WO2017043773A1

WO2017043773A1 - Hydrogenation reactor

Info

Publication number: WO2017043773A1
Application number: PCT/KR2016/008611
Authority: WO
Inventors: 안우열; 양혜림; 장재규; 최성업
Original assignee: 한화케미칼 주식회사
Priority date: 2015-09-10
Filing date: 2016-08-04
Publication date: 2017-03-16
Also published as: KR20170030858A; TW201711748A; TWI645898B; KR101872511B1

Abstract

The present invention relates to a hydrogenation reactor. More specifically, the present invention relates to a hydrogenation reactor with improved stability and reaction efficiency of hydrogenation. The hydrogenation reactor of the present invention is provided with a hydrogen circulation pipe to recirculate hydrogen gas flowing in the upper region of a reaction chamber to a reaction system by means of the hydrogen circulation pipe, thereby being capable of improving the efficiency of hydrogenation.

Description

【Specification】

[Name of invention]

Hydrogenation reaction machine [technical field]

Cross citation with related application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0128298 dated September 10, 2015, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

The present invention relates to a hydrogenation reactor. In more detail, it is related with the hydrogenation reaction machine which improved the reaction efficiency and stability of a hydrogenation reaction reaction.

[Technique to become background of invention]

In general, hydrogenation or hydrogenation processes for organic compounds are reactions applied to reducing specific functional groups or converting unsaturated compounds to saturated compounds, such as ketones, aldehydes, imines, and the like. Compounds having the same unsaturated functional groups can be applied to various compounds such as reduction of compounds with alcohols, amines, etc., or saturation of unsaturated bonds of olefin compounds. It is one of the important reactions.

Such hydrogenation reaction is generally carried out by contacting a reaction object to be subjected to hydrogen and a hydrogenation reaction with a noble metal catalyst. Reactors for hydrogenation reaction are typically trickle bed reactors and loop reactors. ).

Among these, the trickle bed reactor has the advantage of low investment and operating costs, but due to the risk of pressure drop, the particle size of the catalyst to enter the reactor has to be large, so that the contact area between the catalyst and the reaction product is reduced and the reaction efficiency is low.

On the contrary, the loop type reactor does not have a limitation on the size of the catalyst, and because of the excellent compatibility between the liquid phase and the gas phase, the efficiency of the catalyst is excellent. However, the loop-type reaction device is to perform hydrogenation reaction in a gaseous reaction mixture of gaseous hydrogen gas and a liquid phase reaction liquid, and does not dissolve in the reaction system. There is a disadvantage in that it is necessary to inject a lot of hydrogen gas because the hydrogen gas coming out of this space inevitably exists.

Problem to be solved

In order to solve the above problems, it is to provide a hydrogenation reactor that improves the efficiency of the hydrogenation reaction by recirculating the hydrogen gas flowing in the upper region of the reaction chamber of the reaction chamber back to the reaction system.

[Task solution]

Accordingly, according to one embodiment of the present invention,

A reaction chamber in which the hydrogenation reaction takes place;

A reaction mixture injecting reactant including hydrogen, a reaction target to be hydrogenated, and a solvent;

A semi-ungmul supply unit which is located in connection with the reaction product and supplies the reactant into the reaction chamber;

A reaction product discharge part disposed under the reaction chamber and discharging the hydrogenated reaction product to the outside of the reaction chamber;

A hydrogen supply pipe connected to the reactant supply unit and additionally supplying hydrogen to the reaction chamber through the reaction system; And

One end is connected to the upper portion of the reaction chamber, the other end is connected to the interruption of the hydrogen supply pipe, including a first hydrogen circulation pipe for circulating hydrogen gas flowing in the upper region of the reaction chamber to the reaction water supply portion Provide a hydrogenation reaction.

【Effects of the Invention】

According to the hydrogenation reaction machine of this invention, it is equipped with the hydrogen circulation piping, The efficiency of the hydrogenation reaction can be improved by recycling the hydrogen gas flowing in the upper region of the chamber back into the reaction system by the hydrogen circulation pipe.

In addition, in the case of including a plurality of the hydrogen circulation pipe according to an embodiment of the present invention, the flow rate of hydrogen circulated from the upper portion of the reaction tank to the semi-water supply portion is increased more than if only one, and the fluidity of the gas is much higher It can be improved so that the efficiency of the hydrogenation reaction can be further improved.

[Brief Description of Drawings]

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the structure of a general loop type hydrogenation reaction reactor. 2 is a diagram illustrating a structure of a hydrogenation reaction reactor according to an embodiment of the present invention.

