Bubble column reactor and apparatus for producing oligomers comprising same

Abstract

The present invention provides a bubble column reactor and an apparatus for producing oligomers comprising same, the bubble column reactor comprising: a liquid region in which reactions occur and a gas region located above the liquid region; a partition that divides the liquid region longitudinally into first and second areas; a liquid-level measurement device, connected to the second area of the liquid region, for measuring the level of the liquid in the second area; and a downstream pipe, provided on the side of the second area in the liquid region, for discharging the liquid stream, wherein the partition is provided in the liquid region so as for one end thereof to be positioned at the boundary between the liquid and gas regions so that the overflow liquid stream from the first area that flows over the partition is stored in the second area.

Description

Bubble column reactor and oligomer production device including the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0188410, filed December 21, 2023, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to a bubble column reactor and an oligomer production device including the same, and more particularly, to a bubble column reactor and an oligomer production device including the same, which can prevent pipe clogging by minimizing bubble entrainment in a liquid stream including a reaction product.

[0005] Alpha-olefins are widely used commercially as important substances used as comonomers, detergents, lubricants, and plasticizers. In particular, 1-hexene and 1-octene are widely used as comonomers to control the density of linear low-density polyethylene (LLDPE) during the production of polyethylene.

[0006] These alpha olefins can be produced by performing an oligomerization reaction in a state where ethylene is dissolved in a solvent in the presence of a catalyst, and the oligomerization reaction can be performed, for example, in a bubble column reactor.

[0007] The above bubble column reactor is installed at the bottom thereof and a distribution device (e.g., a sparger, a multi-tube, a spray nozzle, etc.) that forms a large number of bubbles is introduced into a liquid region containing a solvent, a catalyst, etc., and the raw material gas is dispersed while rising in the form of bubbles, and the dispersed gas is mixed within the liquid region while generating turbulence, thereby performing an oligomerization reaction.

[0008] At this time, the liquid level within the reactor must be maintained constant because it affects the control of reaction conditions such as pressure and temperature, the catalyst residence time, and the resulting ethylene conversion and calorific value. To this end, it is very important to indicate the liquid level within the reactor.

[0009] In the liquid region where the oligomerization reaction takes place in the above reactor, the composition of the liquid phase changes as the solvent, ethylene dissolved in the solvent, and the liquid substance (oligomer) generated by conversion from the ethylene coexist, so the density of the liquid phase after the reaction changes compared to the liquid phase before the reaction. In particular, the density within the entire liquid volume can be significantly reduced depending on the amount of gas bubbles (gas hole up) accompanying the liquid phase. In this way, the density is affected by the characteristics (temperature, pressure, composition, viscosity, etc.) of the liquid substance within the reactor.

[0010] In order to measure the liquid level within the reactor during the production of such oligomers, a differential pressure type level transmitter (LT) is typically used. However, depending on the degree of reaction, the density of the liquid phase may change, resulting in an incorrect liquid level indication. If the liquid level indication by the differential pressure type LT is significant, it is difficult to maintain a constant liquid level within the actual reactor.

[0011] In addition, if a large amount of bubbles are included in the liquid substance produced by the above oligomerization reaction and are transferred to the liquid discharge pipe connected to the lower part of the reactor, a serious blockage phenomenon may occur due to an increase in the two-phase in the pipe.

[0012] The present invention is intended to solve the problems mentioned in the background technology of the above invention, and aims to provide a bubble column reactor capable of preventing pipe clogging by minimizing bubble entrainment in a liquid stream containing a reaction product.

[0013] A bubble column reactor is provided, comprising: a partition wall dividing the liquid phase into first and second zones in a longitudinal direction; a liquid level gauge connected to the second zone of the liquid phase zone for measuring the liquid level of the second zone; and a downstream pipe provided on the side of the second zone in the liquid phase zone for discharging a liquid stream, wherein the partition wall is provided within the liquid phase zone such that one end thereof is positioned at the boundary between the liquid phase zone and the vapor phase zone, so that the liquid stream of the first zone overflowing above the partition wall is stored in the second zone.

[0014] Additionally, according to the present invention, an oligomer production device including the bubble column reactor is provided.

