KR20110122435A - Reactor for the hydroformylation of olefin and method for the hydroformylation using the same - Google Patents

Abstract

PURPOSE: The hydroformylation apparatus of olefin and a hydroformylation method using the same are provided to arrange a sufficient reacting area by widening the contact surface area of olefin and synthetic gas. CONSTITUTION: The hydroformylation apparatus of olefin includes a spraying unit, a reactor outlet(40), and a reactor. The spraying unit is mounted at the upper side of the reactor. The spraying unit sprays olefin and synthetic gas to a catalyst mixed solution in the reactor. The reactor outlet is located at the lower side of the reactor. The resultant of the olefin and the synthetic gas is discharged through the reactor outlet. The reactor is arranged the spraying unit and the reactor outlet. The reactor includes a dispersing plate(50) converting the flow of the olefin and the synthetic gas. The dispersing plate satisfies an equation, 0.2<=d/D<=0.7. In the equation, the d is the diameter of the dispersing plate. The D is the inner diameter of the reactor.

Description

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

The present invention relates to a hydroformylation reaction apparatus for olefins and a hydroformylation method using the same, and more particularly, by specifying the dispersion plate provided in the reactor with appropriate parameters, the gas-liquid contact is facilitated, and the reaction mixture The present invention relates to a hydroformylation reaction apparatus for olefins capable of circulating ethylene and a hydroformylation method using the same.

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

Various aldehydes synthesized by 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 type of ligand and the operating conditions applied (iso) of linear (normal) to branched (iso ) isomers) are different. More than 70% of the world's oxo plants employ a low pressure OXO process with rhodium-based catalysts.

A representative example of hydroformylation is the production of octanol (2-ethylhexanol) from propylene using a rhodium-based catalyst. Such octanol is mainly used as a raw material for PVC plasticizers such as DOP (Dioctyl Phathalate), and is used as an intermediate raw material such as 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 fresh 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 hydrogenation reactor are transferred to the fractionation column, and the light / heavy end is separated to produce octanol product.

The hydroformylation reaction can be carried out continuously, semicontinuously or batchwise, and a typical hydroformylation reaction process is a gas or liquid recycle system. In 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.

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, the conventional methods including this have limitations in improving the efficiency of the hydroformylation reaction, and since a single reactor alone does not provide a satisfactory aldehyde product, it is generally desired to give a high reaction residence time or to connect two or more reactors in series. Will produce products.

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

In order to solve the above problems, in the present invention, as a hydroformylation reaction apparatus for olefins, injection means for injecting olefins and syngas (CO / H ₂ ) into a catalyst mixture solution charged in the reactor is mounted on the reactor. ; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And a reactor mounted between the injection means and the reactor outlet and equipped with a dispersion plate for switching the flow of olefins and syngas; It includes, the dispersion plate is the following equation 1

[Equation 1]

0.2 ≤ d / D ≤ 0.7

(Where d is the diameter of the dispersion plate and D is the inner diameter of the reactor)

It is characterized by satisfying.

In addition, in the present invention, the hydroformylation of the olefin using the above-described reaction apparatus as a hydroformylation method, the flow rate of the reaction mixture for recovering and circulating the reactant is 0.01 to 20 times the reactor charge capacity per minute do.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the present invention, the injection means for injecting the olefin and the synthesis gas (CO / H ₂ ) in the catalyst mixture solution is charged in the reactor; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And a reactor mounted between the injection means and the reactor outlet and equipped with a dispersion plate for switching the flow of olefins and syngas; Provided is a hydroformylation reaction apparatus of an olefin comprising a, but by setting the appropriate parameters for the dispersion plate has the technical characteristics to improve the reaction rate and efficiency.

That is, the flow of the olefin and the mixed gas injected by the dispersion plate is switched, the residence time in the reactor of the reaction raw material is long by the conversion of the reaction raw material flow, thereby improving the reaction efficiency. On the other hand, the conversion of the reaction raw material flow is determined according to a number of variables, such as the position and shape of the dispersion plate, the bending angle, it is possible to adjust the reaction efficiency.

It is preferable to satisfy the following equation 1 as one of these variables in view of reaction speed and efficiency.

[Equation 1]

0.2 ≤ d / D ≤ 0.7

(Where d is the diameter of the dispersion plate and D is the inner diameter of the reactor)

In addition, it is preferable that the dispersion plate satisfies the variable of Equation 2 in view of reaction speed and efficiency.

[Equation 2]

0.2 ≤l / L ≤0.9

(Wherein l is the distance from the top of the reactor to the center of the dispersion plate and L is the total length of the reactor)

In this case, the dispersion plate may be a flat form, a convex form or a concave form with respect to the reactor outlet, and when using a double convex form or a concave form, the bending angle from the center of the dispersion plate is 10 ° to 45 It is preferably in the range. FIG. 2 is a cross-sectional view of the dispersion plate, in which FIG. 2 (a) shows a flat shape, (b) shows a convex shape, and (c) shows a concave shape.

