KR20130018428A - Apparatus for producing alcohol from olefin - Google Patents

Abstract

PURPOSE: A manufacturing method of an alcohol from olefin is provided to increase the gas contact surface area of olefin and mixed gas by having a dispersion plate inside a hydroformylation reactor, thereby being capable of production efficiency of aldehyde. CONSTITUTION: A manufacturing apparatus of olefin from alcohol comprises: a hydroformylation reactor(100) which comprises a spraying unit(120), a reactor outlet(130), a dispersion plate, and a circulation pipe(150); a catalyst/aldehyde separator(200) which comprises a separation pipe(210), a catalyst/aldehyde separator(220), a catalyst mixed solution supply pipe(230), and an aldehyde circulation pipe(240); a hydrogenation reactor(300) which adds hydrogen to the aldehyde; a distillation apparatus part(400) which comprises an inlet(410), a lower boiling point discharge part(420), a middle boiling point discharge part(430), and a high boiling point discharge part(440).

Description

[0001] Apparatus for Producing Alcohol From Olefin [0002]

The present invention relates to a process for producing an alcohol from an olefin, and more particularly, to a hydroformylation reaction unit; A catalyst / aldehyde separation unit; A hydrogenation reaction unit; And an apparatus for producing an alcohol from an olefin comprising a distillation unit.

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.

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 fed to the oxo reactor using the catalyst along with syngas (CO / H ₂ ) to produce normal-butylaldehyde and iso-butylaldehyde. The resulting aldehyde mixture is sent to the separation system together with the catalyst mixture to separate into hydrocarbon and catalyst mixture, then the catalyst mixture is circulated to the reactor and the hydrocarbon component is transferred to the stripper. The hydrocarbons in the stripper are stripped by fresh syngas to recover unreacted propylene and syngas in the oxo reactor and the butylaldehyde is transferred to the fractionation column and separated into normal and iso-butylaldehyde, respectively. The normal-butylaldehyde in the bottom of the fractionation column is transferred to a hydrogenation reactor and is made into n-butanol by hydrogenation. Or n-butylaldehyde is introduced into an aldol condensation reactor to produce 2-ethylhexanoic acid by condensation and dehydration reaction, and then transferred to a hydrogenation reactor, which is produced by hydrogenation with octanol (2-ethylhexanol) .

The hydroformylation reaction can be carried out continuously, semicontinuously or batchwise, and a typical hydroformylation process is a gas or liquid recirculation 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. For this purpose, a continuous stirred tank reactor (CSTR), which stirs liquid and vapor components uniformly in the reactor, has been used. U.S. Patent No. 5,763,678 also discloses a hydroformylation process that replaces agitation through circulation by applying a series of loop shaped reactors. However, the above methods have limitations in improving the efficiency of the hydroformylation reaction, and since a satisfactory aldehyde product can not be obtained with only a single reactor, generally, a reaction residence time is increased or two or more reactors are connected in series, Products.

In addition, the hydrogenation process of aldehydes is usually carried out using a reactor mainly filled with a nickel-based or copper-based solid hydrogenation catalyst. Evaporating the starting aldehyde to carry out the reaction on the vapor phase, or introducing the starting aldehyde into the reactor as a liquid to carry out in a liquid phase.

However, despite the catalytic species and the vapor phase or liquid phase reaction, undesirable side reactions such as esterification, acetalization, and etherification occur in the reaction, and the selectivity of the reaction is deteriorated.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a hydroformylation reaction apparatus capable of improving the production efficiency of aldehyde by increasing the contact area between liquid olefins and gaseous mixture gas, And a method for producing an alcohol from an olefin using the same. The present invention also provides an apparatus for producing an alcohol from olefins.

In order to solve the above-mentioned problems, the present invention provides a combustion apparatus comprising: injection means mounted on an upper portion of a reactor for injecting olefin and syngas (CO / H ₂ ) into a catalyst mixture solution charged in a reactor; A reactor outlet located at the bottom of the reactor to discharge the reaction mixture of olefin and syngas; A distributor plate mounted between the injection means and the reactor outlet for switching the flow of olefin and synthesis gas; A hydroformylation reaction unit connected to the reactor outlet and the injection unit, the circulation pipe including a circulation pipe for withdrawing the reaction mixture from the reactor outlet and supplying the reaction mixture to the injection unit to circulate the reaction mixture;

A separation pipe separated from any one of the circulation pipes to separate the reaction mixture from the circulation flow; A catalyst / aldehyde separation unit connected to the separation line for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And a catalyst / aldehyde separation unit connected to the catalyst / aldehyde separation unit and containing an aldehyde recovery pipe for recovering aldehyde;

A hydrogenation reaction unit for adding hydrogen to the recovered aldehyde; And

An inlet portion through which the hydrogenation reaction product passing through the hydrogenation reaction portion flows; A low boiling point component discharge portion through which the low boiling point component is discharged from the hydrogenation reaction product; A middle boiling point component discharging portion for discharging a middle boiling point component in the hydrogenation reaction product; And a high-boiling-point component discharge portion through which the high boiling point component is discharged from the hydrogenation reaction product; ≪ RTI ID = 0.0 > a < / RTI >

Another object of the present invention is to provide a process for producing olefins and syngas by forming fine bubbles of olefins and syngas by spraying olefin and synthesis gas (CO / H ₂ ) into a catalyst mixture solution, A hydroformylation step of reacting the fine bubbles and the catalyst mixed solution to obtain an aldehyde;

A hydrogenation step of adding hydrogen to the aldehyde as a product of the hydroformylation step to obtain a hydrogenation product containing alcohol; And

And separating the structural isomer of the alcohol by fractional distillation of the hydrogenation product as a product of the hydrogenation step.

Hereinafter, an apparatus for producing an alcohol from olefin according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a schematic view of an apparatus for producing an alcohol from olefins according to an embodiment of the present invention. Referring to FIG.

An apparatus for producing an alcohol from olefins according to an embodiment of the present invention includes:

Injection means 120 mounted on the reactor 100 for injecting olefin and synthesis gas (CO / H ₂ ) into the catalyst mixture solution charged in the reactor; A reactor outlet 130 located below the reactor and through which a reaction mixture of olefin and synthesis gas is discharged; A dispersion plate (140) mounted between the injection means and the reactor outlet for switching the flow of olefin and synthesis gas; A hydroformylation reaction unit (100) connected to the reactor outlet and the injection unit, and a circulation pipe (150) for circulating the reaction mixture through recovery of the reaction mixture from the reactor outlet and supply to the injection unit;

A separation pipe 210 separated from any one of the circulation pipes 150 to separate the reaction mixture from the circulation flow; A catalyst / aldehyde separation unit 220 connected to the separation pipe 210 for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe 230 connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And an aldehyde recovery pipe (240) connected to the catalyst / aldehyde separation device for recovering aldehyde (240);

A hydrogenation reaction unit 300 for adding hydrogen to the recovered aldehyde; And

An inlet 410 through which the hydrogenation reaction product passing through the hydrogenation reaction unit flows; A low boiling point component discharge portion 420 through which the low boiling point component is discharged from the hydrogenation reaction product; A middle boiling point component discharge portion 430 through which the intermediate boiling point product is discharged from the hydrogenation reaction product; And a high boiling point component discharge unit 440 through which the high boiling point product is discharged from the hydrogenation reaction product.