[0015] The bubble column reactor according to the present invention is provided with a partition wall portion that divides the lower liquid region where the reaction takes place into first and second zones, and has a height located at the boundary between the gas phase region and the liquid phase region, so that the liquid stream of the first zone, which is higher than the boundary height, can be stored in the second zone, and since the liquid stream stored in the second zone has bubbles removed by the partition wall portion, density changes can be minimized. Thereafter, by measuring the height of the liquid phase in the second zone of the liquid region where gas-liquid separation has occurred and controlling the discharge amount of the liquid stream, the liquid level of the reactor can be ultimately maintained stably.

[0016] In addition, the liquid stream discharged from the second zone of the above liquid region has a suppressed amount of bubbles, which can facilitate the flow of oligomer products in the liquid discharge pipe, prevent clogging, and reduce ethylene gas emission to the downstream stream.

[0017] Figure 1 illustrates a bubble column reactor according to one embodiment of the present invention.

[0018] Figures 2 and 3 illustrate the bubble column reactor used in the comparative example.

[0019] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0020] As used herein, the terms “include” or “contain” specify a particular characteristic, area, integer, step, operation, element, or component, but do not exclude the addition of other particular characteristics, areas, integers, steps, operations, elements, or components.

[0021] The term "stream" as used herein may refer to the flow of fluid within a process, or may refer to the fluid itself flowing within a pipe. Specifically, the stream may refer to both the fluid itself flowing within the pipe connecting each device and the flow of the fluid. Furthermore, the fluid may include one or more components of gas, liquid, and solid.

[0022] The term "upper" as used herein, unless otherwise specified, means a point 0 to 50% in height downward from the top of the device, and may specifically mean the top (top). In addition, the term "lower" means a point 50 to 100% in height downward from the top of the device, and may specifically mean the bottom (bottom).

[0023] Additionally, the “pressure” referred to herein means gauge pressure measured relative to atmospheric pressure.

[0024]

[0025] Hereinafter, the present invention will be described in detail with reference to the attached drawings.

[0026] One embodiment of the present invention relates to a bubble column reactor for performing an oligomerization reaction or the like.

[0027] Referring to FIG. 1, a bubble column reactor (100) according to the present invention includes an upper gas phase region (110) and a lower liquid phase region (120) where a reaction takes place, and the liquid phase region (120) is divided into a first zone (D1) and a second zone (D2) in the longitudinal direction by a partition wall (130), and a liquid level gauge (20) and a downstream pipe (30) for discharging a liquid stream can be connected to the second zone (D2).

[0028] The above bubble column reactor (100) receives ethylene gas and a solvent from a liquid region (120), specifically, a first zone (D1), and performs an oligomerization reaction. For example, ethylene gas is supplied from a gas inlet pipe (122) to a liquid region (120) where the solvent is supplied together with a catalyst through a solvent inlet pipe (121), and the ethylene gas rises in the form of bubbles through a distribution device (e.g., a sparger, a multi-tube, a spray nozzle, etc.) installed at the bottom of the liquid region (120) to form a large number of bubbles, and is dispersed to generate turbulence and mixed within the liquid region, so that an oligomerization reaction can be performed.

[0029] The above oligomerization reaction may refer to a reaction in which monomers are oligomerized. Depending on the number of monomers polymerized, it is called trimerization or tetramerization, and these are collectively called multimerization. For example, alpha olefins such as 1-hexene and 1-octene can be produced through trimerization or tetramerization of ethylene.

[0030] The ethylene gas supplied to the bubble column reactor may be a stream containing ethylene (C2) separated from naphtha pyrolysis.

[0031] The solvent for dissolving the above ethylene gas may include at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, octane, cyclooctane, decane, dodecane, benzene, xylene, 1,3,5-trimethylbenzene, toluene, ethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene. In some cases, two types of the above solvents may be mixed and used. Through this, the ethylene gas can be liquefied at a higher temperature, and the dissolution rate of the ethylene gas in the solvent can be improved.

[0032] In the above ethylene oligomerization reaction, a compound containing a transition metal may be used as a catalyst to promote reaction activity. For example, the catalyst may be a compound containing at least one selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) tris(2,2,6,6-tetramethyl-3,5-heptaneindionate), chromium (III) benzoylacetonate, chromium (III) hexafluoro-2,4-pentaneindionate, chromium (III) acetate hydroxide, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, and chromium (III) stearate.