3 is a diagram illustrating a structure of a hydrogenation reaction reactor according to another embodiment of the present invention.

4 is a view showing a state seen from above the hydrogenation reaction counter according to an embodiment of the present invention.

[Specific contents for implementation of the invention]

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Also, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, step, component, or combination thereof, that includes one or more other features or steps, Does not preclude the existence or possibility of addition of components or any combination thereof It must be understood.

In addition, in the present invention, when each component is first to be formed "on" or "on" of each component, it means that each component is directly formed on each component, or other components are each It can be formed additionally between the layer, the object, the substrate.

Hereinafter, the hydrogenation reaction reactor of the present invention will be described in more detail with reference to the accompanying drawings. Hydrogenation reaction according to an embodiment of the present invention, the reaction chamber in which the hydrogenation reaction occurs; A semi-ungmul injecting unit for injecting a reaction product including hydrogen, a reaction object to be hydrogenated, and a solvent; A reactant supply unit located in connection with the reaction water injector and supplying the reaction water to the reaction chamber; A reaction product discharge part disposed under the reaction chamber and discharging a hydrogenation reaction product outside the reaction chamber; A hydrogen supply pipe which is connected to the semi-flounder supply part and additionally supplies hydrogen to the reaction additive through the semi-flounder supply part; And a first hydrogen circulation pipe having one end connected to an upper portion of the reaction chamber and the other end connected to an interruption of the hydrogen supply pipe to circulate hydrogen gas flowing in an upper region of the reaction chamber to the reaction product supply unit. do. Commercially used reaction reactors for such hydrogenation include trickle bed reactors, loop reactors, and the like.

Among these, the trickle bed reactor has the advantage of low investment cost and operating cost, but the contact area of the catalyst and the reactant is reduced because the size of the catalyst entering the reactor due to the risk of pressure drop has a disadvantage of low reaction efficiency.

On the contrary, the loop reactor has no limitation on the size of the catalyst and has excellent efficiency of the catalyst because of excellent compatibility between the liquid phase and the gas phase. The loop-type reaction device undergoes a hydrogenation reaction in a reaction system in which a gas phase of hydrogen gas and a liquid phase reaction object and a solvent are mixed. Accordingly, hydrogen gas that does not dissolve in the reaction system and exits into the space where the reaction object is absent is There is a disadvantage in that it is necessary to add a relatively large amount of hydrogen gas in order to complement this can not exist.

The hydrogenation reaction group of the present invention reduces unsaturated functional groups such as ketones, aldehydes, imines, etc., or saturates carbon-carbon double bonds or triple bonds present in olefinic compounds, aromatic compounds, petroleum resins, and other organic compounds or resins. It can be applied to various hydrogenation reactions or hydrogenation processes, and is not particularly limited.

According to one embodiment of the invention, the hydrogenation reactor can be used for the hydrogenation reaction of dicyclopentadiene (DCPD) resin. Dicyclopentadiene resin is a resin obtained by thermal polymerization of DCPD, and has excellent compatibility with a base polymer such as a metallocene polymer and has a low molecular weight, and thus is used as an adhesive or an adhesive in various fields. However, since the DCPD resin has a yellowish brown color and gives off a bad smell, it needs to be modified into a colorless and odorless resin by saturating by adding hydrogen to a carbon-carbon backbone bond through hydrogenation reaction. In addition, the DCPD resin subjected to the hydrogenation reaction has the advantage that the thermal stability and weather resistance is significantly improved.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the structure of a general loop type hydrogenation reaction reactor. Referring to FIG. 1, the hydrogenation reaction vessel 9 includes a reaction product inlet 1, a reactant supply 3, a reaction product outlet 4, a reaction chamber 5, and a hydrogen supply pipe 6. do. The reaction liquid supply part 3 is located in the upper part of the reaction chamber 5 and the reaction liquid supply nozzle 2a communicating with the reaction liquid injection part 1, and is located inside the reaction chamber 5, and supplies the reaction product And a semi-coagulant diffuser 2b for diffusing the semi-coagulum supplied from the nozzle 2a into the reaction chamber 5.

A reaction mixture comprising hydrogen, a reaction object to be hydrogenated, and a solvent is injected from the reaction product injection section 1 through the reaction product supply nozzle 2a of the reaction product supply section 3 into the reaction chamber 5 at a constant speed. do. The injected reaction mixture diffuses through the reactant diffusion section 2b into the space in the reaction chamber 5, and the reaction object to be hydrogenated in the presence of the catalyst present in the reaction chamber 5 reacts with the hydrogen to perform the reaction reaction. Done.

