 200 bar, respectively. The linear velocity of the injected olefin and the syngas is preferably 5 m / s to 40 m / s.

The third step is a step of performing the reaction while switching the injection flow of the olefin and the synthesis gas. By changing the flow of the reaction raw material, the residence time of the reaction raw material in the reactor is lengthened, . Olefin and syngas can be achieved by mounting a diffuser between the venturi and the outlet of the reactor when injected through a nozzle mounted ejector and a venturi tube connected thereto.

The reaction is preferably carried out at a temperature of 50 to 200 ° C, and more preferably at a temperature of 50 to 150 ° C. Further, the reaction is preferably carried out at a pressure of 5 to 100 bar, more preferably at a pressure of 5 to 50 bar.

In the method of hydroformylation of olefins according to the present invention, it is preferable that the step further comprises the step of recovering the reaction mixture after the third step and feeding the reaction mixture into the reactor to circulate the reaction mixture. The reaction mixture discharged through the outlet of the reactor is recovered and the reaction material is sufficiently mixed with the reaction mixture by the circulation system supplied into the reactor to improve the reaction efficiency. The reaction mixture contains unconverted olefins, reaction by-products and catalyst mixture solutions in addition to the target aldehydes (normal- and iso-butylaldehyde).

This circulation system can be achieved by circulating piping coupled to the reactor outlet and the injecting means of the reactor and the circulation pump coupled thereto. The flow rate of the circulated 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, the flow rate of the reaction mixture circulated per minute is preferably 0.1 to 200 L / min when the reactor loading catalyst amount is 10 liters.

Specifically, when the olefin which is the starting material of the hydroformylation process is propylene, the reaction mixture contains butylaldehyde, more specifically up to 99% of n-butylaldehyde and at least 1% of iso-butylaldehyde, Butylaldehyde is introduced into the aldol condensation reactor and is condensed and dehydrated to produce 2-ethylhexanoic acid. The 2-ethylhexanoic acid is then transferred to a hydrogenation reactor, which can produce octanol (2-ethylhexanol) by hydrogenation have.

Figure 2 schematically illustrates the hydroformylation process of olefins according to one embodiment of the present invention. In FIG. 2, various standard items used in factories such as a valve, a temperature measuring device, a pressure regulating device, and the like which can be easily recognized by those skilled in the art have been omitted.

The olefin (for example, propylene) and the syngas are supplied through the olefin supply pipe 10 and the syngas supply pipe 11, respectively, to the nozzles 20 .

In order to increase the efficiency of the gas-liquid reaction, a nozzle 20 and a venturi 30, which are coupled to the nozzle, are provided in the oxo reactor 100. The supplied olefin and the synthesis gas are supplied through the nozzle 20 Is continuously injected and supplied into the Venturi (30). The olefin and synthesis gas injected into the oxo reactor 100 undergo hydroformylation reaction in the presence of a catalyst to produce a reaction mixture. The reaction mixture includes unconverted olefins, reaction by-products and catalyst solutions in addition to the objective aldehydes (e.g., normal- and iso-butylaldehyde).

The reaction mixture containing the aldehyde is recovered through the recycle line 12 using the circulation pump 50 and then circulated through the recycle line 13, 14, 15, 16 to the nozzle 20 provided in the reactor. The recovered aldehyde can be treated with a conventional distillation apparatus or the like to separate and recover various aldehydes and condensation products. The aldehyde as a target material is recovered from the reaction mixture and the remaining catalyst mixture is supplied to the recycle line 15 of the oxo reactor 100 via the catalyst solution recycle line 18.

The reaction mixture of the recycled catalyst mixture and the combined reactor is passed through the heat exchanger 60 and the olefin and synthesis gas fed through the olefin feed pipe 10 and the synthesis gas feed pipe 11 to the oxo reactor 100 And is injected and supplied into the oxo reactor 100 through the nozzle 20 provided. In view of the fact that the catalyst used in the present invention is of a slurry type, there is provided a filter separator 80 of a filter type, such as a simple membrane filter which separates the product from the upper part of the reactor nozzle or the circulation line.

Further, a heat exchanger 60 may be provided between the recirculation pipes 15 and 16, but the position thereof 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 hydroformylation reaction conditions.

According to the present invention, since a loop type reactor capable of high pressure reaction and high reaction efficiency is used as a reaction device and a hetero catalyst having a relatively low activity is used as a reaction catalyst, the CO partial pressure can be freely The N / I selectivity can be controlled and the product and the catalyst can be separated relatively easily by the filter, so that it is not necessary to carry out a complicated catalyst separation process at a high temperature.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a conventional continuous stirred reactor (CSTR) and a reactor used in the hydroformylation of olefins in the use of a homogeneous catalyst;
2 is a schematic diagram showing the venturi-loop apparatus of the present invention and the reaction apparatus used in the hydroformylation process of olefins in the use of a heterogeneous catalyst.

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 1 and Example 1-3 were carried out in the same manner as in Example 1, except that the benzuryl-loop reactor + hetero catalyst according to the present invention and the conventional CSTR reactor + homocatalyst were used. .