[0033] In addition, a cocatalyst may be additionally used to increase the activity of the catalyst, and for example, the cocatalyst may include at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, modified methylaluminoxane, and borate.

[0034] The above oligomerization reaction can be operated under conditions commonly applied in the field, for example, at a temperature of 30°C to 150°C or 50°C to 120°C and a pressure of 20 bar to 65 bar or 20 bar to 40 bar.

[0035] When this oligomerization reaction is performed, a liquid stream containing ethylene polymerized oligomer products, by-products, solvent, unreacted gas dissolved in the solvent, etc. exists in the lower liquid region (120) of the bubble column reactor (100), and unreacted ethylene gas that is not dissolved in the solvent and thus does not participate in the oligomerization reaction can rise to the upper gaseous region (110).

[0036] The liquid stream present in the liquid region (120) of the bubble column reactor may have a density that varies depending on the amount of liquid oligomer product generated by conversion from ethylene and the amount of bubbles derived from unreacted gas dissolved in the solvent. If an error occurs in the liquid level measurement due to such density change, it may be difficult to maintain the liquid level in the reactor stably.

[0037] To overcome these problems, in the present invention, a baffle (130) that acts as a weir is installed vertically in the longitudinal direction within the liquid region (120) of the bubble column reactor, and the liquid level after gas-liquid separation is measured in the space where the liquid stream passing over the baffle is stored.

[0038] Specifically, the partition wall (130) may be provided so that one end is positioned at the boundary between the liquid region (120) and the gas region (110) while dividing the liquid region (120) into a first zone (D1) and a second zone (D2) in the longitudinal direction, and there is no particular limitation as long as it has a shape that can confine a liquid stream within the liquid region (120).

[0039] For example, as shown in FIG. 1, the partition wall (130) can confine a liquid stream in a form having a vertical wall in the longitudinal direction and a horizontal plate extending transversely from the lower end of the vertical wall and contacting the side surface of the second liquid region, and the horizontal plate can be adjacent to or spaced apart from the lowest surface of the liquid region (120).

[0040] As another example, the partition wall (130) can confine the liquid stream in the form of a vertical wall extending upward from the lowest surface of the liquid region (120). In this case, in the liquid region (120) divided by the partition wall (130), the lower part of the first zone (D1) can be configured to open a distribution device (e.g., a sparger having multiple holes, a multi-tube, a spray nozzle, etc.) to disperse ethylene gas supplied from a gas inlet pipe (122) into the first zone (D1), while the lower part of the second zone (D2) can be blocked to prevent ethylene gas from passing through.

[0041] As another example, the baffle member (130) can be configured in the form of a vertical tube with a donut-shaped rim and a closed bottom to confine a liquid stream, and the donut-shaped baffle member can be provided at various locations, such as the center or edge of the liquid region (120).

[0042] Meanwhile, the first zone (D1) and the second zone (D2) of the liquid region divided by the partition wall (130) may have an area ratio of 100:1 to 5:1. If the area ratio is out of the above range, that is, if the area of ​​the second zone (D1) is less than 1% of the area of ​​the first zone (D1), the space for controlling the height of the liquid phase is insufficient, so that the residence time of the liquid phase within the second zone (D2) decreases, making it difficult to accurately control the liquid level. In addition, if the area of ​​the second zone (D1) exceeds 20% of the area of ​​the first zone (D1), the residence time of the liquid phase in the second zone (D2) excessively increases, causing additional side reactions to occur, and the size of the entire reactor must be increased, so that the equipment cost may increase.

[0043] Through this structure, while an oligomerization reaction is taking place in the liquid region (120) of the bubble column reactor, the liquid stream of the first zone (D1) that is higher than the boundary height between the gas phase region (110) and the liquid phase region (120) can overflow to the upper portion of the partition wall (130) and be stored in the second zone (D2). That is, due to the difference in boiling points between the liquid and gas phases at the boundary between the liquid and gas phases, ethylene gas passes through the first zone (D1) of the liquid phase region (120) in the form of bubbles, then passes through the gas phase region (110) and is discharged through the upper pipe (111), while the liquid phase is transferred to the second zone (D2) through the partition wall (130). Bubble entrainment can be suppressed in the liquid phase stored in the second zone (D2).