At this time, undissolved hydrogen gas in the liquid reaction mixture And flows in the upper region 7 of the chamber 5, such that the upper region 7 which is an empty space without hydrogen, the reaction object to be hydrogenated, and the solvent is present in the reaction system 8 together. The hydrogen gas raised to) does not participate in the hydrogenation reaction and thus the reaction efficiency decreases.

Thus, a hydrogen supply pipe (6) is separately included to complement the hydrogen gas leaving the reaction system (8), and the reaction chamber (5) intermittently from the hydrogen supply pipe (6) intermittently as necessary in the middle of the hydrogenation reaction. ) Supply hydrogen gas in a complementary manner. The hydrogen supply pipe 6 is connected with the semi-atom water supply part 3 at a position near the reactant supply nozzle 2a, so that the hydrogen gas supplied from the hydrogen supply pipe 6 is injected near the reactant supply nozzle 2a. It is combined with the reaction mixture to be supplied into the reaction chamber (5) through the reaction mixture diffusion (2b).

However, since hydrogen gas is an expensive raw material, there is a problem in that the production cost increases due to supplemental injection of excess hydrogen gas and thus the economical efficiency is lowered.

On the other hand, the counterunggi according to an embodiment of the present invention, by recirculating the hydrogen gas that does not participate in the reaction back into the reaction system to solve the above problems and achieved the effect of significantly increasing the efficiency of the hydrogenation reaction. 2 is a diagram illustrating a structure of a hydrogenation reaction reactor according to an embodiment of the present invention.

Referring to FIG. 2, the hydrogenation reaction machine 100 according to an embodiment of the present invention includes a reaction product injection part 10, a reaction product supply part 30, a reaction product discharge part 40, a reaction product chamber 50, And a hydrogen supply pipe 60 and a first hydrogen circulation pipe 90. The half water supply 30 is located in connection with the half water injection 10, and the half water supply 30 is also located at the top of the reaction chamber 50 and communicates with the half water injection 10. A supply nozzle 20a and a semi-coagulant diffuser 20b, which is located inside the reaction chamber 50 and diffuses the reaction product supplied from the reaction product supply nozzle 20a, into the reaction chamber 50.

In the hydrogenation reaction vessel 100 according to an embodiment of the present invention, one end of the first hydrogen circulation pipe 90 is connected to the upper portion of the reaction chamber 50, and the other end is supplied with hydrogen. It is connected to the interruption of the pipe 60 in the form of a T and serves to circulate the hydrogen gas flowing in the upper region 70 of the reaction chamber 50 to the semi-water supply portion 30.

More specifically, first, the reaction mixture (banung mixture) including hydrogen, a reaction object to be hydrogenated, and a solvent is supplied from the reaction product injection unit 10 through the reaction product supply nozzle 20a to form the reaction chamber 50. Sprayed into it at a constant speed. The injected reaction mixture is diffused into the space in the reaction chamber 50 through the reaction mixture diffusion portion 20b, and the reaction object to be hydrogenated in the presence of a catalyst present in the reaction chamber 50 reacts with the hydrogen to react with the hydrogenation reaction. Will perform.

The present invention is not limited thereto, but the semi-coupling diffuser 20b has a tubular shape extending in the longitudinal direction of the counter-coupling chamber 50 for more effective diffusion of the counter-coupling, wherein the diameter of the middle portion of the tube It may have the narrowest, funnel shape with diameters that extend toward the top and bottom. The diameter of the reagent supply nozzle (20a) can be changed by the performance of the target output and the pump is not particularly limited, in one embodiment of the present _invention: it can be from about 20 to about 1000mm, banung water supply nozzle (20a) Depending on the diameter of the semi-ungmul diffusion 20b may also vary.

For example, according to one embodiment of the present invention, the length of the semi-acre water diffusion part 20b may be about 20 to about 50 times, preferably about 30 to about 40 times the diameter of the semi-acre water supply nozzle 20a. . In addition, the diameter of the middle portion of the narrowest portion in the semi-acre water diffusion part 20b may be about 1 to about 4 times, preferably about 1.2 to about 2 times the diameter of the semi-water supply nozzle 20a, and the reactant diffuser 20b The diameter of the widest bottom portion of N) may be about 1 to about 10 times, preferably about 4 to about 8 times the diameter of the reactant feed nozzle 20a. When the length and diameter of the reactant diffusion part 20b have the above ranges, the reaction product can be more effectively diffused into the reaction chamber to increase the efficiency of the hydrogenation reaction reaction.