In addition, the dispersion plate is not limited thereto, but may be made of a material such as stainless steel or Teflon.

Furthermore, the dispersion plate preferably satisfies the variable of Equation 3 below.

&Quot; (3) &quot;

0.1 ≤t / d ≤0.3

(Wherein t is the thickness of the dispersion plate and d means the diameter of the dispersion plate)

Such distribution plate-related variables are preferable if one or more of them are satisfied, and if the range for all the variables are satisfied, the optimum reaction rate and efficiency will be produced.

On the other hand, the injection means comprises an ejector equipped with a nozzle, it is preferable to use a venturi tube coupled to the ejector, the venturi tube is a diffusion portion which is directed to the inlet and the reactor outlet coupled to the ejector Including, the diameter of the inlet may be smaller than the diameter of the diffusion.

The length of such venturi tubes is in the range of 0.2 to 0.8 times the total length of the reactor, where the dispersion plate is more preferably located between 1/3 and 2/3 of the venturi and reactor outlet.

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

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

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

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

The type of catalyst / aldehyde separator is not limited so long as it is a means for separating the catalyst mixture solution and the aldehyde from the reaction mixture. Recycling of the catalyst mixture solution in which the target substance is separated may be continuously performed, and in some cases, a part of the recycled reaction mixture is discharged to regenerate the catalyst, or a new catalyst solution or a reactivated catalyst solution is recycled to the reaction mixture. Can be added to the flow.

The method of hydroformylation using the apparatus configured as described above is generally known, and in particular, the catalyst mixture solution is first charged into the reactor, and the catalyst mixture solution loaded in the reactor is generally used. As used in the hydroformylation reaction, it may include metal-carbonyl complex catalysts and ligands. The metal-carbonyl complex catalyst can be used without limitation as long as it is 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.

In addition, the ligand may be a trisubstituted phosphine (Phosphine), phosphine oxide (Phosphine Oxide), amines (Amine), amides (Amide), or isonitrile (Isonitrile) and the like, using a trisubstituted phosphine It is preferable. Trisubstituted phosphines include, but are not limited to, triaryl phosphine, triaryl phosphite, alkyldiaryl phosphine and the like, more specifically triphenylphosphine, tritolylphosphine, triphenylphosphite and n -Butyl diphenyl phosphine, etc. 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.

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 to 30 wt% for the ligand.

Then, as a second step, the reaction raw material olefin and syngas are supplied into the reactor, and the mixed gas as the reaction raw material is injected into the catalyst mixed 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. This injection of olefins and syngas can be performed using an ejector equipped with a nozzle and a venturi tube coupled thereto.

As the olefin usable in the present invention, an olefin having 2 to 20 carbon atoms may be used, and more specifically, ethylene, propylene, butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpropene, 2- Pentene, 2-hexene, 2-heptene, 2-ethylhexene, 2-octene, styrene, 3-phenyl-1-propene or 4-isopropylstyrene, and the like, ethylene, propylene, 1-butene, or 1- It is more preferable that it is 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.

Since the reaction is carried out by switching the injection stream of the olefin and syngas by the dispersion plate optimized in the present invention, the residence time of the reaction raw material in the reactor is increased by the conversion of the reaction raw material flow, accordingly The efficiency is improved. 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. As such, the reaction mixture discharged through the reactor outlet is recovered and the reaction raw materials are sufficiently mixed with the reaction mixture by a circulation system supplied into the reactor, thereby improving the reaction efficiency. The reaction mixture contains unconverted olefins, reaction by-products, and catalyst mixed solution in addition to the target aldehydes (normal- and iso-butylaldehyde).

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

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

At this time, a part 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 flow. Specifically, when the 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. And then separated into aldehyde and catalyst mixture, the catalyst mixture is circulated to the reactor and the aldehyde component is sent to the fractionation tower to separate normal- and iso-butylaldehyde, respectively.

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

1 is a view illustrating a hydroformylation process of an olefin according to an embodiment of the present invention. Figure 1 omits the devices of various standard items actually used in the factory, such as valves, temperature measuring devices, pressure regulators that can be easily recognized by those skilled in the art.

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. At this time, a portion of the circulating reaction mixture may be led to the catalyst / aldehyde separation device 70 from the recirculation pipe through the separation pipe 17 to separate the aldehyde. The recovered aldehyde is sent to a separate recovery apparatus or the like (not shown) through the aldehyde recovery pipe 19, and can be separated and recovered by various aldehydes and condensation products by treatment with a conventional distillation apparatus or the like.

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.