The hydroformylation reaction unit 100 will be described in more detail as follows.

The olefin and the syngas are injected into the catalyst mixture solution charged in the reactor 110 by the injection means 120 mounted on the reactor 100.

The injector 120 is not particularly limited as long as it can inject the olefin and the syngas into the catalyst mixture solution charged in the reactor. For example, the injector 121 equipped with the nozzle may be used. The nozzle mounted on the ejector 121 functions to increase the speed by reducing the injection cross sectional area of the olefin and the syngas fed into the reactor at a high pressure. The diameter of the nozzle may vary depending on the size of the reactor, and is preferably 0.1 to 500 mm.

Further, it is preferable that the venturi pipe 122 is coupled to the ejector 121. The venturi pipe 122 includes an inlet 122a in the form of an intact pipe and a diffusion part 122b in the form of a pipe extending in a downward direction. The inlet 122a is connected to an ejector 121 and the diameter of the inlet portion 122a is equal to the diameter of the inlet of the diffusion portion 122b and smaller than the diameter of the outlet of the diffusion portion 122b. At the same time, the outlet direction of the diffusion portion 122b is preferably directed toward the lower portion of the reactor. The diameter of the inlet portion is preferably 0.2 to 1000 mm, and the length of the inlet of the diffusion portion is preferably 1/50 to 1/2 of the total length of the reactor. It is preferable that the diameter of the diffusion portion inlet is equal to the diameter of the inlet portion and the diameter of the diffusion portion outlet is 1.0 to 10 times the diameter of the diffusion portion inlet. The length of the diffusion portion is preferably 0.1 to 10 times the length of the inlet portion and the length of the total venturi tube including the inlet portion and the diffusion portion is preferably 0.01 to 0.95 times the reactor body length and 0.05 to 0.75 More preferable.

The olefins and the mixed gas as the reaction raw materials are injected into the reactor through the ejector 121 and the venturi pipe 122 connected to the injector 121. The injected olefin and the mixed gas are charged into the reactor while forming fine bubbles In the catalyst mixture solution. Since the minute bubbles of the olefin and the mixed gas are brought into contact with the catalyst mixture solution, the gas-liquid contact surface area is wide, thereby providing a sufficient reaction area.

And the flow of the olefin and the mixed gas injected by the dispersing plate 140 mounted between the injecting means 120 and the outlet 130 of the reactor is switched. This change in the reaction raw material flow lengthens the residence time of the reaction raw material in the reactor, thereby improving the reaction efficiency. The conversion of the reaction material flow is determined depending on the position and the shape of the dispersion plate 140, and thus the reaction efficiency can be controlled.

The dispersion plate 140 is preferably located between 1/3 and 2/3 of the length from the reactor outlet 130 to the venturi tube 122 outlet in the direction of the venturi tube, between 1/2 More preferably located at. FIGS. 3 and 4 show the reactivity of the hydroformylation reaction unit according to the position of the dispersion plate.

In FIG. 4, the horizontal axis indicates the radius of the lower outlet pipe, and the vertical axis (product composition) indicates that the reaction is relatively faster. In FIG. 4 (a), it is seen that the circulation flow rate is low, and (e) is the highest at the flow rates (b) to (e), and is higher at the outlet wall surface.

Further, it may be flat depending on the shape of the dispersion plate 140, convex with respect to the diffusion tube outlet direction, or concave, and concave is most preferable. 2 is a cross-sectional view of a diffuser plate. FIG. 2 (a) shows a flat shape, (b) shows a convex shape, and FIG. 2 (c) shows a concave shape.

The size of the dispersing plate may be 10% to 75% of the inner diameter of the reactor 100.

The attached figures 5 and 6 show the reactivity according to the form of the dispersion plate of the hydroformylation reaction apparatus. Referring to FIG. 6, it can be seen that (C) is most advantageous in reactivity.

As described above, the olefin and the synthesis gas are injected into the catalyst mixture solution, and the hydroformylation reaction proceeds. Accordingly, the reaction including the aldehyde, the catalyst mixture solution, the untransferred olefin, the synthesis gas and other reaction by- The mixture is present. This reaction mixture is recovered at the bottom of the reactor by the circulation pipe (150) connected to the reactor outlet and the injection means and supplied to the injection means at the top of the reactor. By this circulation, the reaction mixture is injected together 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 160 provided in the circulation pipe.

Also, the circulation pipe 150 may be provided with a heat exchanger 170, and its position is not limited to a specific position on the circulation pipe. The heat exchanger 170 serves to maintain the reaction mixture circulated in the reactor at a temperature suitable for hydroformylation reaction conditions.

The reaction mixture separated at any one of the circulation pipes of the hydroformylation reaction part is separated into the catalyst mixture solution and the aldehyde by the catalyst / aldehyde separation part 200, the catalyst mixture solution is circulated to the reactor 110, Is transferred to the hydrogenation reaction section (300).

Hereinafter, the catalyst / aldehyde separation unit 200 will be described in more detail.

The catalyst / aldehyde separation unit 200 is separated from the circulation pipe 150 of the hydroformylation reaction unit and separates the reaction mixture from the circulation flow. A catalyst / aldehyde separation unit 220 connected to the separation pipe 210 for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe 230 connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And an aldehyde recovery pipe 240 connected to the catalyst / aldehyde separation unit for recovering aldehyde.

The reaction mixture in the hydroformylation reaction unit 100 is separated from the circulation pipe 150 by the separation pipe 210 of the catalyst / aldehyde separation unit and supplied to the catalyst / aldehyde separation unit 220. The catalyst mixture solution separated in the catalyst / aldehyde separation unit 220 is circulated to the hydroformylation reaction unit through the catalyst mixture solution supply pipe 230 connected to one of the circulation pipes 150. The aldehyde separated in the catalyst / aldehyde separation unit 220 is transferred to the hydrogenation reaction unit through the aldehyde recovery pipe 240 connected to the catalyst / aldehyde separation unit.

The type of the catalyst / aldehyde separation unit 220 is not limited as long as it is a means for separating the catalyst mixture solution and the aldehyde from the reaction mixture. For example, a vaporizer may be used for discharging aldehyde as a low boiling point component in a vapor state in the reaction mixture through a heat exchange process, and discharging the catalyst mixture solution as a high boiling point component in a liquid phase.

