JPS63123433A - Reactor - Google Patents

Abstract

PURPOSE:To prevent excessive rise of catalytic reaction temp. by pressurizing gas separated through gas-liquid separation with a circulation gas compressor, and introducing it from the upper ends of annular spaces of respective pipes packed with a granular solid catalyst. CONSTITUTION:Central pipes 19 are positioned at the centers of a plurality of reaction pipes 11. The reaction pipes 11 are fitted to the tube plates 14, 15 of the upper and lower parts, and the upper ends of the central pipes 19 are fitted to a partition plate 18 and the lower ends thereof are closed with end covers 21. A granular solid catalyst 12 is packed in the reaction pipes 11. Gas produced by a steam reforming method or the like is introduced into the central pipes 19 as replenishment gas 1 of a reactor 7. The reactor having the following structure is obtained wherein the ratio of CO, CO2 to H2 can be made smaller in comparison with a conventional method in case of bringing circulated nonreactive gas 4 having a low-concn. of methanol into contact with the catalyst 12 packed in the reaction pipes 11.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel multi-tubular reactor for methanol synthesis.

[Conventional technology]

A well-known method is to steam-reform a gas mainly composed of hydrocarbons to obtain a mixed gas mainly consisting of hydrogen, carbon monoxide, and carbon dioxide, and to synthesize methanol using this as a raw material.

An example of this type of methanol synthesis is shown in Table 1 (Source: Catalyst Society of Japan, Catalysis Course A6 "Catalytic Reactor and Its Design", p. 294,
Published by Kodansha Suentei.

Figure 6 shows the equipment arrangement and piping system of a commonly used methanol synthesis plant (December 1958).

In FIG. 6, a synthesis raw material gas 1 mainly consisting of hydrogen, carbon monoxide, and carbon dioxide obtained from a hydrocarbon steam reforming system is compressed by a synthesis gas compressor 2 and then separated by a methanol separator 3. After being mixed with the circulating gas 4 and further compressed by the circulating gas compressor 5, it is heated by the heat exchanger 6, and then supplied to the methanol synthesis reactor 7, where a methanol synthesis reaction is performed. The synthesized gas is cooled in the heat exchanger 8 and sent to the methanol separator 3, where it is separated into unreacted gas and crude methanol liquid 9, which becomes the circulating gas 4. A part of the circulating gas 4 is sent to the purge gas 10. Although some of it is released outside the system, the majority is recycled as described above.

The methanol synthesis reactor 7 shown in Fig. 6 consists of: 1) A plurality of reaction tubes are filled with a granular solid catalyst, and a pressurized mixed gas containing hydrogen, carbon monoxide, and carbon dioxide as significant substances is supplied to the catalyst layer. 2111, -1- Co -+ (
The exothermic reaction of formula (1) is caused by placing pressurized water under saturated conditions at a temperature lower than the appropriate reaction temperature on the outer surface of the reaction tube. A reactor that attempts to maintain the reaction temperature within an appropriate condition range by converting the heat generated as the reaction progresses into the latent heat of vaporization of water by heat transfer through the tube wall of the reaction tube (Japanese Patent Publication No. 56-22854)
(Refer to the above publication) and ■ The reactor previously proposed by the present inventors, that is, a center tube is located in the center of a plurality of reaction tubes, and the annular space surrounded by the reaction tubes and the center tube is filled with granular catalyst. A reactor for carrying out an exothermic reaction in which unreacted supply gas flows from the bottom to the top of the central tube, and gas flows from the top to the bottom in the annular catalyst layer,
A central tube through which unreacted feed gas flows is connected to one or more mixing chambers located above, into which cold unreacted feed gas is introduced at a lower temperature than the unreacted feed gas leaving the central tube. There is a reactor equipped with a section (Japanese Patent Application No. 59-80055).

A schematic diagram of the reactor (2) above is shown in FIG. This reactor is equipped with a plurality of reaction tubes 11 (only one is shown in the figure), and the tubes 11 are filled with a solid granular catalyst 12 as shown in FIG. While the gas is moving, dimethatol is generated through a catalytic reaction, and the reaction heat is transferred to the water in contact with the outside of the reaction tube 11 to obtain water vapor.

The gas (unreacted gas) is pressurized by the compressor (2 and 5 in Figure 6) and preheated by the heat exchanger (6 in Figure 6).
In the figure, the tube is fed into a space (3) partitioned by an upper tube plate 15 and an upper tube plate 14. This gas flows into the plurality of reaction tubes 11 in a dispersed manner, causing the catalytic reaction of equation (1).
1 from top to bottom, flows out into a space @ partitioned by a lower tube plate 15 and a lower mirror 16, and is then taken out from a gas outlet nozzle provided in the lower mirror 16. Upper and lower tube plate 1a
, 15, the shell 17, and the reaction tube 11, pressurized water at a saturated temperature is introduced into the space θ.

Furthermore, a schematic diagram of the reactor (2) above is shown in FIG.

This reactor uses gas that does not pass through a heat exchanger (6 in Figure 6). Therefore, the temperature of the gas introduced into the reactor must be 50 to 150 DEG C., which is low enough to cause a catalytic reaction, and this is different from the reactor described in (2) above.

This unreacted gas flows into the space surrounded by the lower mirror 16 and the partition plate 18 in FIG.