In addition, the catalyst solution recirculation pipe 18 was connected between the recirculation pipes 14 and 15 to remove the aldehyde, and the remaining catalyst solution or the reactivated catalyst solution was introduced into the reactor system, and between the recirculation pipes 15 and 16. May be equipped with a heat exchanger 60, 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.

The hydroformylation apparatus for olefins according to the present invention provides a sufficient reaction area because the contact surface area of the olefin and the synthesis gas as a reaction material is wide by specifying the dispersion plate provided in the reactor with appropriate parameters, and the reaction mixture is circulated. Therefore, the reaction raw material is sufficiently mixed with the reaction mixture, and the reaction efficiency is excellent.

1 is a schematic process diagram showing a hydroformylation process of an olefin according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a dispersion plate provided in the hydroformylation apparatus of the olefin of the present invention, showing (a) a flat plate shape, (b) a convex shape above, and (c) a convex shape below.

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 : Dispersion  Related Parameters d / D

As in FIG. 1, a venturi-loop reactor having a 3 liter capacity was manufactured and installed. The diameter of the nozzle mounted on the reactor was 1.7 mm, the diameter of the venturi tube was 8.0 mm, and the length was 200 mm. Each dispersion plate having a length (d) of 0.1 times, 0.3 times, 0.5 times, 0.7 times, and 0.9 times the diameter of the dispersion plate relative to the reactor inner diameter (D) was provided in the reactor. At this time, the type of concave plate to the top of the reactor was used.

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

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

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

The flow rate of the syngas supplied to the reactor was measured over time while maintaining the internal temperature of the venturi-loop reactor at 90 ° C. through an automatic temperature controller to be connected to the reactor.

After the reaction for 2 hours, the mixed gas was shut off, the operation of the circulating pump was immediately stopped, the reactor temperature was lowered to room temperature, the pressure was released, the weight of the butylaldehyde produced by the reaction, and the total flow meter installed in the mixed gas supply pipe. The total amount of mixed gas consumed was measured and the results are shown in Table 1 below.

d / D value 0.1 0.3 0.5 0.7 0.9 Butylaldehyde production amount (g) 441 457 465 449 431 Syngas consumption rate (L / min) 5.1 5.3 5.4 5.2 5.0

As shown in Table 1, the dispersion plate-related parameter d / D was found to be in the range of 0.3 to 0.7 has a high reaction rate and excellent reaction efficiency.

Example  2: Dispersion  Related Parameters l / L

In the same reactor as in Example 1, a dispersion plate was provided in the reactor such that the distance l from the top of the reactor was 0.5 times, 0.7 times, and 0.9 times relative to the total length L of the reactor, and the parameter d / D value was 0.5. The same experiment as in Example 1 was repeated except that adjustment was made.

After the reaction for 2 hours, the mixed gas was shut off, the operation of the circulating pump was immediately stopped, the reactor temperature was lowered to room temperature, the pressure was released, the weight of the butylaldehyde produced by the reaction, and the total flow meter installed in the mixed gas supply pipe. The total amount of mixed gas consumed was measured and the results are shown in Table 2 below.

l / L value 0.5 0.7 0.9 Butylaldehyde production amount (g) 460 465 442 Syngas consumption rate (L / min) 5.3 5.4 5.1

As shown in Table 2, the dispersion plate-related parameters l / L was in the range of 0.7 to 0.9 it was confirmed that the reaction rate is high and the reaction efficiency is excellent.

Example  3: Dispersion  Curved angle

Dispersion plate is provided in the same reactor as in Example 1, but the deflection angle is 5 °, 10 °, 30 °, 45 °, and 60 ° with respect to the center of the dispersion plate, and the parameter d / D value is 0.5. The same experiment as in Example 1 was repeated except that it was adjusted to.

After the reaction for 2 hours, the mixed gas was shut off, the operation of the circulating pump was immediately stopped, the reactor temperature was lowered to room temperature, the pressure was released, the weight of the butylaldehyde produced by the reaction, and the total flow meter installed in the mixed gas supply pipe. The total amount of mixed gas consumed was measured and the results are shown in Table 3 below.

Bending angle (°) 5 10 30 45 60 Butylaldehyde production amount (g) 459 465 464 452 440 Syngas consumption rate (L / min) 5.3 5.4 5.4 5.2 5.1

As shown in Table 3, the bending angle based on the center of the dispersion plate was found to be within 10 to 45 ° in terms of reaction rate and reaction efficiency.

Example  4( Dispersion  Change of form-1)

Example 1 except that the inside of the reactor as in Example 1 has a convex shape above (b) of the dispersion plate shape of Figure 2, the bending angle is adjusted to 10 degrees, the parameter I / L value satisfies 0.7. It was carried out in the same manner as.

