KR101379989B1 - A Method For Manufacturing Aldehyde from Olefin, And An Apparatus for the Method - Google Patents

Abstract

The present invention relates to a method for producing aldehyde from olefin and a reaction apparatus used therein, the constitution of which is carried out by hydroformylation reaction of an olefin in a hydroformylation main reactor in the presence of a synthesis gas of hydrogen and carbon dioxide, to produce an aldehyde. The catalyst is separated from the aldehyde-containing product and recycled, wherein the hydroformylation reaction is further performed in the hydroformylation further reactor using the aldehyde-containing product under the syngas atmosphere.
According to the present invention, by further performing the hydroformylation reaction, the reaction conversion rate is improved, and heavy components such as dimer and trimer are also produced, resulting in higher reaction selectivity and improved reaction yield. Have

Description

Method for manufacturing aldehydes from olefins, and reaction apparatus used therein {A Method For Manufacturing Aldehyde from Olefin, And An Apparatus for the Method}

FIELD OF THE INVENTION The present invention relates to a process for preparing aldehydes from olefins, and to reactors used therein, and more particularly, by carrying out a gas phase pretreatment reaction, reaction conversion is improved and heavy such as dimers and trimers It is directed to a process for preparing aldehydes from olefins, and the reaction apparatus used therein, which result in less components, resulting in higher reaction selectivity and improved reaction yield.

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.

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.

1 is a process chart for performing a hydroformylation process of an olefin using a continuous stirred reactor (CSTR) alone, by connecting a catalyst solution recirculation pipe between the recirculation pipes to remove aldehyde from the catalyst separator or the remaining catalyst solution or An example of introducing the reactivated catalyst solution into the reactor system is shown.

That is, the olefin (for example, propylene) and the synthesis gas are supplied to the nozzles provided on the upper portion of the oxo reactor through which the catalyst solution is loaded, through the olefin supply pipe and the syngas supply pipe, respectively.

In order to increase the efficiency of the gas-liquid reaction, a nozzle is provided inside the oxo reactor, and the supplied olefin and synthesis gas are continuously injected and supplied into the oxo reactor through the nozzles. The olefin and synthesis gas injected into the oxo reactor are subjected to 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 target aldehydes (eg, normal- and iso-butylaldehyde).

The reaction mixture containing the aldehyde is recovered through the recycle pipe using a circulation pump and then circulated to the reactor through the recycle pipe. At this time, a part of the circulating reaction mixture may be led to the catalyst / aldehyde separator through the separation pipe from the recycle pipe to separate the aldehyde. That is, it is sent to a separation recovery apparatus and the like, and treated with a conventional distillation apparatus or the like to separate and recover various aldehydes and condensation products. Aldehyde, which is a target substance, is recovered from the reaction mixture, and the remaining catalyst mixture is supplied to the recirculation piping of the oxo reactor through the catalyst solution recirculation piping.

In addition, a heat exchanger may be provided between the recirculation pipes, but the position is not limited to a specific position on the circulation cycle. At this time, the heat exchanger serves to maintain the reaction mixture recycled to the oxo reactor at a temperature suitable for the hydroformylation reaction conditions.

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, this also had a limitation in improving the efficiency of the hydroformylation reaction in view of low N / I selectivity, such as 8 to 10%, since the reactor was changed in shape and followed the liquid phase reaction mechanism using a rhodium catalyst. Since the reactor alone cannot obtain a satisfactory aldehyde product, there are generally disadvantages such as a large reaction residence time or two or more reactors in series.

It is therefore an object of the present invention to provide an improved method which can sufficiently improve the efficiency of the hydroformylation reaction.

In addition, another object of the present invention is to provide a hydroformylation reaction apparatus for achieving the above object.