The hydrogen supply pipe 60 is connected with the reactant supply unit 30 at a position near the semi-flood supply nozzle 20a, so that the hydrogen gas intermittently supplied from the hydrogen supply pipe 60 is the semi-flounder supply nozzle 20a. It is combined with the reaction mixture injected in the vicinity and supplied into the reaction chamber 50 through the reaction mixture diffusion part 20b. On the other hand, due to the solubility characteristics of hydrogen gas, hydrogen, reaction to be hydrogenated There is a hydrogen gas that flows in the upper region 70 of the reaction chamber 50 without dissolving in the reaction system 80 in which the object and the solvent are present together.

According to the hydrogenation reaction reactor 100 of the present invention shown in FIG. 2, the hydrogen gas leaving the reaction system 80 is sucked through the first hydrogen circulation pipe 90 due to the pressure difference, and thus the hydrogen supply pipe 60 is removed. ) Is moved around the reactant supply nozzle 20a of the reaction product supply part 30, and the hydrogen gas stream 90a is combined with the reaction product sprayed at a constant rate from the reaction product supply nozzle 20a and reacts again. 50 is fed into. Therefore, the gas holdup of the hydrogen gas participating in the reaction in the reaction system 80 can be increased to achieve a high hydrogenation reaction reaction rate.

In addition, the hydrogenation reaction reactor 100 of the present invention also includes a hydrogen supply pipe 60 for replenishing hydrogen gas, as in the conventional hydrogenation reactor, but inside the reaction system 80 by the first hydrogen circulation pipe 90 Since there is a flow rate of the hydrogen gas recycled to the reactor, the amount of hydrogen gas replenished as compared with the conventional hydrogenation reactor may be significantly reduced, or a complement layer of hydrogen gas may not be required. For example, the amount of hydrogen gas replenished through the hydrogen supply piping 60 is reduced by about 1/25 to about 1/45 times under the same operating conditions as compared to not including the first hydrogen circulation piping 90. Can be.

In addition, even if the first hydrogen circulation pipe (90) is included, the degree of pressure drop at the semi-aeration water supply nozzle (20a) is not significantly different from when the first hydrogen circulation pipe (90) is not included. It is not necessary to increase the performance of the pump to compensate the furnace pressure drop, and it is economically advantageous because the reaction efficiency of the reaction can be maintained.

According to one embodiment of the present invention, the diameters of the hydrogen supply pipe 60 and the first hydrogen circulation pipe 90 may each independently be the same or different, and each of about 0.5 to about about the diameter of the semi-atom water supply nozzle 20a. It may be three times, preferably about 0.5 to about 1.5 times, but the present invention is not limited thereto.

Referring to Figure 3, the hydrogenation reactor 200 according to an embodiment of the present invention Reactant inlet 10, reaction product supply 30, reaction product outlet 40, reaction chamber 50, hydrogen supply piping 60, first hydrogen circulation piping 90 and second hydrogen circulation piping ( 95). The reactant feeder 30 is located in connection with the reactant inlet 10, and the reactant feeder 30 is also located at the top of the reactant inlet chamber 50 and in communication with the reactant feeder 10. 20a and a reactant diffuser 20b positioned inside the reaction chamber 50 and diffusing the reaction product supplied from the reaction product supply nozzle 20a into the reaction chamber 50.

Exemplary shapes and diameter ranges of the semi-aerated water supply nozzle 20a, the semi-aerated water supply nozzle 20a, and the semi-aerated water diffusion part 20b are the same as those described with reference to FIG.

In addition, similarly to the hydrogenation reactor shown in FIG. 2, the hydrogen supply pipe 60 is connected to the semi-flop water supply part 30 at a position near the half-water supply nozzle 20a, and thus intermittently from the hydrogen supply pipe 60. The hydrogen gas supplied thereto is combined with the reaction mixture injected in the vicinity of the reaction product supply nozzle 20a and supplied into the reaction chamber 50 through the reaction product diffusion portion 20b.