[0044] In this way, the liquid stream stored in the second zone (D2) of the liquid region has bubbles removed by the partition wall (130) and gas-liquid separation has been achieved, so there is no need to install a separate gas-liquid separator outside the reactor.

[0045] In the existing technology, olefin is produced by oligomerization of ethylene in the liquid region of a bubble column reactor, and a liquid stream containing the olefin is withdrawn from the reactor and transferred to an external gas-liquid separator to separate unreacted gas. In this process, there was a problem that by-products such as polymers were precipitated due to a decrease in temperature depending on the residence time of the liquid phase, and to prevent this, an additional device was required to maintain the temperature of the gas-liquid separator. However, in the present invention, since gas-liquid separation is performed inside the bubble column reactor, precipitation of by-products due to a decrease in temperature can be prevented, and since no additional device is required, it is advantageous in terms of equipment cost and maintenance cost.

[0046] The gas-separated liquid stream in the second zone (D2) of the above liquid region (120) is measured by a liquid level gauge (20) connected to the second zone (D2).

[0047] The above liquid level gauge may be, but is not limited to, a differential pressure type level transmitter (LT) commonly used in the field.

[0048] The liquid stored in the second zone (D2) of the above liquid region (120) does not undergo significant changes in density because bubbles are removed and the liquid composition does not change. Therefore, unlike the first zone (D1) where changes in liquid composition occur, the possibility of an error occurring when measuring the liquid level within the second zone (D2) is low.

[0049] Accordingly, the height of the liquid phase with suppressed density change is measured using the liquid level gauge (20) connected to the second zone (D2), and the liquid level of the bubble column reactor can be stably maintained by discharging the liquid stream within the second zone (D2) according to the signal of the liquid level gauge (20).

[0050] The liquid stream in the second zone (D2) of the above liquid region (120) can be discharged through a downstream pipe (30) connected to the second zone (D2), and at this time, the discharge amount of the liquid stream can be controlled by controlling the opening and closing of a control valve (CV) provided in the downstream pipe (30) according to a signal from a liquid level gauge (20).

[0051] In addition, the liquid stream discharged from the second zone (D2) of the liquid region (120) can minimize the amount of bubbles, thereby facilitating the flow of oligomer products in the pipe and preventing clogging, and reducing the emission of ethylene gas to the downstream stream.

[0052] The present invention further provides an oligomer production device including the bubble column reactor.

[0053] The liquid stream discharged through the downstream pipe (30) from the above bubble column reactor can be supplied to a separation tower (not shown), and by further separating unreacted gas, solvent, etc. in the separation tower, a purified oligomer product can be obtained.

[0054] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present invention, and the scope of the present invention is not limited to these examples alone.

[0055]

[0056] Comparative Example 1:

[0057] As shown in Fig. 2, in a bubble column reactor including an upper gas phase region (110), a lower liquid phase region (120), a liquid level gauge (20), and a downstream pipe (30), an oligomerization reaction was performed by supplying a solvent and a catalyst to the lower liquid phase region (120) through a solvent inlet pipe (121) and supplying ethylene gas through a gas inlet pipe (122).

[0058] The height of the liquid stream containing the oligomer product obtained by the above reaction, the solvent, and the unreacted ethylene gas dissolved in the solvent was measured using a differential pressure type level transmitter (LT) as a liquid level gauge (20), and the liquid stream was discharged through a downstream pipe (30) of the reactor. At this time, the discharge amount of the liquid stream was controlled using a control valve (CV) according to the liquid level measurement value, thereby maintaining the liquid level in the reactor. Meanwhile, the gaseous stream containing the unreacted ethylene gas was discharged through the upper pipe (111) of the gaseous region (110).