As a means for solving the said subject, the manufacturing method of the aldehyde from the olefin of this invention,

The olefin is hydroformylated in a stirred type hydroformylation main reactor to produce an aldehyde, wherein some of the aldehyde containing product separates the catalyst and recycles to the hydroformylation main reactor,

Some of the product containing the aldehyde-containing product undergoes a hydroformylation further reaction under a syngas atmosphere of hydrogen and carbon dioxide in a hydroformylation further reactor and forms an aldehyde-containing reaction mixture, wherein the aldehyde-containing reaction mixture is hydroformylated. It is characterized in that it is circulated to the main reactor.

Moreover, as a means for solving the said subject, the aldehyde manufacturing apparatus from the olefin of this invention,

Hydroformylation main reactor for hydroformylation of olefins to produce aldehydes;

A hydroformylation addition reactor for receiving an aldehyde-containing product obtained in the hydroformylation main reactor through a circulation pump and a circulation pipe to perform hydroformylation addition reaction under a syngas atmosphere; And

Consisting of a catalyst separation device having a pipe for separating the aldehyde reaction product, the catalyst and the unreacted olefin from the reaction product discharged from the hydroformylated main reactor, the double catalyst and the unreacted olefin to the olefin supply pipe; It features.

Hereinafter, the present invention will be described in detail.

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 such as ethylene, propylene, 1-butene, 1-hexene, Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 1-octadecene, 2-hexene, 2-hexene, 2-octene, styrene, 3-phenyl-1-propene or 4-isopropylstyrene, , 1-butene, 2-butene or 1-octene.

Suitable catalysts suitable for use in the present invention include, but are not limited to, cobalt (Co) and rhodium (Rh) systems currently used in the oxo process, and the hetero- As used in the milling reaction, it may include a metal-carbonyl complex catalyst and a 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 ] can be used.

The ligand may be a trisubstituted phosphine (Phosphine), phosphine oxide (Phosphine Oxide), amines (Amine), amides (Amide), or isonitrile (Isonitrile), and the use of trisubstituted phosphine desirable. Trisubstituted phosphines include, but are not limited to, triaryl phosphines, triaryl phosphites, alkyldiaryl phosphines, and the like, more specifically triphenylphosphine (TPP), tris-p-tolylphosphine ( TPTP), tris-o-tolylphosphine (TPTP), 1-naphthyldiphenylphosphine, 4-methoxyphenyldiphenylphosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tris ( Triaryl type single seat phosphines, such as 3, 5- diphenylphenyl) phosphine and 4-dimethylaminophenyl di-2- naphthyl phosphine; Diphenyl-n-propylphosphine, n-octadecyldiphenylphosphine, di (3-t-butyl-2-naphthyl) methylphosphine, isopropyl-2-naphthyl-p-tolylphosphine, 2 Single seat phosphine of the diaryl monoalkyl type, such as ethylhexyldi (4-fluorophenyl) phosphine; Dimethylphenylphosphine, diethyl-4-methoxyphenylphosphine, di-n-octylphenylphosphine, t-butyl-n-octyl-3,5-dimethylphenylphosphine, diisopropyl-2-naphthyl Monoaryldialkyl type single-dented phosphines such as phosphine and isobutyl-n-pentyl-4-acetylphenylphosphine; Trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tri-n-octadecylphosphine, n-octadecyldimethylphosphine, Diethyl-n-octylphosphine, ethylmethyl-n-propylphosphine, tri-2-ethoxyethylphosphine, isobutyl neopentyl-n-hexylphosphine, tri-2-ethylhexylphosphine, tribenzyl Phosphine, trineopentylphosphine, triisopropylphosphine, tri-t-butylphosphine, tri-2-butylphosphine, di-n-hexyl-1,1-dimethylpropylphosphine, 3-phenylpropyl Trialkyl type single seat phosphines, such as di-t- butyl phosphine and 2-butyl- n-propyl-3, 3- dimethoxy propyl phosphine, etc. are mentioned.

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.

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 to 30 wt% in the case of the ligand.