< Comparative Example  1-3>

As shown in FIG. 1, a CSTR reactor having a capacity of 3 liters was prepared and installed. Instead of the external heat exchanger, the reactor was fed with heat medium oil in a jacket so that the internal temperature of the reactor could be kept constant. 0.8 g of triphenylphosphine (TPP) 48 g and rhodium triphenylphosphine phosphineacetyl acetonate carbonyl (ROPAC) were dissolved in 800 g of purified toluene to prepare a catalyst solution. The reason why toluene is used as a solvent is to facilitate N / I selectivity analysis of the generated aldehyde. The catalyst solution thus prepared was charged into the reactor and the circulating pump was operated to circulate the catalyst solution slowly at a rate of 2 liters per minute while the entire system was purged three times with purified nitrogen gas through the upper nozzle of the reactor.

While maintaining the external circulation pump at a rate of 2 liters per minute, the temperature inside the reactor was raised to 90 캜 by flowing thermal oil through the jacket outside the reactor. When the temperature stabilized at 90 DEG C, propylene was fed at a flow rate of 12 g / min until the internal pressure of the reactor reached 16.2 bar. The reaction was started by confirming that the internal temperature of the reactor was maintained at 90 ° C for 5 minutes after the supply, and a pre-set synthesis gas at a supply pressure of 18.8 bar was injected to a CO partial pressure of 2.5 mol%.

While maintaining the internal temperature of the reactor at 90 占 폚, the rpm of the stirring apparatus was maintained at 1000 to measure the flow rate of the synthesis gas supplied to the reactor over time. The maximum flow rate was 3.9 liters per minute. After 1.5 hours of reaction, the mixture gas was shut off, the circulation 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 by separation piping and weighed The total weight of the reaction solution was 1.210 g, and thus the weight of the butylaldehyde produced by the reaction was 361 g. The N / I selectivity of the aldehyde produced through gas chromatography was 89.7%.

The experiment was carried out in the same procedure except that the proportion of the synthesis gas was adjusted so that the CO partial pressure was 0.5 mol% and 3.5 mol%, and the results are summarized in Table 1.

division Comparative Example 1 Comparative Example 2 Comparative Example 4 CO concentration (%) 2.5 0.5 3.5 Production of butylaldehyde (g) 361 340 375 Synthetic gas consumption rate (L / min) 3.7 3.5 3.8 N / I selectivity (%) 89.7 91.3 88.1

<Aging Test>

Carbon monoxide and nitrogen were injected such that the vapor-phase molar ratio of carbon monoxide was as shown in Table 2 below, and the pressure in the reactor was maintained at 18.8 bar. At 120 ° C, After the aging test, the temperature was lowered to room temperature, and the internal gas was removed. Then, the catalytic activity test was performed in the same manner as the above method. The results are shown in Table 2 below.

At this time, the catalytic activity of each condition was expressed as a relative value based on the catalytic activity of the catalyst solution (fresh catalyst solution) in which the aging test was not performed, and the catalytic activity was determined based on the weight of the butylaldehyde produced during the reaction for 2 hours Respectively.

division CO gas partial pressure, Mol% Catalyst 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>

As shown in FIG. 2, a 3 liter capacity venturi-loop reactor was prepared and installed. Instead of the external heat exchanger, the reactor was fed with heat medium oil in a jacket so that the internal temperature of the reactor could be kept constant. The diameter of the nozzles mounted on the Venturi-loop reactor was 1.7 mm, the diameter of the dilatation was 8.0 mm, and the length was 200 mm.

4.0 g of a heterogeneous catalyst (catalyst content 0.5% w / w) anchoring catalyst HRh (CO) (PPh ₃ ) ₃ to phospholithic acid was added to a Zeolite-Y support previously prepared in 800 g of purified toluene to prepare a catalyst solution Respectively. The catalyst solution thus prepared was charged into the reactor and the circulating pump was operated to circulate the catalyst solution slowly at a rate of 2 liters per minute while the entire system was purged three times with purified nitrogen gas through the upper nozzle of the reactor.

While maintaining the external circulation pump at a rate of 2 liters per minute, the temperature inside the reactor was raised to 90 캜 by flowing thermal oil through the jacket outside the reactor. When the temperature stabilized at 90 deg. C, propylene was fed at a flow rate of 12 g / min until the internal pressure of the reactor reached 33 bar. After confirming that the internal temperature of the venturi-loop reactor was kept at 90 ° C for 5 minutes after the supply, a pre-set synthesis gas at a supply pressure of 40 bar was injected so that the CO partial pressure became 2.5 mol% 1, 10) and the reaction was started.