In the hydrogenation reaction vessel 200 according to an embodiment of the present invention, one end of the first hydrogen circulation pipe 90 is connected to the upper portion of the reaction chamber 50, and the other end is connected to the stop of the hydrogen supply pipe 60. The hydrogen gas flowing in the upper region 70 of the reaction chamber 50 in the form of a ruler is circulated to the reaction product supply section 30. In addition, one end of the second hydrogen circulation pipe 95 is connected to the upper portion of the reaction chamber 50, and the other end thereof is connected to an interruption of the reactant supply unit 30, in particular, in the vicinity of where the reactant supply nozzle 20a is located. It serves to circulate hydrogen gas flowing in the upper region 70 of the 50 to the semi-furnace supply 30 additionally.

In more detail, first, a reaction mixture including hydrogen, a reaction object to be hydrogenated, and a solvent is supplied from the reaction product injection unit 10 to the reaction chamber 50 through the reaction product supply nozzle 20a. Sprayed. The injected semicoal water is diffused into the space in the reaction chamber 50 through the semicoalm diffusion portion 20b to perform a hydrogenation reaction.

At this time, due to the solubility characteristics of the hydrogen gas, hydrogen, reaction target to be hydrogenated, and the solvent are not dissolved in the reaction system 80, which is present together. There is hydrogen gas flowing in the upper region 70 of the chamber 50.

According to the hydrogenation reaction reactor 200 of the present invention, the hydrogen gas leaving the reaction system 80 is thus sucked by the first hydrogen circulation pipe 90 due to the pressure difference and reactant supply portion through the hydrogen supply pipe 60. It is moved around the semi-flop water supply nozzle 20a of the 30, and the hydrogen gas is also sucked in through the second hydrogen circulation pipe 95, and around the semi-flop water supply nozzle 20a of the half-frozen water supply part 30. Will be moved to. The hydrogen gas stream 90a thus formed is combined with the semicoagulum injected at a constant rate from the semicoagulant supply nozzle 20a and fed back into the reaction chamber 50. Accordingly, the flow rate of the hydrogen gas stream 90a and the gas holdup of the hydrogen gas participating in the reaction in the reaction system 80 can be increased significantly to achieve a high hydrogenation reaction rate.

According to an embodiment of the present invention, when the hydrogenation reaction reactor 200 further includes one second hydrogen circulation pipe 95 in addition to the first hydrogen circulation pipe 90, the hydrogen supply pipe 60 may be used. The amount of complementary hydrogen gas may be significantly reduced compared to the case where neither the first hydrogen circulation pipe 90 nor the second hydrogen circulation pipe 95 is included, or no supplement of hydrogen gas may be required. For example, the amount of hydrogen gas that is complemented through the hydrogen supply pipe 60 is about 1 / at the same operating conditions as compared to the case where both the first hydrogen circulation pipe 90 and the second hydrogen circulation pipe 95 are not included. It may be reduced by 60 to about 1/80 times, and may be reduced by about 1 / 1.5 to about 1/10 times under the same operating conditions as compared to including only the first hydrogen circulation pipe 90.

Further, even if the first and second hydrogen circulation pipes 90 and 95 are included, the degree of pressure drop at the semi-aeration water supply nozzle 20a may be such that the first and second hydrogen circulation pipes 90. 95 are reduced. There is no significant difference from not including it, so it is not necessary to increase the performance of the pump to further compensate for the pressure drop, and it is economically advantageous as the reaction efficiency of the reaction can be maintained.

According to one embodiment of the invention, the second hydrogen circulation pipe 95 may be provided with one or more. In addition, the first hydrogen circulation pipe 90 and one or more second hydrogen circulation pipe 95 may be provided at equal intervals with respect to the circumference of the reaction chamber. In addition, according to an embodiment of the present invention, the diameters of the hydrogen supply pipe 60, the first hydrogen circulation pipe 90, and the second hydrogen circulation pipe 95 may be the same or different from each other independently. The water supply nozzle 20a may be about 0.5 to about 3 times the diameter, and preferably about 0.5 to about 1.5 times, but the present invention is not limited thereto.

4 is a view showing a view from above of the hydrogenation reaction reactor of the present invention to show the arrangement of the first hydrogen circulation pipe and the second hydrogen circulation pipe.

FIG. 4A is a diagram when the first hydrogen circulation pipe and one second hydrogen circulation pipe are included, and FIG. 4B includes the first hydrogen circulation pipe and two second hydrogen circulation pipes. FIG. 4C is a diagram when the first hydrogen circulation pipe and three second hydrogen circulation pipes are included. FIG. In FIGS. 4A to 4C, since the first hydrogen circulation pipe 90 is connected to the interruption of the hydrogen supply pipe 60 and is not visible from the top of the reactor, the connection position is indicated by a dotted line.