In this case, as the hydroformylation main reactor, a vertical stirred reactor or a venturi-loop reactor may be used. In addition, the hydroformylation further reactor is preferably, but not limited to, two stages of a gas phase reactor and a liquid phase reactor (see an example of the reactor shown in FIGS. 2 and 3).

In this case, the aldehyde-containing reaction product supplied from the hydroformylation main reactor is preferably supplied into the gas phase reactor, which is maximized when the aldehyde-containing reaction product is injected at high speed through the nozzle into the liquid phase under a gaseous atmosphere supplied with synthesis gas. Because it can.

Preferably, the injection means in the gas phase reactor includes an ejector equipped with one or more nozzles, and the diameter of the unit 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 includes an inlet coupled to the ejector and a diffuser directed towards the reactor outlet, wherein the diameter of the inlet is smaller than the diameter of the diffuser.

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. .

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 45:55, and most preferably 45:55 to 55:45. 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.

Further, the olefin and the syngas are preferably injected at a pressure of 1 to 200 bar, respectively. The linear velocity of the olefin and the synthesis gas is preferably 2 to 50 m / s.

The olefin is supplied in a form in which the aldehyde-containing reaction product is circulated in a gaseous reaction space under a pre-supplied atmosphere of synthesis gas, and is directly supplied to the hydroformylation main reactor together with a recycle catalyst.

On the other hand, the gas phase reaction space is preferably provided with a capacity of 0.5 to 60 times the volume of the liquid reaction space connected to the lower side in consideration of operating conditions and reaction efficiency, it is most preferably provided with a capacity of 1 to 4 times. .

The reaction is preferably carried out at a temperature of 50 to 200 ℃, more preferably at a temperature of 50 to 150 ℃ the gas phase conditions. 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.

Reaction mixtures formed by further reactions include syngas, unreacted reactants, aldehydes, catalysts, and the like. The reaction mixture formed is fed to the liquid phase reactor connected through the lower outlet of the gas phase reactor to perform the reaction to improve the reaction efficiency.

The advantages of carrying out the reaction in the liquid phase are that the control of the reactor is relatively simple and that fairly good heat transfer occurs, thus eliminating the need for a separate heat exchanger in the reactor. Preferably, the reaction is preferably carried out at a temperature of 50 ~ 200 ℃ and a pressure of 5 ~ 100 bar in terms of yield, more preferably at a temperature of 75 ~ 120 ℃ and a pressure of 5 ~ 50 bar. Do.

Figure 2 is a view showing the reaction flow in a further reactor according to the present invention for the hydroformylation further reaction of the olefin, Figure 2 is a plant, such as valves, temperature measuring devices, pressure regulators that can be easily recognized by those skilled in the art The devices of various standard items actually used are omitted.

The present invention is described in detail with reference to FIG. 2 as follows: First, the hydroformylation further reactor 10 of the present invention includes a gas phase reactor 10a and a liquid phase reactor 10b. The gas phase reactor 10a and the liquid phase reactor 10b each consist of a reaction chamber adapted to operate under supercritical conditions. The aldehyde-containing reaction product supplied through the circulation pump 8 and the circulation pipes 7a and 7b in the hydroformylation main reactor 1 sequentially passes the supply pipe 10, the ejector (not shown) and the spray nozzle 12. To the reaction chamber in the gas phase reactor (10 a), the synthesis gas is introduced through the synthesis gas supply pipe 11 provided on the side wall facing the side wall provided with the nozzle 12 to perform the gas phase reaction do.

In this way, the aldehyde-containing reaction product dispersed at high speed through the spray nozzle 12 reacts immediately with the syngas supplied oppositely and further performs the hydroformylation reaction.

The reaction mixtures are then introduced into the reaction chamber of the liquid phase reactor 10b via a transfer space consisting of an outlet 20 of the gas phase reactor and an inlet 30 of the liquid phase reactor. At this time, the liquid phase reactor secondary inlet 30 corresponding to the actual outlet of the gas phase reactor is 0.3 to 0.9 times the diameter of the liquid phase reactor primary inlet 20 corresponding to the outlet of the gas phase reactor 10a, preferably Is 0.4 to 0.7 times to enable a dense supply when introduced into the liquid phase reactor is effective in improving the reaction efficiency.