The recycle of the catalyst mixture solution in which the aldehyde as the target substance is separated can be continuously carried out and the catalyst can be regenerated by discharging a part of the reaction mixture which is occasionally circulated, Can be added to the circulation flow.

The aldehyde separated in the catalyst / aldehyde separation unit 200 is transferred to the hydrogenation unit 300 and is converted into alcohol by hydrogenation reaction.

The hydrogenation reaction unit 300 includes injection means 312 for injecting the recovered aldehyde and hydrogen gas into the catalyst mixture liquid charged in the reactor 311; A reactor outlet 315 located in the lower portion of the reactor where the hydrogenation reaction mixture of aldehyde and hydrogen gas and aldehyde is discharged; And a circulation pipe 316 connected to the reactor outlet 315 and the injection means 312 for recovering the hydrogenation reaction mixture of aldehyde and hydrogen gas and aldehyde from the reactor outlet and supplying the hydrogenation reaction mixture to the injection means to circulate the hydrogenation reaction mixture do.

The hydrogenation reaction mixture of aldehyde, hydrogen gas and aldehyde is injected into the catalyst mixture liquid charged in the reactor 311 by the injection means 312.

The ejection unit 312 may use an ejector 312 equipped with a nozzle. The nozzle mounted on the ejector 312 functions to increase the speed by reducing the injection cross sectional area of the aldehyde and the hydrogen gas supplied into the reactor at high pressure.

The diameter of the nozzle may vary depending on the size of the reactor, and is preferably 1 to 500 mm.

Further, it is preferable that a venturi tube 314 is coupled to the ejector 312. The venturi tube 314 includes an inlet 314a and a diffusion 314b as is known in the art and the inlet 314a is coupled to the ejector 312 and has a tube diameter Is equal to the diameter of the inlet of the diffusion portion 314b and is smaller than the diameter of the diffusion portion outlet. At the same time, the outlet of the diffusion portion 314b is preferably directed to the lower portion of the reactor. Preferably, the diameter of the inlet portion is 0.2 to 1000 mm, the diameter of the inlet of the diffusion portion is equal to the diameter of the inlet portion, and the diameter of the outlet portion of the diffusion portion is 1.0 to 10 times the inlet diameter of the diffusion portion. The length of the diffusion portion is preferably 0.1 to 100 times the length of the inlet portion and the length of the entire Venturi tube including the inlet portion and the diffusion portion is preferably 0.01 to 0.95 times the reactor body length and 0.05 to 0.75 times desirable.

The hydrogenation reaction mixture of the aldehyde, the hydrogen gas and the aldehyde is injected into the reactor through the ejector 312 and the venturi tube 314 coupled to the injector 312. The aldehyde and the mixed gas injected in this way form a fine bubble, And is injected into the catalyst mixture liquid charged inside. The minute bubbles of the aldehyde and the hydrogen gas are brought into contact with the catalyst mixture solution, so that the gas-liquid contact surface area is wide and a sufficient reaction area is provided. As a result, the efficiency of the hydrogenation reaction of the aldehyde is improved.

The aldehyde and hydrogen gas injected into the reactor react in the presence of a catalyst mixture to produce an alcohol as a reaction product. Thus, the hydrogenation reaction mixture is recovered at the lower portion of the reactor by the circulation pipe 316 connected to the outlet of the reactor and the injection means, so that the upper portion of the reactor To the spraying means (312). By this circulation, the hydrogenation reaction mixture is injected together with the reaction raw material and sufficiently mixed to improve the reaction efficiency. This circulation can be controlled by the circulation pump 317 provided in the circulation pipe 316.

Also, the circulation pipe 316 may be provided with a heat exchanger 318, and its position is not limited to a specific position on the circulation pipe. The heat exchanger 318 serves to maintain the hydrogenation reaction mixture circulated in the reactor at a temperature suitable for the hydrogenation reaction.

The catalyst mixed solution charged in the reactor 311 is a fluid containing nickel or copper, which will be described later.

Further, the hydrogenation reaction unit separates the hydrogenation reaction mixture from any one of the circulation pipe 316 (319a), separates it into a catalyst mixture solution and an alcohol in a catalyst mixture solution and an alcohol separation unit 319, The hydrogenation reaction mixture containing alcohol can be transferred to the distillation apparatus section through the catalyst mixture liquid supply pipe 319b connected to any one of the circulation pipe 316 and circulated to the hydrogenation reactor 311. [

Alternatively, as shown in FIG. 7, the hydrogenation reactor 300 may include an injector 322 injecting the recovered aldehyde and hydrogen gas into the reactor 321; A nickel catalyst layer 323a on the side where aldehyde and hydrogen are introduced, and having high activity; A low activity copper catalyst layer 323b located under the nickel catalyst layer; And a reactor outlet 324 located below the reactor and through which the hydrogenation reaction mixture is discharged.

The aldehyde and hydrogen gas are injected into the reactor 321 by the injection means 322. The injected aldehyde and hydrogen in turn pass through the nickel catalyst layer 323a having high activity and the copper catalyst layer 323b having low activity, and hydrogen is added to the aldehyde to generate alcohol.

Generally, the hydrogenation reaction of aldehyde uses a single catalyst of nickel or copper, but in the present invention, it is characterized in that a two-layer catalyst 323 of nickel and copper is used. Generally, when only a highly active nickel catalyst is used, the temperature rises due to the exothermic reaction, and the temperature increases at the outlet of the reactor, thereby causing a side reaction. There is a problem due to occurrence of a side reaction rather than an increase in reaction efficiency due to a catalyst having a high activity. In the present invention, the reaction rate is increased by using a highly active nickel catalyst (323a) at the inlet of the reactor having a high concentration of the reactant to be converted, and a low activity copper catalyst layer 323b are used to suppress the side reaction.

The aldehyde and the hydrogen gas injected into the reactor pass through the two-layer catalyst layer to produce alcohol as a reaction product. The hydrogenation reaction product containing the alcohol that has passed through the hydrogenation unit 300 is transferred to a distillation unit 400 for fractional distillation.

The distillation unit 400 includes an inlet 410 through which the hydrogenation reaction product having passed through the hydrogenation reaction unit flows; A low boiling point component discharge portion 420 through which the low boiling point component is discharged from the hydrogenation reaction product; A middle boiling point component discharge unit 430 discharging a middle boiling point component of the hydrogenation reaction product; And a high boiling point component discharge unit 440 through which the high boiling point product is discharged from the hydrogenation reaction product.

The inlet and each outlet of the distillation unit are divided by a dividing wall, and the dividing wall is designed to be insulated so that the inlet and each outlet are individually regulated in temperature and pressure. The hydrogenation reaction product passing through the hydrogenation reaction unit includes alcohol, aldehyde, hydrogen, reaction by-products and the like. Each substance is fractionally distilled according to boiling point.