Referring to FIG. 4A, when the hydrogenation reaction reactor of the present invention includes one first hydrogen circulation pipe 90 and one second hydrogen circulation pipe 95, the first hydrogen circulation pipe 90 is provided. And the second hydrogen circulation pipe 95 are arranged at equal intervals with respect to the circumference of the reaction chamber 50. That is, the angles Ql and Q2 between the first hydrogen circulation pipe 90 and the second hydrogen circulation pipe 95 may be arranged at substantially equal intervals such that Q1 Q2 is 180 degrees.

Referring to FIG. 4B, when the hydrogenation reaction reactor of the present invention includes one first hydrogen circulation pipe 90 and two second hydrogen circulation pipes 95, the first hydrogen circulation pipe 90 is provided. And two second hydrogen circulation pipes 95 are arranged at equal intervals with respect to the circumference of the reaction chamber 50. That is, the angles (Q3, Q5) between the first hydrogen circulation pipe 90 and the adjacent second hydrogen circulation pipe 95, and the angle formed by the two second hydrogen circulation pipes 95 adjacent to each other ( Q4) may be arranged at substantially equal intervals to be Q3-Q4-Q5-120 degrees.

Referring to FIG. 5C, when the hydrogenation reactor of the present invention includes one first hydrogen circulation pipe 90 and three second hydrogen circulation pipes 95, the first The hydrogen circulation pipe 90 and three second hydrogen circulation pipes 95 are arranged at equal intervals with respect to the circumference of the reaction chamber 50. That is, angles Q6 and Q9 between the first hydrogen circulation pipe 90 and the adjacent second hydrogen circulation pipe 95 and the angles Q7 formed by the second hydrogen circulation pipe 95 adjacent to each other are formed. Q8) may be arranged at substantially equal intervals such that Q6-Q7-Q8-Q9 is 90 degrees.

On the other hand, (A) to (C) of Figure ⁴ is the second Although shown as including one to three of the hydrogen circulation pipe ^(95), not necessarily the invention is not limited to, various numbers, as needed And a second hydrogen circulation pipe in the form.

As exemplarily shown in FIGS. 3 and 4, when the hydrogenation reaction reactor according to an embodiment of the present invention further includes a second hydrogen circulation pipe, it is compared with the case where only the first hydrogen circulation pipe is included. Improved asymmetrical flow due to the hydrogen gas flow in the upper region of the chamber being supplied in only one direction, allowing the mixed flow of hydrogen and reactant to be maintained well in the counter-fuel diffusion to increase reaction efficiency There is this.

That is, when the hydrogen gas is recycled to the reaction product supply only by the first hydrogen circulation pipe, the flow rate of the hydrogen gas recycled into the reaction chamber increases, but the vicinity of the upper region of the reaction chamber where the first hydrogen circulation pipe is located. Since the hydrogen gas flow occurs only in a portion of the region, the hydrogen gas flow is unbalanced. This unbalanced flow of hydrogen gas leads to poor flow in the reactant diffusion. Accordingly, the efficiency improvement effect of the hydrogenation reaction may be reduced, or the operating life of the half-unggi due to the asymmetrical flow during the long-time half-unggi operation may be shortened.

This disadvantage may be ameliorated by recycling hydrogen gas to the semi-water feed by the first hydrogen circulation pipe and the second hydrogen circulation pipe according to another embodiment of the present invention. That is, by circulating the hydrogen gas in addition to the first hydrogen circulation pipe by one or more second hydrogen circulation pipes, the imbalance of the hydrogen gas is eliminated and the problem caused by this is prevented, and the flow rate of the hydrogen gas is also increased so that the second hydrogen The efficiency of the hydrogenation reaction can be further increased compared to the case without the circulation pipe. At this time, such hydrogen gas In order to maximize the effect of reducing the imbalance of the flow and improving the efficiency of the hydrogenation reaction, the first hydrogen circulation pipe and the at least one second hydrogen circulation pipe are equally spaced from each other with respect to the circumference of the reaction chamber as illustrated in FIG. 4. It is preferable to arrange.

On the other hand, when the hydrogenation reaction of the DCPD resin is carried out using the hydrogenation reaction of the present invention, the temperature in the reaction chamber is about 90 to about 300 ^° C, preferably about 120 to about 300 ^° C, the pressure is about 5 to About 120 barg, preferably about 50 to about 100 barg.