On the other hand, the liquid phase reactor (10b) is to include one or more diaphragms as the inner loop (30a). The diaphragm plays a desirable role in mixing and reaction by inducing a flexible flow over the entire area of the liquid phase reactor, but if the diaphragm is too large or the gap is too narrow, rather than two to four is appropriate. By the formation of such a diaphragm type, the residence time of the reaction raw material in the reactor is increased by switching the reaction raw material flow in the reactor, thereby improving the reaction efficiency. The average residence time in such a liquid phase reactor depends on the catalyst concentration and is usually within the range of 20 minutes to 7 hours.

On the other hand, at the bottom of the liquid phase reactor (10b) is provided with a liquid level control device 13 to maintain a constant level in the liquid phase reactor.

The reaction mixtures thus subjected to further reaction are fed to the hydroformylation main reactor (1) through the circulation pipe (12) through the bottom of the liquid phase reactor and then through the olefin feed pipe (2) and the recycle catalyst feed pipe (6). The reaction with the unreacted olefin and the recycle catalyst may be further carried out. The reaction mixture contains unconverted olefins, reaction by-products, and catalyst mixed solution in addition to the target aldehydes (normal- and iso-butylaldehyde).

At this time, some reaction liquid passes through the circulation pipe 7a by the circulation pump 8 and then sequentially passes through the supply pipe 7b, the ejector (not shown), and the spray nozzle 12 as described above. Into the reaction chamber and most of the product is passed through a transfer pipe (3) to the catalyst separator (4) to separate the catalyst and residual olefins and then to the hydroformylation main reactor (1) via a circulation pipe (6). The aldehyde product may be separated through the separation pipe 5 to carry out a post process (hydrogenation or aldol condensation, etc.).

As described above, the reaction mixture discharged through the liquid phase reactor outlet 30 is hydroformylated main reactor (1) in a state in which the reaction raw material is sufficiently mixed with the reaction mixture by the circulation system supplied into the reactor and the reaction efficiency is improved. Is fed to the reaction with unreacted olefins to increase the reaction selectivity and consequently significantly improve the overall reaction yield. Such a circulation system can be achieved by a circulation pipe coupled to the gas phase reactor outlet, the liquid phase reactor outlet, and the 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 in the reactor, and the flow rate of the reaction mixture circulated per minute is preferably 0.01 to 20 times the capacity of the reactor charged catalyst. 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 addition, the lower portion of the liquid phase reactor is provided with a liquid level control device to continuously operate while maintaining a constant liquid level by adjusting the height of the liquid phase in the liquid phase reactor (see Fig. 4).

From the liquid phase reactor, the reaction mixture is introduced into the hydroformylation main reactor through the reactor bottom piping, and some of the product produced through the hydroformylation reaction from the main reactor is continuously or intermittently hydroformylated through the circulation pump. Specifically, it is recycled through the high velocity dispersion into the gas phase reactor. In addition, most of the reaction product is transferred to the catalyst separation device is separated from the catalyst, and then only the aldehyde reaction product passes through the hydrogenation reactor or the aldol condensation reactor and the separation distillation column sequentially. In this case, the separated catalyst and the unreacted olefin are supplied to the olefin feed pipe and directly supplied to the hydroformylation main reactor. During the total residence time of the process, the unreacted olefin is recycled during a predetermined number of cycles.

In summary, in the present invention, as an additional reactor for hydroformylation of olefins, the reactor includes a gas phase reactor for performing a reaction in gas phase conditions, and the gas phase reactor includes a catalyst and an olefin liquid reactant inlet, a synthesis gas inlet, and a reactor bottom outlet. It includes, The liquid reactant inlet is provided with a spray nozzle for high-speed injection with the catalyst solution is olefin is recycled from the olefin supply pipe, the syngas inlet is spray nozzle to perform an effective reaction with the supplied olefin Included in the side wall facing the side wall provided, the lower outlet of the gas phase reactor is connected to the inlet of the liquid phase reactor for performing the liquid phase reaction.