The inlet is preferably operated at a pressure between 20 and 100 < 0 > C and between 1.0 and 5.0 bar. The low boiling point component of the hydrogenation reaction product in the inlet portion, such as normal / iso-aldehyde, water, iso-alcohol, etc., is vaporized and moved to the low boiling point component discharge portion 420 and discharged through the low boiling point component discharge pipe 421. The low boiling point component outlet 420 is preferably operated at a pressure of 30 to 120 ℃ and 0.1 to 5.0 bar. The middle boiling point component that has not been vaporized in the inflow portion and the low boiling point component discharge portion 420 is moved to the middle boiling point component discharge portion 430 and discharged through the middle boiling point component discharge pipe 431. The main component of the above-mentioned intermediate boiling point components in the hydrogenation reaction product is a normal-alcohol and iso-alcohol mixture. The middle boiling point component discharge portion 430 is preferably operated at a pressure of 40 to 170 ° C and a pressure of 0.01 to 5.0 bar. The high boiling point component not vaporized also moves to the high boiling point component discharge section 440 and is discharged through the high boiling point component discharge pipe 441 in the middle boiling point component discharge section. The high boiling point component of the hydrogenation reaction product includes a n-alcohol, an aldehyde dimer, and an aldehyde trimer. The high boiling point component discharge portion 440 is preferably operated at a pressure of 60 to 250 ° C and a pressure of 0.1 to 5.0 bar.

The apparatus for producing an alcohol from the olefin comprises a distillation unit 500 for separating aldehyde into n-aldehyde and iso-aldehyde after the hydroformylation reaction unit as shown in FIG. And

And an aldol condensation reaction unit 600 for producing an aldehyde having an increased carbon number by aldol condensation of the normal-aldehyde.

The distillation unit 500; And the aldol condensation reaction unit 600, an alcohol having two times more carbon atoms than the aldehyde generated after the hydroformylation reaction unit can be produced.

* For example, when the hydroformylation reaction is carried out with propylene, normal-butylaldehyde and iso-butylaldehyde are produced, and 2-ethylhexanoic acid is produced by aldol condensation. The hydrogenation step can be carried out with an aldehyde with increased carbon number to produce octanol (2-ethylhexanol).

The present invention also

A hydroformylation step of spraying an olefin and a syngas (CO / H ₂ ) into the catalyst mixture solution, and performing a reaction while switching the injection flow of the olefin and the synthesis gas to obtain an aldehyde;

A hydrogenation step of adding hydrogen to the aldehyde as a product of the hydroformylation step to obtain a hydrogenation product containing alcohol; And

And separating the structural isomer of the alcohol by fractional distillation of the hydrogenation product, which is the product of the hydrogenation step, to a process for producing an alcohol from olefins.

The hydroformylation step may be carried out by injecting olefins and syngas (CO / H ₂ ) into the catalyst mixture solution to form minute bubbles of olefins and syngas, And then reacting the solution to obtain an aldehyde.

Olefin and syngas are sprayed to form fine bubbles, and the fine bubbles are brought into contact with the catalyst mixture solution, thereby providing a sufficient reaction area because the vapor-liquid contact surface area is wide. In addition, the reaction is carried out while the injection flow of the olefin and the syngas is switched to increase the residence time of the reaction raw material in the reactor, thereby improving the reaction efficiency.

This hydroformylation step is preferably carried out using the hydroformylation unit described above.

The catalyst mixture solution of the hydroformylation step is generally used in a hydroformylation reaction and may include a transition metal catalyst and a ligand.

Examples of the transition metal catalyst include cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt) , Palladium (Pd), iron (Fe), or nickel (Ni) may be used. Specifically, cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonatodicarbonyldium [Rh (AcAc) (CO) ₂ ], acetylacetonatocarbonyltriphenylphosphinedium [Rh (AcAc) ( CO) (TPP)], hydridocarbonyltri (triphenylphosphine) rhodium [HRh (CO) (TPP) ₃ ], acetylacetonatodicarbonyliridium [Ir (AcAc) (CO) ₂ ] and hydrido One or more complex catalysts selected from the group consisting of carbonyltri (triphenylphosphine) iridium [HIr (CO) (TPP) ₃ ] can be used.

The ligand may be a tri-substituted phosphine, a phosphine oxide, an amine, an amide, or an isonitrile, or may be a tri-substituted phosphine, . The tri-substituted phosphines include, but are not limited to, triaryl phosphine, triaryl phosphite, alkyldiaryl phosphine, and more specifically triphenyl phosphine, tritolyl phosphine, triphenyl phosphite, and n -Butyldiphenylphosphine and the like can be used.

Examples of the solvent used in the catalyst mixture solution include, but are not limited to, aldehydes such as propanaldehyde, butylaldehyde, pentylaldehyde, and valeraldehyde; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or cyclohexanone; Alcohols such as ethanol, pentanol, octanol, and pentanol; Aromatics such as benzene, toluene and xylene; Ethers such as tetrahydrofuran, dimethoxyethane and dioxane; And paraffin hydrocarbons such as heptane. Preferably, the reaction products such as propanaldehyde, butylaldehyde, pentylaldehyde, valeraldehyde and the like are used. The concentration of the catalyst mixture solution is preferably 30% to 99% of the total solution weight.

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 2 to 20 carbon atoms can be used. More specifically, olefins having 1 to 20 carbon atoms such as ethylene, propylene, 1-butene, Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-octadecene, 1-pentadecene, 2-butene, 2-hexene, 2-octene, styrene, 3-phenyl-1-propene Propylene, 1-butene, 2-butene 1-pentene, 2-pentene, 2-methyl butene and the like are more preferable.

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.

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 1 m / sec to 50 m / sec, and more preferably 5 m / sec to 30 m / sec. The pressure difference after the catalyst mixture liquid passes through the injection means 120 is preferably 0.1 to 10 bar, more preferably 0.5 to 5 bar.

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.

Further, the hydroformylation step preferably further comprises a reaction mixture circulation step of recovering the reaction mixture and feeding it into the catalyst mixture solution together with the olefin and the synthesis gas.

The reaction mixture discharged through the outlet of the reactor is recovered and the reaction material is thoroughly mixed with the reaction mixture by the circulation device 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 device can be achieved by means of a circulation line connected to the reactor outlet and to the means of injection of the reactor, and a circulation pump coupled thereto. The flow rate of the circulating reaction mixture is preferably 0.01 to 20 times the reactor charge capacity per minute.

The hydroformylation step may further include separating a part of the reaction mixture to be separated into a catalyst mixture solution and an aldehyde, supplying the separated catalyst mixture solution to the circulation flow, and recovering the aldehyde.

Specifically, when the olefin which is the starting material of the hydroformylation process is propylene, the reaction mixture contains butylaldehyde, more specifically, n-butylaldehyde and iso-butylaldehyde, and the reaction mixture includes a catalyst / To separate the aldehyde and catalyst mixture and then the catalyst mixture is circulated to the reactor and the aldehyde component is transferred to the hydrogenation step.