In addition, according to one embodiment of the present invention, the reaction mixture supplied into the reaction chamber may be a mixed mixture such that the volume ratio of hydrogen gas (¾) is about 10 to about 50 vol% with respect to the total volume of the reaction mixture. Can be.

In addition, according to one embodiment of the present invention, the semi-coupling water injected from the semi-coupling water supply nozzle may be injected into the reaction chamber at a speed of about 30 to about 70 m / sec.

In addition, according to one embodiment of the invention, the hydrogen gas flowing in the upper region of the reaction chamber, the velocity of about 5 to about 20 m / sec through the first hydrogen circulation pipe and optionally included second hydrogen circulation pipe May be sucked into the reaction stream and supplied to the semi-fung supply. As such, the hydrogen gas stream sucked into the reactant supply unit may be combined with the reactant sprayed at a constant rate from the reactant supply nozzle and supplied back into the reaction chamber to be recycled.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are intended to help a concrete understanding of the present invention, but the scope of the present invention is not limited to Examples or Comparative Examples. <Example>

Example 1

As shown in FIG. 2, one end is connected to the upper part of the reaction chamber 50, and the other end includes a first hydrogen circulation pipe 90 which is connected in a T-shape to the interruption of the hydrogen supply pipe 60. The reaction chamber was designed to have a height of 10 m and a maximum diameter of 3 m. The diaphragm supply nozzle 20a had a diameter of 0.2m and the total length of the semicoultice diffuser 20b was 6m, and the diameter of the widest lower portion of the semiconductor diffused portion 20b was 0.96m, and the hydrogen supply pipe (60). ) Was 0.15 m in diameter and the diameter (inner diameter) of the first hydrogen circulation pipe 90 was 0.1 ⁵ m.

In addition, the silver content of the reaction chamber 50 during the hydrogenation reaction is

At 270 ^° C., the pressure was kept at 90 barg.

A reaction mixture containing a volume ratio of hydrogen gas (¾) and a DCPD resin from the reactant injector 10 at a weight ratio of 3: 7 and 100 parts by weight of cyclohaxane as a solvent based on 100 parts by weight of the DCPD resin was added. The feed nozzle 20a was injected into the reaction chamber 50 at a rate of 10 m / sec. Hydrogen gas flowing in the upper region of the reaction chamber 50 is sucked through the first hydrogen circulation pipe 90 at a rate of about 5 m / sec at an average speed and then injected through the reaction product supply nozzle 20a. The mixture was recycled into the reaction chamber 50 together. Example 2

As shown in FIG. 3, one end is connected to the upper part of the reaction chamber 50, and the other end is connected to the first hydrogen circulation pipe 90 so as to be connected in a T-shape to the interruption of the hydrogen supply pipe 60. 1st hydrogen circulating pipe which is connected to the upper part of reaction chamber 50 at the angle which forms 180 degree angle with 1 hydrogen circulation pipe 90, and the other end is connected to the reactant supply nozzle 20a of the reactant supply part 30 And a hydrogenation reaction reactor having a height of 10 m and a maximum diameter of 3 m. The reactant supply nozzle 20a had a diameter of 0.2m, the total length of the semicoultane diffuser 20b was 6m, and the diameter of the widest lower portion of the semiconducted diffuser 20b was 0.96m, and the hydrogen supply pipe 60 was used. The diameter (inner diameter) was 0.15 m, and the diameter (inner diameter) of the crab 1 hydrogen circulation pipe 90 and the second hydrogen circulation pipe 95 was 0.15 m.

The hydrogen gas flowing in the upper region of the reaction chamber 50 has an average speed of about 5 ra / sec through the first hydrogen circulation pipe 90, and an average speed of about 5 through the second hydrogen circulation pipe 95. Sucked up at a rate of m / sec and recycled into the reaction chamber 50 together with the reaction mixture sprayed through the reaction product supply nozzle 20a. The remainder was subjected to the hydrogenation reaction of DCPD resin under the same conditions as in Example 1. Comparative Example 1

As shown in FIG. 1, a hydrogenation reaction machine was designed in which the required hydrogen was supplied through the hydrogen supply pipe 6 without the hydrogen circulation pipe. The conditions and reaction conditions of the remaining hydrogenation reaction was performed in the same manner as in Example 1 to carry out hydrogenation reaction of the DCPD resin.

As the hydrogenation reaction proceeded, the hydrogenation reaction was carried out while continuously supplying hydrogen gas through the hydrogen supply pipe 6 at an average speed of about 0.1 to about 0.5 m / sec. For Examples 1 and 2, Comparative Example 1, the pressure drop degree of the reaction vessel, hydrogen flow rate and fluidity through the first and second hydrogen circulation pipe were evaluated and shown in Table 1 below.