The liquid phase reactor includes a reactant inlet, an inner loop and a reactor outlet, the reactant inlet connected to a lower outlet of the gas phase reactor, and the inner loop is adapted to increase the flowability of the supplied reaction mixture. The reactor outlet is characterized in that the reaction mixture is introduced into the hydroformylation reactor through the reactor bottom pipe. In this case, the inner loop diameter is 0.1 to 0.9 times the diameter of the main reactor in terms of reaction efficiency. It is preferable and it is more preferable that they are 0.2 times-0.7 times.

The first advantage of the hydroformylation addition reactor described above is that the reaction efficiency can be improved by carrying out the further reaction under gaseous and liquid phase conditions. A second advantage is achieved by using a reactor with an inner loop as the liquid phase reactor, in particular good heat transfer from the reaction mixture by reaction under liquid phase conditions through the loop, thus achieving a uniform temperature profile, and a higher It has a slurry density and results in better mixing.

In addition, although a liquid phase reactor is further provided in the present invention, a short residence time is possible by providing a loop in the liquid phase reactor, and as a result, the catalyst is deactivated. This means that when the catalyst is withdrawn from the liquid phase reactor through the outlet and circulated, the catalyst still has high activity.

Syngas, unreacted reactants, aldehydes and solvents from the liquid phase reactor are fed to the hydroformylation main reactor to carry out the reaction again, and some of them are transferred to the additional reactors through circulation pipes through circulation pumps, and then the Dispersed, most of the mixture is transferred to the catalyst separator for separation.

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

Of course, the recovered aldehyde may be treated with a conventional distillation apparatus or the like to separate and recover various aldehydes and condensation products.

The process for preparing aldehydes from olefins according to the present invention and the reaction apparatus used therewith are subjected to hydroformylation addition reactions which sequentially carry out liquid phase reactions followed by gas phase reactions, thereby improving reaction conversion rate and dimer or trimer. Since fewer heavy components are produced, the reaction selectivity is increased and the reaction yield is improved.

1 is a schematic diagram of a reactor used for the hydroformylation process of an olefin using a continuous stirred reactor (CSTR) according to the prior art.
2 is a schematic view of a hydroformylation further reactor 10 of olefins according to the present invention.
3 is a cross-sectional view showing an example having two inner loops 30a in the liquid phase reactor 10b according to the present invention.
4 is a schematic diagram of a reactor used for the hydroformylation process of olefins using the hydroformylation further reactor 10 shown in FIGS. 2 and 3 according to the present invention.

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.

Example (Gas reaction + spray nozzle-> liquid reaction-> Hydroformylation  Main reaction)

In the present embodiment, the result obtained when the reaction as shown in FIG. 4 is performed using the inner loop 30a in the hydroformylation additional reactor 10 of the olefin of FIG. 2 and the liquid phase reactor 10b of FIG. Observed.

That is, the reactor of the gas phase reactor 10a having a size of 3 liters (diameter 200 mm x height 200 mm) as the reaction apparatus of FIG. 2 reacts the liquid phase reactor 10b having a size of 1.5 liters (diameter 100 mm x height 200 mm). Connection to the chamber constituted a hydroformylation further reactor 10.

The diameter of the nozzle mounted on the gas phase reactor 10a (with an ejector (not shown)) is 3.0 mm, and the diameter of the liquid phase reactor primary inlet 20 corresponding to the outlet of the gas phase reactor 10a is 200 mm. The diameter of the secondary inlet 30 corresponding to the actual outlet of the gas phase reactor was 100 mm, and the vertical distance between the primary inlet 20 and the secondary inlet 30 was 30 mm.