In the hydrogenation step, hydrogen is added to the aldehyde, which is a product of the hydroformylation step, to obtain a hydrogenation product including an alcohol. The method for hydrogenating the aldehyde can be carried out as commonly used in the art, but it is preferably carried out as follows.

In the hydrogenation step, the recovered aldehyde and hydrogen gas are sprayed into the catalyst mixture solution to form microbubbles of aldehyde and hydrogen gas, and the microbubbles and the catalyst mixture are reacted.

It is preferable that the catalyst mixture solution contains Raney-Ni or copper powder. As the catalyst mixture solution, a solvent may be used, and as an appropriate solvent, aldehyde or alcohol is preferable. Specifically, when the olefin which is a starting material of the hydroformylation process is propylene and the substance to be fed into the hydrogenation reaction portion is butylaldehyde, normal or iso-butyl alcohol is preferable as a solvent. The composition of the solvent is preferably 2% to 99%, more preferably 20% to 90% based on the weight ratio.

Or the method of hydrogenating the aldehyde is preferably carried out by sequentially passing recovered aldehyde and hydrogen gas through a catalyst layer composed of a Ni catalyst layer having high activity and a Cu catalyst layer having low activity.

Generally, the hydrogenation reaction of aldehyde uses a single catalyst of nickel or copper, but the present invention uses a catalyst layer composed of a double layer of nickel and copper. The catalyst layer composed of the double layer passes the liquid phase aldehyde and hydrogen gas in a fixed phase.

Generally, when only a highly active nickel catalyst is used, the temperature rises due to the exothermic reaction, and the temperature increases at the outlet of the reactor, thereby causing a side reaction. This is a problem due to the occurrence of side reactions rather than the increase of the reaction efficiency by the catalyst having high activity.

Therefore, in the present invention, the reaction rate is increased by using a high-activity nickel catalyst layer at the initial stage of the reaction with a high concentration of the reactant to be converted, and a side reaction is performed using the copper catalyst layer having low activity at the low- .

The aldehydes in the hydrogenation step are preferably those which comprise from 1 to 20 carbons and at least one aldehyde group due to the hydroformylation reaction of olefins, including but not limited to. For example, there may be mentioned formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, n-valaldehyde, iso-valeraldehyde, n-hexaldehyde, n- Ethylhexanal, n-decanal, 2-ethylbutanal, propargylaldehyde, acrolein, glyoxal, crotonaldehyde, furfural, aldol, hexahydrobenzaldehyde, alpha-citronellal, citral , Chlal, trimethylacetaldehyde, diethylacetaldehyde, tetrahydrofurfural, phenylaldehyde, cinnamaldehyde, or hydrocinnamaldehyde. Preferably propionaldehyde, n-butylaldehyde and iso-butylaldehyde, or n-valerealdehyde and iso-valeraldehyde.

For example, when the hydroformylation reaction is carried out with propylene, normal-butylaldehyde and iso-butylaldehyde are produced, and the hydrogenation step can proceed to produce normal-butylalcohol and iso-butylalcohol.

The aldehyde is preferably sprayed at a rate of 0.1 to 100 m / sec. As the aldehyde is injected at a constant rate, the hydrogen gas is sucked into the hydrogenation reactor.

The molar ratio of the aldehyde and the hydrogen gas is preferably 1:10 to 10: 1. The reaction temperature is preferably 50 to 300 ° C, and the reaction pressure is preferably 2 to 100 bar.

The separation step separates the structural isomer of the alcohol by fractional distillation of the hydrogenation product, which is the product of the hydrogenation step.

Hydrogenation products include aldehydes, hydrogen, reaction by-products and the like as well as alcohol as a target material. As a method for separating alcohol as a target substance, a method commonly used in the art can be used, but it is preferable to use the following method.

The hydrogenation reaction product may utilize a column having a divided wall by dividing walls. The dividing walls are designed to be adiabatic, and each of the dividing regions may be different in temperature and pressure from the operating temperature and pressure of the conventionally used column depending on the position and structure of the dividing region, and may be appropriately adjusted according to the design It is also possible. The hydrogenation product is fractionally distilled according to boiling point passing through each partition. The lower boiling point components of the hydrogenation product, such as normal and iso-aldehyde, water, iso-alcohol, etc., are vaporized in the regulated region at a relatively low temperature and pressure and discharged to the upper portion of the column. Also, the iso-alcohol and the normal-alcohol which are intermediate boiling point components are not vaporized, are liquefied in vaporization, and are discharged from the middle boiling point section of the column. High-boiling components such as trace amounts of normal-alcohol, aldehyde dimer and aldehyde trimer are not vaporized but are discharged in the liquid phase through the lower part of the column.

For example, when the hydroformylation reaction is carried out with propylene, normal-butylaldehyde and iso-butylaldehyde are produced, and the hydrogenation step and the distillation purification step are carried out to convert n-butyl alcohol and isobutyl alcohol into a final product .

A step of separating aldehyde, which is a product of the hydroformylation step, after the hydroformylation step into a normal-aldehyde and an iso-aldehyde; And an aldol condensation step of aldol condensation of the n-aldehyde to obtain an aldehyde having an increased carbon number, to carry out the hydrogenation step with an aldehyde having an increased carbon number. If these steps are additionally carried out, an increased number of carbon atoms can be produced.

For example, when the hydroformylation reaction is carried out with propylene, n-butylaldehyde and iso-butylaldehyde are produced, and 2-ethylhexanoic acid is produced by aldol condensation. The hydrogenation step can be carried out with an aldehyde with increased carbon number to produce octanol (2-ethylhexanol).

The hydroformylation reaction unit included in the apparatus for producing an alcohol from olefins according to the present invention provides a sufficient reaction area because the contact surface area of the olefin and the synthesis gas as reaction materials is wide by the dispersing plate provided therein, The reaction raw material is sufficiently mixed with the reaction mixture to make the aldehyde production efficiency excellent. Also, the hydrogenation reaction part of the aldehyde suppresses the side reaction and improves the production efficiency of the alcohol.

According to the apparatus for producing alcohol from olefins according to the present invention, the investment cost for producing alcohol from olefin is reduced by the improved process as described above, and the production efficiency is high.