[0059]

[0060] Comparative Example 2:

[0061] In a bubble column reactor including an upper gas phase region (110), a lower liquid phase region (120), and an overflow pipe (20) connected to the boundary position of the gas phase region and the liquid phase region as shown in Fig. 3, an oligomerization reaction was performed by supplying a solvent and a catalyst to the lower liquid phase region (120) through a solvent inlet pipe (121) and supplying ethylene gas through a gas inlet pipe (122).

[0062] The liquid stream containing the oligomer product obtained by the above reaction, the solvent, and the unreacted ethylene gas dissolved in the solvent was discharged through the overflow pipe (10) when it rose above the boundary position between the gas phase region (110) and the liquid phase region (120), thereby maintaining the liquid level in the reactor. Meanwhile, the gas phase stream containing the unreacted ethylene gas was discharged through the upper pipe (111) of the gas phase region (110).

[0063]

[0064] Example 1:

[0065] In a bubble column reactor including an upper gas phase region (110), a lower liquid phase region (120), a partition wall (130) having a height positioned at the boundary between the gas phase region and the liquid phase region to divide the liquid phase region (120) into a first zone (D1) and a second zone (D2), a liquid level gauge (20), and a downstream pipe (30), as shown in Fig. 1, an oligomerization reaction was performed by supplying a solvent and a catalyst to the first zone (D1) of the lower liquid phase region (120) through a solvent inlet pipe (121) and supplying ethylene gas through a gas inlet pipe (122).

[0066] During the above reaction, the liquid stream of the first zone (D1) that rose higher than the boundary height of the gas phase region (110) and the liquid phase region (120) overflowed to the upper part of the partition wall (130) and was stored in the second zone (D2). At this time, due to the difference in boiling points between the liquid and gas phases at the boundary between the liquid and gas phases, ethylene gas passed through the first zone (D1) of the liquid phase region (120) in the form of bubbles, then passed through the gas phase region (110) and was discharged through the upper pipe (111), while the liquid phase was transported to the second zone (D2) through the partition wall (130) in a state where bubbles were removed.

[0067] Thereafter, in the second zone (D2) of the liquid region (120), the liquid level of the bubble-removed, i.e., gas-separated liquid stream was measured using a differential pressure LT as a liquid level gauge (20) connected to the second zone, and the liquid stream was discharged through a downstream pipe (30) provided in the second zone (D2). At this time, the discharge amount of the liquid stream was controlled using a control valve (CV) provided in the liquid discharge pipe (30) according to the liquid level measurement value, thereby maintaining the liquid level in the reactor. Meanwhile, the gaseous stream including unreacted ethylene gas was discharged through the upper pipe (111) of the gaseous region (110).

[0068]

[0069] The results of liquid level measurement and liquid phase maintenance in the reactor according to the above examples and comparative examples are shown in Table 1 below.

[0070] Liquid leakage location Liquid level measurement target Liquid level maintenance result Comparison example 1 Downstream pipe Liquid level rise in entire reactor Liquid level area Comparison example 2 Overflow pipe - reactor liquid level maintenance / large amount of gas discharged through overflow pipe Example 1 Downstream pipe Liquid level maintenance in the second section (D2) of the liquid area divided by the partition wall of the reactor

[0071] As can be seen in Table 1 above, Example 1 is provided with a partition wall that divides a first zone (D1) where a reaction takes place in the lower liquid zone (120) and a second zone (D2) where a liquid stream from which bubbles have been removed is stored, with a height located at the boundary between the gas phase zone and the liquid phase zone, so that the liquid stream of the first zone, which is higher than the boundary height, is stored in the second zone while performing gas-liquid separation by the partition wall. As a result of measuring the height of the liquid phase, it was found that there was almost no change in density due to bubbles in the liquid phase of the second zone, so that the error of the differential pressure LT was minimized. Therefore, the amount of liquid discharge was controlled through a level control valve (CV) connected to the differential pressure LT, so that the liquid level of the reactor was ultimately maintained constant.

[0072] In addition, by minimizing the amount of bubbles in the liquid stream in the second zone (D2) of the liquid region (120), the flow of oligomer products in the downstream pipe was facilitated, thereby preventing clogging, and the content of ethylene gas to be recovered in the pipe was reduced.