3, the inner loop 30a in the liquid phase reactor 10b was provided with two diaphragms in a 100 mm liquid phase reactor chamber with a diameter of 30 mm and 70 mm.

24 g of triphenylphosphine (TPP) and 0.4 g of rhodium triphenylphosphine acetylacetonatecarbonyl (ROPAC) were weighed and dissolved in purified normal-butylaldehyde to prepare a total weight of 400 g of normal-butylaldehyde catalyst solution. .

The catalyst solution thus prepared was introduced into a jacketed CSTR having a temperature control of 2.1 liters as a main reactor (1), and a circulating pump was operated to slowly circulate the catalyst solution at a rate of 0.2 liters per minute while the nozzle at the top of the reactor. The entire system was purged three times with purified nitrogen gas.

While maintaining the external circulation pump at a rate of 0.4 liters per minute, an external heat exchanger was run to maintain the temperature inside the main reactor 1 at 90 ° C. When the temperature stabilized at 90 ° C., propylene was injected and supplied until the internal pressure of the main reactor 1 became 16.2 bar, and it was confirmed that the internal temperature of the CSTR main reactor 1 was maintained at 90 ° C. for 5 minutes after the supply. .

At the same time, some of the aldehyde-containing reaction product produced in the main reactor 1 is intermittently or continuously through the circulation pump 8 and the circulation piping 7a, 7b of the gas phase reactor 10a in the further reactor 10. It was injected at a flow rate of 6 g / min through the nozzle 12 provided on the side wall, in particular the side wall opposite the side to which the synthesis gas is supplied, the injection speed was in the range of 5 to 30 m / s.

In addition, the reaction product and the unreacted reactants generated in the gas phase reaction space together with the catalyst solution are the liquid phase reactor primary inlet 20 corresponding to the gas phase reactor outlet and the liquid phase reactor secondary inlet 30 corresponding to the actual gas phase reactor outlet 30. And into the reaction chamber of the liquid phase reactor 10b via a transfer space consisting of

The administered reaction mixture was moved between the two diaphragm type inner loops 30a provided in the reaction chamber of the liquid phase reactor 10b in a fluidized bed to allow further reaction to proceed. The diameters of the two loops used were 30 mm and 70 mm, respectively. The liquid phase reaction space and the main reaction apparatus 1 were each equipped with a liquid level control device so as to be able to react while maintaining a constant liquid level.

The reaction mixture discharged from this apparatus was supplied to the hydroformylation main reactor (1), and most of the product was sent to the catalyst separator (4) to separate the catalyst, and the separated catalyst and the remaining olefin were recycled to the catalyst transfer pipe ( The circulation was started through 6) to the hydroformylation main reactor (1).

After confirming that the temperature and pressure of the entire reaction system are kept constant at 90 ° C. and 18 bar for 1 hour, add the pre-set syngas (mixture of 50:50 molar ratio of carbon monoxide and hydrogen) at a feed pressure of 18.8 bar The reaction was started at the same time as supplying to the synthesis gas supply pipe (11) of the reactor (10).

During the reaction, the reaction pressure was maintained at 18 bar. For this purpose, propylene and syngas were supplied in an equivalent ratio.

In this way, the reaction proceeded continuously for 18 hours. The weight of butylaldehyde obtained through the catalyst separation device was 2,880 g, and the amount of butylaldehyde produced per unit weight of the catalyst was 0.40. The product was analyzed by GC. Except for the light component, the dimer and trimer contents of the dimer and trimer were 1.2% and 0.7%, respectively.

Comparative Example  1 (previous experiment result according to FIG. 1)

The same process as in Example 1 was repeated except that no hydroformylation further reactor 10 was used according to the process flow diagram of FIG. 1.

The butylaldehyde obtained continuously for 18 hours weighed 2,304 g, and the butylaldehyde production per unit weight of the catalyst was 0.32. The GC analysis showed that the average content of dimer and trimer except for light was average. 2.3% and 1.8%.