After the reaction for 2 hours, the mixed gas was shut off, the operation of 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. It was found that the total weight of the reaction solution was 1.265 g, and thus the weight of butylaldehyde produced by the reaction was 456 g. In addition, when the total amount of mixed gas consumed was measured through an integrated flow meter installed in the mixed gas supply pipe, the maximum consumption rate of the syngas during the reaction was 5.3 liters per minute.

Example  5 ( Dispersion  Change of form-2)

Example 2 except that the (c) the convex shape of the dispersion plate form of FIG. 2 inside the same reactor as in Example 1, the bending angle is 10 °, the parameter l / L value is adjusted to satisfy 0.7. It carried out by the same method as 1.

After the reaction for 2 hours, the mixed gas was shut off, the operation of 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. As a result, the total weight of the reaction solution was 1.265 g, and thus the weight of butyl aldehyde produced by the reaction was 443 g. In addition, when the total amount of mixed gas consumed was measured through an integrated flow meter installed in the mixed gas supply pipe, the maximum consumption rate of the syngas during the reaction was 5.1 liters per minute.

Comparative example  One( Dispersion  Not installed)

The same method as in Example 1 was repeated without installing a dispersion plate in the same reactor as in Example 1.

After the reaction for 2 hours, the mixed gas was shut off, the operation of 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. It was found that the total weight of the reaction solution was 1.265 g, and thus the weight of butylaldehyde produced by the reaction was 439 g. In addition, when the total amount of mixed gas consumed was measured through an integrated flow meter installed in the mixed gas supply pipe, the maximum consumption rate of the syngas during the reaction was 5.1 liters per minute.

10: olefin supply piping 11: syngas supply piping
12, 13, 14, 15, 16: Circulation piping 17: Separation piping
18: catalyst solution supply piping 19: aldehyde recovery piping
20: ejector 30: venturi tube
40: reactor outlet 50: dispersion plate
60: circulating pump 70: catalyst / aldehyde separation device
80: heat exchanger 100: oxo reactor

Claims (12)

Injection means mounted on the reactor and injecting olefin and syngas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; And a reactor mounted between the injection means and the reactor outlet and equipped with a dispersion plate for switching the flow of olefins and syngas; As a hydroformylation reaction apparatus of an olefin comprising a,
The dispersion plate is characterized by satisfying the following equation
Hydroformylation Reactor of Olefin
[Equation 1]
0.2 ≤ d / D ≤ 0.7
(Where d is the diameter of the dispersion plate and D is the inner diameter of the reactor)
The method of claim 1,
The dispersion plate is characterized by satisfying the following equation
Hydroformylation Reactor of Olefin
[Equation 2]
0.7 ≤l / L ≤0.9
(Wherein l is the distance from the top of the reactor to the center of the dispersion plate and L is the total length of the reactor)
The method of claim 1,
The dispersion plate is characterized in that the flat shape, the convex shape with respect to the reactor outlet, or concave shape.
Hydroformylation reactor of olefins.
The method of claim 3, wherein
The convex or concave dispersion plate is characterized in that it has a bending angle of 10 ° to 45 ° relative to the center
Hydroformylation reactor of olefins.
The method of claim 1,
The dispersion plate is characterized by satisfying the following equation
Hydroformylation Reactor of Olefin
[Equation 3]
0.1 ≤t / d ≤0.3
(Wherein t is the thickness of the dispersion plate and d means the diameter of the dispersion plate)
The method of claim 1,
The injection means includes an ejector equipped with a nozzle, the ejector is characterized in that the venturi tube is coupled
Hydroformylation reactor of olefins.
The method according to claim 6,
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 smaller than the diameter of the diffuser.
Hydroformylation reactor of olefins.
The method of claim 7, wherein
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 8,
The dispersion plate is located between 1/3 and 2/3 of the venturi and the reactor outlet
Hydroformylation reactor of olefins.
The method of claim 1,
It is connected to the outlet of the reactor and the injection means mounted to the upper portion of the reactor, and further comprising a circulation pipe for recovering the reaction mixture from the reactor outlet to supply to the injection means mounted on the reactor to circulate the reaction mixture
An olefin hydroformylation reaction apparatus characterized by the above-mentioned.
The method of claim 10,
A separation pipe separating at any one of the circulation pipe to separate the reaction mixture from the circulation flow; A catalyst / aldehyde separation device connected to the separation pipe and separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixed solution supply pipe connected to one of the catalyst / aldehyde separator and the circulation pipe to supply the catalyst mixed solution to the circulation pipe; And an aldehyde recovery pipe connected to the catalyst / aldehyde separator for recovering aldehydes.
Hydroformylation reactor of olefins.
Hydroformylation of the olefin using the apparatus of any one of claims 1 to 11,
The flow rate of the reaction mixture to recover and circulate the reactants is characterized in that 0.01 to 20 times the reactor charge capacity per minute
Hydroformylation of Olefin.

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