FIG. 1 (a) is a schematic view showing a process for producing an alcohol from olefin according to an embodiment of the present invention. FIG. 1 (b) is a schematic view showing the process of producing an alcohol from the inlet portion 122a and the diffusion portion 122b of the venturi diffusion tube 122. As shown in FIG.
2 is a cross-sectional view of a dispersion plate included in a hydroformylation reaction unit of an olefin of the present invention.
FIG. 3 and FIG. 4 show the results of simulation of the hydroformylation reaction using the hydroformylation reaction unit according to the present invention, showing the reactivity according to the position of the dispersion plate. In FIG. 4, the abscissa indicates the radius of the lower outlet pipe, and the higher value of the ordinate (product composition) means that the reaction is relatively faster. Here, (a) shows the case when the circulating flow rate is small, and (b) to (e) that the flow velocity is high, it can be seen that (e) is the highest.
FIGS. 5 and 6 show the results of a process simulation of the hydroformylation reaction using the hydroformylation reaction apparatus according to the present invention, showing the reactivity according to the form of the dispersion plate.
7 is a schematic process diagram illustrating a process for producing an alcohol from olefin according to an embodiment of the present invention.
FIG. 8 is a schematic diagram showing a process for producing an alcohol from olefin according to an embodiment of 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  1.1> Preparation of catalyst solution

To 28.7 kg of n-butylaldehyde having a purity of 99%, 3.2 kg of triphenylphosphine (TPP) was added to dissolve completely. 45.9 g of acetylacetonatodicarbonyl triphenylphosphine rhodium (ROPAC) catalyst, which had been previously quantified in advance, was further added thereto to obtain a catalyst solution 32 kg.

< Example  1.2> Aldehyde production step

Two 30 liter volume loop reactors were fabricated and a Venturi diffuser tube having a diameter of 5 mm and a diameter of 10 mm diffusion tube inlet diameter, 20 mm diffusion tube outlet diameter and a diffusion tube length of 30 cm was placed in each reactor head . In addition, a flat diffusion plate having a diameter of 70 mm was fixed to the inside of the reactor 200 mm from the lower discharge port. A circulation pump was installed outside the reactor to allow the reaction liquid to be recycled to the injection nozzle of each reactor head at a flow rate of 20 liters per minute. Also, a heat exchanger was installed in the outer circulation line of both reactors, Respectively.

Two reactors were connected in series. One of the two reactors connected in series was connected to one of the circulating lines, and a control device was installed to allow continuous operation of the preceding reactor in a certain liquid state .

The second reactor, which is a second reactor connected in series with the preceding reactor, is also equipped with a control device so that the reaction mixture can be continuously operated in a constant liquid by sending the reaction mixture to an evaporator for separating aldehyde from one of the circulation lines of the reactor, .

Each of the loop reactors connected in series was independently supplied with propylene and syngas as raw materials. As the reaction proceeds, the aldehyde introduced into the evaporator from the downstream reactor enters the hydrogenation reaction section together with the hydrogen gas via the condenser. The aldehyde is recovered through the evaporator and the remaining catalyst solution is passed through a separate pump And recycled to the reactor. 16 kg of each of the catalyst solutions prepared above was charged into the two reactors and purged twice with nitrogen gas and propylene. The reaction temperature was maintained at 89 degrees through the circulation pump 160 and the heat exchanger 170. When the internal temperature of the reactor was stabilized, propylene was fed until the internal pressure of each reactor reached 12 bar.

After the temperature and pressure were stabilized again, the raw propylene was supplied to the preceding reactor at a flow rate of 3.7 kg / hr, and the synthesis gas was supplied to the preceding and following reactor at an average flow rate of 2.2 kg and 0.5 kg per hour. The liquid level of each reactor was maintained at 20 liters, and the pressure and temperature of the preceding reactor were stabilized at 18 barg and 89 degrees and the pressure and temperature of the downstream reactor were 15 barg and 89 degrees, respectively.

As a result, the amount of butylaldehyde produced was measured and the total amount of butylaldehyde was measured. As a result, it was estimated that a total of 1,512 kg of butylaldehyde was produced per hour, and the propylene charged was converted into butylaldehyde The propylene conversion efficiency, which means the ratio, was 99.3%.

< Example  1.3> Hydrogenation step of aldehyde

( Example  1.3.1) Hydrogenation of aldehydes using a loop reactor

In the next step, a total of 16 kg of the catalyst liquid prepared by mixing 2.4 kg of the slurry Raney-nickel catalyst in 100% normal-butyl alcohol was charged into a loop reactor having the same structure and volume as described above and purged twice with nitrogen ), The reaction temperature and pressure were maintained at 110 and 25 barg through the circulation pump 317 and the heat exchanger 318, respectively, and the liquid level was set to 80% through the control device. Once the temperature stabilized, the butylaldehyde produced was fed to the reactor with 0.35 kg hydrogen gas per hour at a rate of 6.3 kg per hour, as described above in Example 1.2, while the flow rate of the circulating pump was maintained at 20 liters per minute . As a result of continuous operation for 90 hours after reaching a steady state while maintaining the liquid level, the total weight of the hydrogenation product, which is the main component of the obtained alcohols, was 587 kg, which was an average of 6.52 kg per hour.

Analysis of the components by gas chromatography showed that the weight ratio of the n-butyl alcohol was 86.9%, the iso-butyl alcohol was 8.7%, the heavy component such as butyl aldehyde trimer was 4.2%, and the water was 0.2%.

( Example  1.3.2) Duplicate Fixed bed  Hydrogenation of aldehydes using a catalytic reactor

 As shown in FIG. 7, a gamma-alumina-supported nickel catalyst was filled from a position 10 cm from the top of the reactor in the form of a column having a diameter of 8 cm and a length of 330 cm to 210 cm and filled with alumina balls to a depth of 230 cm therefrom. The copper catalyst supported on gamma-alumina was filled up to a length of up to 320 cm. A separate circulation pump and an external heat exchanger were used to maintain the reactor outlet temperature at no more than 110 ° C and the reactor internal pressure was maintained at 25 barg. N-Alcohol was used as a solvent medium for the reaction and heat exchange, and the circulation flow rate was maintained at 38 kg per hour. After reaching the steady state, the reactor was operated for 90 hours. The total weight of the hydrogenation product, which is the main component of butyl alcohol, was 581 kg, and an average of 6.45 kg per hour was obtained.

Analysis of the components by gas chromatography showed that the weight ratio of the n-butyl alcohol was 87.1%, the iso-butyl alcohol was 8.6%, the heavy component such as butyl aldehyde trimer was 4.3%, and the water was 0.2%.

( Example  1.4) DWC ( Divided Wall Column ) To purify alcohol

 A DWC (Divided Wall Column) was produced by dividing 10 cm each of both sides of the pipe using a pipe having a diameter of 8 cm and a length of 94 cm and dividing the inside of the pipe evenly vertically by using a metal diaphragm inside the pipe. A glass wool and a rashig ring with an average diameter of 1 cm were placed on the pre-column side to which the feed was introduced and a packed column having a theoretical number of 18 stages based on the result of the process simulation was used. ) And the main column of which the middle boiling point outlet is directed also constitutes a packed column having a theoretical number of stages of 18 stages in the same manner. A packed column was constructed in the lower part of the column equipped with the reboiler (reboiler) and the upper part of the column equipped with the condenser in the same manner as the theoretical step number 6 stages.