[0073] In contrast, Comparative Example 1 directly measured the liquid phase with bubbles in the reactor (100), and thus, an error occurred in which the LT indication decreased at the same liquid level. This is because the ethylene gas supplied from the lower part of the reactor was incorporated into the liquid phase as bubbles as it passed through the liquid phase, and as compared to the liquid phase where only the solvent was present at the beginning of the reaction, the density of the liquid phase decreased as the oligomer product was included after the reaction progressed and the gas hold-up space increased, so that even if the liquid level existed at the same height, the differential pressure decreased, and the LT indication was displayed as a decrease in the liquid level. Due to this error, the control valve was closed to control the liquid level, and ultimately, the actual liquid level in the reactor increased. Due to this increase in the liquid level in the reactor, the catalyst residence time in the reactor increased, which limited the control of the amount of products and the calorific value, and a polymer-induced blockage occurred in the pipe through which the liquid stream was discharged, and the amount of ethylene to be recovered from the pipe increased.

[0074] Meanwhile, in Comparative Example 2, the liquid level of the reactor (100) was controlled by discharging a liquid phase that rose higher than the boundary height between the gas phase region and the liquid phase region containing bubbles through the overflow pipe (10) without separately measuring the liquid level of the reactor, and as a result, a large amount of gas stream including unreacted ethylene in the gas phase region was discharged together with the liquid phase stream through the overflow pipe (10). As a result, it was difficult to predict the ethylene content discharged through the overflow pipe, and a clogging phenomenon occurred due to an increase in the two-phase liquid-gas phase within the pipe.

[0075]

[0076] [Explanation of symbols]

[0077] 100: Bubble column reactor

[0078] 110: Weather zone

[0079] 111: Gas stream discharge pipe

[0080] 120: Liquid zone (D1: Zone 1, D2: Zone 2)

[0081] 121: Solvent inlet tube

[0082] 122: Gas inlet pipe

[0083] 130: Bulkhead

[0084] 10: Overflow pipe

[0085] 20: Liquid level gauge

[0086] 30: Downstream pipe

[0087] CV: Liquid level control valve

Claims

1. A liquid region where the reaction takes place and a gaseous region located above it; A partition wall dividing the liquid region into first and second zones longitudinally; a liquid level gauge connected to a second zone of the above liquid region; and In the above liquid region, a downstream pipe is provided on the side of the second zone to discharge the liquid stream, A bubble column reactor in which the baffle section is provided within the liquid zone such that one end thereof is positioned at the boundary between the liquid zone and the gas zone, so that the liquid stream of the first zone overflowing from the upper portion of the baffle section is stored in the second zone.

2. In paragraph 1, The above liquid zone is a bubble column reactor in which ethylene gas and a solvent are supplied and an oligomerization reaction is performed.

3. In paragraph 1, A bubble column reactor comprising a top piping for discharging a gaseous stream containing unreacted gases from the above gaseous region.

4. In paragraph 1, A bubble column reactor in which the above-mentioned baffle section is provided with a vertical wall in the longitudinal direction and a horizontal plate extending laterally from the lower end of the vertical wall and contacting the side surface of the second liquid region.

5. In paragraph 1, A bubble column reactor in which the horizontal plate of the above baffle section is adjacent to or spaced apart from the lowest surface of the liquid region.

6. In paragraph 1, The above baffle section is a bubble column reactor in the form of a vertical wall extending upward from the lowest surface of the liquid region.

7. In paragraph 1, The above baffle section is a bubble column reactor in the form of a vertical tube with a donut-shaped rim and a closed bottom.

8. In paragraph 1, A bubble column reactor in which the first zone and the second zone in the above liquid region are divided with an area ratio of 100:1 to 20:

1.

9. In paragraph 1, A bubble column reactor in which a liquid stream stored in a second zone of the above liquid region has undergone gas-liquid separation.

10. In paragraph 1, The above liquid level gauge is a bubble column reactor in which the liquid level of the liquid stream separated from the gas is measured in the second zone of the liquid region.

11. In paragraph 1, A bubble column reactor, wherein the liquid discharge pipe connected to the lower part of the second zone in the above liquid region includes a valve for controlling the amount of liquid discharged according to the signal of the liquid level gauge.

12. An oligomer manufacturing device comprising a bubble column reactor according to Article 1.

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