Test Example  1 (gas reaction space and liquid phase Between reaction spaces  Optimal Size Selection Experiment)

This experiment is an example to select the optimum size between the gas phase reaction space and the liquid phase reaction space.

First, the same experiment as in Example 1 was carried out for 18 hours except that 1.0 liter of gas phase reactor 10a was connected to 1.5 liter of liquid phase reactor 10b, and the weight of butylaldehyde obtained was 2,664 g. The amount of butylaldehyde produced per unit weight of catalyst per unit time was 0.37.

GC analysis showed that the average content of dimer and trimer except for light was 1.4% and 0.6%, respectively.

Also, except that the size of the gas phase reactor 10a was changed to 1.5 liters, the same experiment as in Example 1 was carried out for 18 hours, and the weight of the obtained butylaldehyde was 2,736 g, and the catalyst unit weight per unit time. The amount of sugar butylaldehyde produced was 0.38.

As a result of GC analysis, the content of dimer and trimer except for light was 1.3% and 0.7%, respectively.

Also, except that the size of the gas phase reactor 10a was changed to 6 liters, the same experiment as in Example 1 was carried out for 18 hours, and the weight of the obtained butylaldehyde was 2,881 g, and the catalyst unit weight per unit time. The amount of sugar butylaldehyde produced was 0.40.

As a result of GC analysis, the content of dimer and trimer except for light was average 1.5% and 0.7%, respectively.

In summary, it was confirmed that the gas phase reactor has a capacity of 0.5 to 40 times that of the liquid phase reactor.

Comparative Example  2 (gas reactor (without spray nozzle)-> liquid reactor)

In Example 1, the same process was repeated except that the ejector (not shown) and the spray nozzle 12 were used instead of only 1/4 inch tubes.

After the reaction was carried out for 18 hours in this manner, the weight of butylaldehyde obtained was 2,376 g, and the amount of butylaldehyde produced per unit weight of the catalyst was 0.33.

GC analysis showed that the average content of dimer and trimer except for light was 2.1% and 1.7%, respectively.

As can be seen from the above, in the case of the embodiment (gas phase reactor + spray nozzle-> liquid phase reaction-> hydroformylation main reaction) according to the method of the present invention, Comparative Example 1 (jacket reactor + heat exchanger), Comparative Example It was confirmed that the reaction efficiency was significantly improved compared to all experiments of 2 (gas phase reactor-> liquid phase reactor without spray nozzle).

1,1 ': hydroformylation main reactor
2,2 ': Olefin supply piping
3,3 ', 7a, 7b: reaction product delivery piping
4,4 ': catalytic separator
5,5 ': separation of aldehyde reaction product
6,6 ': Recycle catalyst transfer piping
8: circulation pump
9,9 ': Supply of olefin and catalyst mixture liquid
10: hydroformylation further reactor
10a: gas phase reactor
10b: liquid phase reactor
11: Syngas supply piping
12: Nozzle
13: liquid level control
20: liquid phase reactor primary inlet
30: liquid phase reactor secondary inlet
30a: inner loop (diaphragm type)
40: reactor outlet

Claims (13)