Therefore, the pre-column pre-column at the feed inlet portion is 18 stages, and the main column at the middle boiling point discharge outlet is all 30 stages. Start The hydrogenation reaction product as described in Example 1.3 above was fed to the column at a flow rate of 6.4 kg per hour at the sixth stage of the pre-column through the start and stabilization stages, the middle boiling point component was continuously recovered at the 12th stage from the top of the main column. The total steady-state operating time was 86 hours. A total of 1.07 kg of water and less than 20 g of iso-butyl alcohol were obtained from the top of the column.

Through the intermediate boiling point outlet, a ternary mixture containing 47.7 kg of iso-butyl alcohol, 476.6 kg of n-butyl alcohol and 5 g or less of water was obtained. At the bottom of the column, 23 kg of aldehyde trimer and normal-butyl alcohol of 0.5 kg or less were obtained. Converting the power supplied to the column from the reboiler under steady state operating conditions resulted in an average of 1.49 MCal per hour.

< Example  2> Aldol Condensation reaction  through Carbon number Increased  Preparation of alcohol

( Example  2.1) Aldol Condensation reaction  through Carbon number Increased  Production of aldehyde

A 20 liter liquid in which a 2.0 liter NaOH aqueous solution and a normal-butyl aldehyde were mixed at a ratio of 1: 2 was charged into a 30 liter vertical tank type continuously stirred reactor (CSTR), and the temperature inside the reactor was raised to 5 barg Respectively.

The aldehyde mixture prepared in Example 1.3 was subjected to fractional distillation to obtain 240 kg of n-butylaldehyde having a purity of 99% as a feed for aldol condensation reaction while maintaining the stirring speed at 300 RPM. The obtained n-butylaldehyde was continuously charged at a rate of 6.3 kg per hour, and the reaction product was recovered by decantering under normal operating conditions for 32 hours while maintaining the liquid level at 20 liters.

The total weight of the reaction product was 158 kg. As a result, ethyl propyl acrolein was produced at an average of 4.74 kg per hour as 96% of ethyl propyl acrylate, 3.9% of n-butyl aldehyde and 0.1% of aldehyde trimer.

( Example  2.2) Through hydrogenation Carbon number Increased  Preparation of alcohol

The same procedure as in Example 1.3.1 was followed, except that the 96% ethyl propyl acrolein reaction product prepared in Example 2.1 was fed at a rate of 4.7 kg per hour with 0.26 kg of hydrogen per hour, The reaction was carried out.

As a result of continuous operation for 28 hours after reaching the steady state while maintaining the liquid level, the total weight of the hydrogenation product, which is the main component of octanol, was 136 kg, and an average of 4.86 kg per hour was obtained.

As a result of analyzing the components through gas chromatography, the content of butanol was 0.5%, the content of octanol was 96%, the content of heavy components such as butylaldehyde trimer was 3.3%, and the content of water was 0.2%.

< Comparative example  1>

Two serially connected Steady-state continuous operation was carried out for 72 hours in the same manner as in Example 1.2 except that a 30 liter vertical tank type continuously stirred reactor (CSTR) was used, resulting in a total of 436 kg of butylaldehyde, resulting in an average of 6.06 kg Butanol was produced. The propylene conversion efficiency was 95.6%, which means that the amount of propylene converted into butylaldehyde was not converted to propane, which is a byproduct.

< Comparative example  2>

The hydrogenation reaction was carried out in the same manner as in Example 1.3.2, except that packing was performed using only a nickel catalyst supported on gamma-alumina as a catalyst. As a result, it was operated for 72 hours after reaching the steady state. The total weight of the hydrogenation product, which is the main component of butyl alcohol, was 465 kg, kg. &lt; / RTI &gt;

Analysis of the components by gas chromatography showed that the weight ratio of the n-butyl alcohol was 84.8%, the iso-butyl alcohol was 8.7%, the water was 0.2%, and the heavy component such as butyl aldehyde trimer was 6.3% by weight.

< Comparative example  3>

Using two pipes of the same diameter and length as in Example 1.3, two theoretical plates with 20 stages of distillation packed columns equipped with a reboiler and a condenser were prepared and connected in series. The same feed as in Example 1.3 was fed to the eighth stage from the top of the first column at the same flow rate of 6.4 kg per hour while the product was recovered from the column top and the bottom product was again fed from the top of the second column to the eighth stage And the product was recovered from the top and top of the second column.

The total steady-state operating time was 70 hours. As a top column product of the first column, a total of 0.89 kg of water and less than 15 g of iso-butyl alcohol were obtained. As a top column of the second column, a ternary mixture comprising 38.7 kg of iso-butyl alcohol, 388.3 kg of normal-butyl alcohol and 7 g of water was obtained. 18.6 kg of an aldehyde trimer and 0.7 kg of normal-butyl alcohol were obtained as a final bottom product.

In steady state operation conditions, the amount of power supplied to the column from the reboiler was converted to calories, resulting in a total of 1.93 MCal / hr. The first column had an average of 0.63 MCal per hour and the second column was 1.32 MCal.

100: a hydroformylation reactor unit 200: a catalyst / aldehyde separation unit
300: hydrogenation reaction unit 400: distillation unit
500: aldehyde distillation unit 600: aldol condensation reaction unit

Claims (29)