TABLE 1

Half-Wheel of Hydrogen Hydrogen Supply Refuse

Pressure drop through the flow-flow piping

(Unit: kg / sec) Hydrogen flow rate in the complemented (unit: bar) region Hydrogen

(Unit: fluidity kg / sec) Aspect Example 1 First hydrogen circulation o_

νλ = ι 5.1489 Asymmetric piping: 0.348

Example 2 5.4025 Symmetric to the first hydrogen cycle

Tubing: 0.374

2nd hydrogen cycle

Tubing: 0.381

Total: 0.755

Comparative Example 1 ΒΛ ㅁ 0.01 5 Asymmetric As shown in Table 1, the implementation II 1 and 2 has a hydrogen flow recycled in the first and / or the second hydrogen circulation pipe, the high yield of the hydrogenation reaction of the DCPD resin without the supplementary layer of hydrogen through the hydrogen supply pipe And the pressure drop was similar to that without the hydrogen circulation pipe.

[Explanation of code]

1, 10: semi-aerated water injection part

2a, 20a: semi-aerated water supply nozzle

2b, 20b: half-dung diffusion

2, 20: reaction product outlet

3, 30: reactant supply unit

4, 40: reaction product outlet

5, 50: reaction chamber

6, 60: hydrogen supply piping

7, 70: upper region of the reaction chamber

8, 80: reaction system

90: first hydrogen circulation piping

95: second hydrogen circulation piping

9, 100, 200: Hydrogenation reaction machine

Claims

[Patent Claims]

[Claim 11

A reaction chamber in which the hydrogenation reaction takes place;

A semi-ungmul injecting unit for injecting a reaction product including hydrogen, a reaction target to be hydrogenated, and a solvent;

A reaction product discharge part positioned below the reaction chamber and discharging a hydrogenation reaction product to the outside of the reaction chamber;

A hydrogen supply pipe which is connected to the half water supply part and additionally supplies hydrogen to the half water additive through the half water supply part; And

A first hydrogen circulation pipe having one end connected to an upper portion of the reaction chamber and the other end connected to an interruption of the hydrogen supply pipe to circulate hydrogen gas flowing in an upper region of the reaction chamber to the reactant supply unit;

Hydrogenation reactor comprising a.

[Claim 2]

The hydrogenation reaction vessel of claim 1, wherein the first hydrogen circulation pipe is connected in a T-shape to the interruption of the hydrogen supply pipe.

[Claim 3]

The hydrogenation reactor of claim 1, further comprising a second hydrogen circulation pipe connected at one end to an upper portion of the reaction chamber and connected at the other end to the semi-manufacture supply.

[Claim 4]

The hydrogenation reaction machine of Claim 3 containing one or more said 2nd hydrogen circulation piping.

[Claim 5] The hydrogenation reaction vessel according to claim 3 or 4, wherein the first and second hydrogen circulation pipes are provided at equal intervals with respect to the circumference of the reaction chamber.

[Claim 6]

According to claim 1, wherein the semi-fung water supply unit Semi-fung water supply nozzle is sprayed the semi-ungmul water; And a semi-coagulant diffusion unit for diffusing the semi-coagulant injected through the reactant supply nozzle into the reaction ram.

[Claim 7]

The method according to claim 6, wherein the semi-coagulant diffuser has a tube shape extending in the longitudinal direction of the reaction chamber, the diameter of the middle portion of the tube is the narrowest, the diameter of the funnel is widened toward the upper portion and the lower portion, Hydrogenation reaction.

[Claim 8]

The method of claim 7, wherein the length of the semi-coupling diffuser is 20 to 50 times the diameter of the semi-coupling supply nozzle, the diameter of the narrowest portion is 1 to 4 times the diameter of the semi-coupling supply nozzle, and the diameter of the widest portion is A hydrogenation reaction machine, which is 1 to 10 times the diameter of the reaction water supply nozzle.

[Claim 9]

The hydrogenation reaction machine according to claim 3 or 4, wherein the diameters of the first and second hydrogen circulation pipes are each independently the same or different, and are 0.5 to 3 times the diameter of the semi-fung water supply nozzle.

[Claim 10]

The hydrogenation reaction reactor of Claim 1, wherein the reaction object to be hydrogenated is a dicyclopentadiene (DCPD) resin.