The olefin is hydroformylated in a stirred type hydroformylation main reactor to produce an aldehyde, wherein some of the aldehyde containing product is separated off of the catalyst and recycled to the hydroformylated main reactor, and some of the aldehyde containing product Conducting hydroformylation further reaction under a syngas atmosphere of hydrogen and carbon dioxide in a hydroformylation further reactor and forming an aldehyde containing reaction mixture, wherein the aldehyde containing reaction mixture is circulated to the hydroformylation main reactor
Process for preparing aldehydes from olefins. The method of claim 1, wherein the hydroformylation further reaction is
i) in a gas phase reactor on the upper side of the hydroformylation further reactor, the high speed dispersed aldehyde containing product conducts a hydroformylation reaction under the syngas atmosphere and forms an aldehyde containing reaction mixture; And
ii) further hydroformylation of the aldehyde-containing reaction mixture in a bottom liquid phase reactor of a further reactor connected to the bottom of the gas phase reactor; Characterized in that sequentially made in two steps
Process for preparing aldehydes from olefins. The method of claim 1, wherein the olefin is ethylene, propylene, 1-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, At least one selected from the group consisting of 2-ethylhexene, 2-octene, styrene, 3-phenyl-1-propene or 4-isopropylstyrene
Process for preparing aldehydes from olefins. The process of claim 1, wherein the aldehyde-containing reaction mixture is introduced into a hydroformylated main reactor to react with unreacted olefins and recycle catalyst; And some of the reactants are sprayed at high speed by the nozzle into the hydroformylation further reactor through the circulation pump and the circulation piping.
Process for preparing aldehydes from olefins. 3. The high velocity jet linear velocity of the reaction mixture to the gas phase reactor in a hydroformylation further reactor is characterized in that it is in the range of 2 to 50 m / s.
Process for preparing aldehydes from olefins. The method of claim 2, wherein the gas phase and liquid phase reaction is carried out at a temperature of 50 to 200 ℃ and a pressure of 5 to 100 bar
Process for preparing aldehydes from olefins. The method of claim 5, wherein the circulating capacity of the reaction mixture is characterized in that 0.01 to 20 times the capacity of the catalyst charged in the gas phase reactor.
Process for preparing aldehydes from olefins. Stirred type hydroformylation main reactors for hydroformylation of olefins to produce aldehydes;
A hydroformylation addition reactor for receiving an aldehyde-containing product obtained in the hydroformylation main reactor through a circulation pump and a circulation pipe to perform hydroformylation addition reaction under a syngas atmosphere; And
Consisting of a catalyst separation device having a pipe for separating the aldehyde reaction product and the catalyst and unreacted olefin from the reaction product discharged from the hydroformylated main reactor, the double catalyst and the unreacted olefin to the olefin feed pipe; Characterized
An apparatus for producing aldehyde from olefins. 9. The method of claim 8,
The hydroformylation further reactor comprises a gas phase reactor for carrying out the reaction in the gas phase conditions and a liquid phase reactor for carrying out the reaction in the liquid phase conditions,
The gas phase reactor is
A reactant inlet provided with a spray nozzle for high-speed injection of the mixed liquid from a supply pipe of the catalyst and olefin mixed liquid, and a side wall opposite to the side wall provided with a spray nozzle for effective reaction with the supplied catalyst and olefin; Syngas inlet, the primary inlet of the liquid phase reactor corresponding to the outlet of the gas phase reactor connected to the inlet of the liquid phase reactor to transfer the reacted mixture, and the actual outlet of the gas phase reactor connected to the primary phase of the liquid phase reactor Includes; the secondary inlet of the liquid phase reactor corresponding to,
The liquid phase reactor is
An inner loop having one or more diaphragms to increase the fluidity of the reaction mixture supplied into the reactor, and a reactor outlet connected to the circulation pipe so that the reaction mixture is circulated by a circulation pump; Characterized in that consists of
An apparatus for producing aldehyde from olefins. The gas phase reactor has a capacity of 0.5 to 60 times that of the liquid phase reactor.
An apparatus for producing aldehyde from olefins. 10. The method of claim 9, wherein in the gas phase reactor, the means for injecting a mixture of catalyst and olefin comprises an ejector equipped with a nozzle having a diameter of 0.1 to 1000 mm.
An apparatus for producing aldehyde from olefins. 10. The method of claim 9, wherein the diameter of the liquid phase reactor secondary inlet, which is the actual outlet of the gas phase reactor, is 0.3 to 0.9 times the diameter of the liquid phase reactor primary inlet.
An apparatus for producing aldehyde from olefins. 10. The liquid level control device according to claim 9, wherein a lower level of the liquid phase reactor is provided.
An apparatus for producing aldehyde from olefins.

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