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; A distributor plate mounted between the injection means and the reactor outlet for switching the flow of olefin and synthesis gas; A hydroformylation reaction unit connected to the reactor outlet and the injection unit, the circulation pipe including a circulation pipe for withdrawing the reaction mixture from the reactor outlet and supplying the reaction mixture to the injection unit to circulate the reaction mixture;
A separation pipe separated from any one of the circulation pipes to separate the reaction mixture from the circulation flow; A catalyst / aldehyde separation unit connected to the separation line for separating the catalyst mixture solution and the aldehyde from the reaction mixture; A catalyst mixture solution supply pipe connected to either one of the catalyst / aldehyde separation unit and the circulation pipe to supply the catalyst mixture solution to the circulation pipe; And a catalyst / aldehyde separation unit connected to the catalyst / aldehyde separation unit and containing an aldehyde recovery pipe for recovering aldehyde;
A hydrogenation reaction unit for adding hydrogen to the recovered aldehyde; And
An inlet portion through which the hydrogenation reaction product passing through the hydrogenation reaction portion flows; A low boiling point component discharge portion through which the low boiling point component is discharged from the hydrogenation reaction product; A middle boiling point component outlet for discharging the middle boiling point component of the hydrogenation reaction product; And a high boiling point component outlet through which the high boiling point component is discharged from the hydrogenation reaction product.
Apparatus for producing an alcohol from an olefin comprising a. The method of claim 1,
Wherein the spraying means of the hydroformylation reaction part comprises an ejector with a nozzle mounted thereon. The method of claim 2,
Wherein the diameter of the nozzle is between 1 and 500 mm. The method of claim 2,
Wherein the ejector comprises a venturi tube. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method of claim 4, wherein
Wherein the venturi tube has an inlet coupled to the ejector and a diffuser facing the reactor outlet wherein the diameter of the inlet of the diffuser is equal to the diameter of the inlet and the diameter of the outlet of the diffuser is 1.0 times the diameter of the inlet of the diffuser To 10 times the weight of the olefin. The method of claim 1,
The dispersion plate is an apparatus for producing alcohol from olefins, characterized in that it is located between 1/3 and 2/3 of the length from the reactor outlet 130 to the venturi tube outlet to the reactor outlet and venturi tube 122 outlet. . The method of claim 1,
Wherein said dispersion plate is flat in shape, convex with respect to the outlet of the diffuser, or concave. The method of claim 1,
The hydrogenation reaction unit is injection means for injecting the recovered aldehyde and hydrogen gas to the catalyst mixture solution charged in the reactor; A reactor outlet located at the bottom of the reactor through which a reaction mixture of aldehyde and hydrogen gas is discharged; And a circulation pipe connected to the reactor outlet and the injection means, and recovering the reaction mixture from the reactor outlet and supplying the reaction mixture to the injection means to circulate the reaction mixture. The method of claim 8,
Wherein the injecting means of the hydrogenation reaction part comprises an ejector equipped with a nozzle. The method of claim 9,
Wherein the diameter of the nozzle is between 1 and 500 mm. The method of claim 9,
Wherein the ejector comprises a venturi tube. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method of claim 11,
Wherein the venturi tube has an inlet coupled to the ejector and a diffuser facing the reactor outlet wherein the diameter of the inlet of the diffuser is equal to the diameter of the inlet and the diameter of the outlet of the diffuser is 1.0 times the diameter of the inlet of the diffuser To 10 times the weight of the olefin. 13. The method of claim 12,
Wherein the length of the diffuser is 0.1 to 100 times the length of the inlet. The method of claim 11,
The length of the venturi diffusion tube is an apparatus for producing alcohol from olefins, characterized in that 0.01 to 0.95 times the length of the reactor body. The method of claim 1,
The hydrogenation reaction unit injection means for injecting the recovered aldehyde and hydrogen gas into the reactor; Nickel catalyst layer having a high activity, located on the side where aldehyde and hydrogen are introduced; A low activity copper catalyst layer positioned below the nickel catalyst layer; And a reactor outlet positioned at the bottom of the reactor through which the hydrogenation reaction mixture is discharged. The method of claim 1,
The inlet of the distillation unit is operated at a pressure of 20 to 100 ℃ and 1.0 to 5.0 bar, the low boiling point component outlet is operated at a pressure of 30 to 120 ℃ and 0.1 to 5.0 bar, the middle boiling point component outlet 40 to 170 ℃ and And a high boiling point component outlet is operated at a pressure of 60 to 250 ° C. and a pressure of 0.1 to 5.0 bar. The method of claim 1,
A distillation unit for separating the aldehyde into n-aldehyde and iso-aldehyde after the hydroformylation reaction apparatus; And
And an aldol condensation reaction unit for aldol condensation of the n-aldehyde to produce an aldehyde having an increased carbon number. Injecting olefins and syngas (CO / H ₂ ) into the catalyst mixture solution to form microbubbles of olefins and syngas, and reacting the microbubbles and the catalyst mixture solution while switching the injection flow of the olefins and syngas to react aldehydes Obtaining hydroformylation step;
A hydrogenation step of adding hydrogen to an aldehyde which is a product of the hydroformylation step to obtain a hydrogenation reaction product including an alcohol; And
And a separation step of separating the structural isomers of the alcohol by fractional distillation of the hydrogenation reaction product which is the product of the hydrogenation step. The method of claim 18,
Wherein the catalyst mixture solution of the hydroformylation step comprises a transition metal catalyst and a ligand. The method of claim 18,
The catalyst mixed solution of the hydroformylation step may include aldehydes such as propane aldehyde, butyl aldehyde, pentyl aldehyde, and baler aldehyde; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and 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; At least one selected from the group consisting of A process for producing an alcohol from an olefin. The method of claim 18,
The olefins in the hydroformylation step may be selected from the group consisting of ethylene, propylene, butene, 1-hexene, 1-octene, 1-nonene, Octene, 1-octadecene, 1-octadecene, 1-octadecene, 1-hexadecene, 1-hexadecene, Wherein the olefin is at least one selected from the group consisting of hexene, 2-octene, styrene, 3-phenyl-1-propene and 4-isopropylstyrene. The method of claim 18,
The hydroformylation step further comprises a reaction mixture circulating step of recovering the reaction mixture and supplying it with the olefin and the synthesis gas into the catalyst mixture solution. 23. The method of claim 22,
The hydroformylation step is characterized in that it further comprises the step of separating the catalyst mixture solution and aldehyde by separating a portion of the circulating reaction mixture, supplying the separated catalyst mixture solution to the circulation flow, and recovering the aldehyde Process for producing alcohol from olefins. The method of claim 18,
Wherein the hydrogenation step comprises spraying the recovered aldehyde and hydrogen gas into a catalyst mixture solution to form microbubbles of aldehyde and hydrogen gas, and reacting the microbubbles and the catalyst mixture solution. 25. The method of claim 24,
Wherein the catalyst mixture solution comprises Raney-Ni or copper powder. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt; The method of claim 18,
The hydrogenation step is carried out by passing the recovered aldehyde and hydrogen gas through a catalyst layer consisting of a double layer of a high activity Ni catalyst layer and a low activity Cu catalyst layer in order to produce an alcohol from olefins. The method of claim 18,
The aldehydes of the hydrogenation stage may be selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, iso-butylaldehyde, n-valaldehyde, iso- valaldehyde, n-hexaldehyde, n-heptaldehyde, Ethylhexanal, n-decanal, 2-ethylbutanal, propargylaldehyde, acrolein, glyoxal, crotonaldehyde, furfural, aldol, hexahydrobenzaldehyde, alpha-citronellal, A process for producing an alcohol from an olefin, characterized in that it is at least one selected from the group consisting of citral, chorale, trimethylacetaldehyde, diethylacetaldehyde, tetrahydrofurfural, phenylaldehyde, cinnamaldehyde, and hydrocinnamaldehyde . The method of claim 18,
Wherein the aldehyde in the hydrogenation step is injected at a rate of 0.1 to 100 m / sec. The method of claim 18,
A step of separating aldehyde, which is a product of the hydroformylation step, after the hydroformylation step into a normal-aldehyde and an iso-aldehyde; And
Wherein the aldol condensation step of aldol condensation of the n-aldehyde to obtain an aldehyde having an increased carbon number is further carried out to proceed the hydrogenation step with an aldehyde having an increased number of carbon atoms.

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