The flow rate of the syngas fed 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 connected to the reactor. The maximum flow rate was 2.8 liters per minute. After the reaction was completed for 2 hours, the mixed gas was shut off, the circulation pump was immediately stopped, the reactor temperature was lowered to room temperature, the pressure was released, and the mixture of the entire catalyst solution and the product was recovered by separation piping 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 adjusted to 0.5 mol%, 10 mol%, and 20 mol%, respectively, and the results were summarized in Table 3 below.

division Example 1 Example 2 Example 3 Example 4 CO concentration (%) 2.5 0.5 10 20 Production of butylaldehyde (g) 364 347 418 443 Synthetic gas consumption rate (L / min) 2.8 2.5 3.1 3.4 N / I selectivity (%) 92.3 95.1 87.0 82.5

<Aging Test>

The same catalyst as the above reaction was injected into a Venturi-loop reactor, carbon monoxide and nitrogen were injected so that the vapor-phase molar ratio of carbon monoxide was as shown in Table 4, and the pressure in the reactor was maintained at 40 bar. After performing the aging test according to time, the catalyst activity test was carried out in the same manner as the above-mentioned method, and the results are shown in Table 4 below.

division CO gas partial pressure, Mol% Catalyst 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, the hydroformylation reaction apparatus according to the present invention uses a loop type reactor capable of high-pressure reaction and high reaction efficiency, and at the same time, has a relatively low activity as a hydroformylation catalyst , The CO partial pressure can be controlled freely, so that the N / I selectivity can be controlled compared to Comparative Examples 1 to 3, and the product and the catalyst can be relatively easily separated by the filter It is confirmed that it is not necessary to carry out a complicated catalyst separation process at a high temperature.

10, 10 ': olefin supply pipe 11, 11': synthesis gas supply pipe
12,12 ', 13,13', 14,14 ', 15,15', 16,16 ': circulating piping
17, 17 ': Separation piping 18': Catalyst solution supply piping
19 ': Aldehyde recovery piping
20, 20 ': ejector 20a, 20a': nozzle
30: Venturi tube 30 ': Impeller
30a: Inflow section 30b: Diffusion section
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)

Injecting means mounted on the venturi-loop hydroformylation reactor for injecting olefin and syngas (CO / H ₂ ) into the hetero- catalytic mixed solution charged in the reactor;
A reactor outlet located downstream of the reactor and through which a reaction mixture of olefin and synthesis gas is discharged; And
A venturi tube mounted between the injection means and the reactor outlet for circulating the flow of olefin and syngas; And a loop type reactor provided with the reactor,
Characterized in that the dispersion plate is located between the third and the third of the outlet of the venturi tube and the reactor at a size of 0.5 to 0.9 times the diameter of the reactor
A device for the hydroformylation of olefins. delete The method according to claim 1,
Wherein the venturi tube comprises an inlet portion from the top and a diffusion portion facing the reactor outlet, the diameter of the inlet portion being smaller than the diameter of the diffusion portion
A device for the hydroformylation of olefins. The method of claim 3,
Characterized in that the inlet diameter of the venturi tube is in the range of 0.1 to 10000 mm
A device for the hydroformylation of olefins. The method according to claim 1,
Wherein the length of the venturi tube is 0.2 to 0.8 times the total length of the reactor
A device for the hydroformylation of olefins. delete delete A first step of charging the heterotrophic catalyst mixed solution into the loop type reactor equipped with the venturi of any one of claims 1 to 5;
A second step of injecting olefin and syngas (CO / H ₂ ) into the heterogeneous catalyst mixed solution charged in the reactor and controlling the partial pressure of CO within the range of 0.5 to 20 mol%; And
And a third step of performing a reaction while switching the injection flow of the olefin and the synthesis gas
A process for the hydroformylation of olefins. 9. The method of claim 8,
The heterocatalyst mixed solution is a metal-carbonyl complex catalyst And a ligand and a support therefor.
A process for the hydroformylation of olefins. 10. The method of claim 9,
Wherein the concentration of the catalyst mixture solution is 10 to 2000 ppm of a metal carbonyl complex catalyst and 1 wt% or less of a ligand
A process for the hydroformylation of olefins. 9. The method of claim 8,
The olefin is at least one member selected from the group consisting of ethylene, propylene, butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-tridecene, Butene, 2-pentene, 2-hexene, 2-heptene, 2-ethylhexene, 2-octene, 1-heptadecene, 1-octadecene, , Styrene, 3-phenyl-1-propene and 4-isopropylstyrene.
A process for the hydroformylation of olefins. 9. The method of claim 8,
The synthesis gas (CO: H ₂ ) is characterized in that the mixing ratio of CO: H ₂ is a molar ratio of 5:95 to 70:30
A process for the hydroformylation of olefins. 9. The method of claim 8,
Wherein the molar ratio of the injected olefin to the synthesis gas is from 95: 5 to 5:95
A process for the hydroformylation of olefins. 9. The method of claim 8,
Wherein the olefin and the syngas are respectively injected and supplied into the oxo reactor at a pressure of 5 to 200 bar
A process for the hydroformylation of olefins. 9. The method of claim 8,
Wherein the linear velocity of the injection of the olefin and the synthesis gas is 5 m / s to 40 m / s
A process for the hydroformylation of olefins. 9. The method of claim 8,
Wherein the reaction of the third step is carried out at a temperature of 50 to 200 DEG C and a pressure of 5 to 100 bar
A process for the hydroformylation of olefins.

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