Thereafter, the flow is dispersed into the central tubes 19 located in a plurality of reaction tubes 11 (only one is shown in the figure), and the central tubes 19
The liquid flows inside from the bottom to the top and flows into the space G partitioned by the upper tube plate 15 and the upper tube plate 14. In the process of rising in the central tube 19, this gas is given heat of contact reaction by heat transfer through the tube wall 19 (heated and raised in temperature). In other words, in this process, the gas is preheated to an appropriate temperature, and Prevent excessive rise in reaction temperature. In this way, the central tube 19 functions as a heat exchanger, and the unreacted gas has a role as a refrigerant.

The unreacted gas flowing into the space e flows from top to bottom through the 12 layers of catalysts filled in the annular columnar space between the reaction tube 11 and the central tube 19, performs a catalytic reaction, and then passes through the lower tube plate. 15
and the partition plate 18, and is then taken out from the gas outlet nozzle.

The heat generated in the process of causing a catalytic reaction while the gas moves through this annular columnar space is given to the gas in the central tube 19, and the pressurized water at a saturated temperature in contact with the outside of the reaction tube 11 is fed into the reaction tube 11. Provided by heat transfer through the tube wall, preventing excessive rise in reaction temperature. The heat given to the water is extracted as steam and used for purposes such as power generation.

By the way, the copper-based catalyst, which is currently available in excellent quantities, has an appropriate reaction temperature range of 220 to 280°C as a catalyst used in the methanol synthesis reactor as mentioned above, and if the temperature exceeds this temperature, the activity of the catalyst decreases. , a decrease in the equilibrium methanol concentration and an increase in undesirable side reaction products occur. This temperature control is a major factor governing the quality of the structure of the reactor for methanol synthesis.

In particular, as the reaction rate increases due to improved catalysts, the amount of heat generated also increases, creating a major problem in temperature control technology, and unless this point is solved, it will not be possible to reduce the space velocity.

If this space velocity can be made small, the gas flow resistance, that is, the pressure loss when the gas moves through the catalyst 1, will be small, and the S dynamic energy (power cost) of the circulating gas compressor can be made small. In addition, there are industrial advantages in that the contact reaction time is long and the amount of methanol produced in the reactor can be increased (closer to equilibrium concentration).

However, in the structure like (2) above, there is a limit to the amount of heat transfer through the wall of the reaction tube, and there is a limit to the performance of the reactor. That is, when water transfers heat while generating water vapor bubbles on a metal wall surface, the heat transfer coefficient α on the water side is approximately IQ, 000.
kcal/L"h"C, and it is impossible to increase this significantly. On the other hand, the heat transfer coefficient between the gas in the reaction tube and the metal wall surface varies slightly depending on the pressure, gas composition, and flow rate, but is α-1,000 to 3. OOOkoa1
/yJ·h·c, and it is impossible to increase this significantly.

Therefore, heat transfer to the water in contact with the outer surface of the reaction tube alone will not be sufficient for future high-performance reactors, and the inventors have positioned a central tube in the center of the reaction tube and used this central tube to transfer heat. They proposed the reactor (2) above, which functioned as a heat tube, that is, a heat exchanger.

In addition, in FIG. 6, the composition of the gas 4 separated by the methanol separator 5 is co, co17m, as is clear from the purge gas composition in Table 1, and the ratio is small, approximately 0.05 at the five points in FIG. be. On the other hand, as is clear from the syngas compressor inlet gas composition in Table 1, gas 1 supplied from the steam reforming system has a large Co, Co,/horse ratio of about 150 at point G in FIG.

This is just an example, and differs depending on the composition 0/Tl ratio of the natural gas supplied to the steam reformer, the performance of the methanol synthesis reactor, etc. However, although there are slight variations in specific values, there is a large difference in the co, co, /4 ratio between the log gas 4 from the methanol separator 5 and the makeup gas 1 from the steam reforming system.

In the methanol synthesis reactor 7 population gas in Table 1, methanol separator outlet gas is mixed with 1 part make-up gas from the steam reforming system at a ratio of 575 parts. This allows co
, fed into the reactor 7 at a coA ratio of about α09,
in contact with the catalyst.

[Problem that the invention seeks to solve]

Figure 9 shows the temperature distribution in the length direction of the reaction tube when a methanol synthesis reaction is carried out using the reactor with the structure of (2) above [Source: Nozawa et al. "Methanol" Chemical Engineering 701, 46]
4? (1982) p. 512]. The 9th station is the same as the reactor shown in FIG. 7, and FIG. 9 (3) shows the temperature distribution at the corresponding position of the 9th station.

As shown in Figure 9(A) and CB+, the temperature rises at the inlet of the catalyst layer because (1) the methanol concentration of the inflowing gas is essentially zero, and the difference from the reaction equilibrium concentration is large; (2) ) This is because the reaction rate is high due to the high concentration of unreacted co, co, (the amount of heat generated per unit pipe length, that is, unit heat transfer area is large), and this is due to the increased catalyst activity and small space velocity. It should be noticeable.

Note that this FIG. 9 also includes the factor of temperature rise-reaction rate rise.

Furthermore, the temperature gradually decreases from the inlet of the catalyst layer, that is, the upper region of the reaction tube in Figure 9 (4), to the lower part, but this is because the gas in contact with the granular solid catalyst contains a significant concentration of methanol. Although there is a difference from the reaction equilibrium concentration, it is not as large as (1) above ■ The reaction rate is lower because the concentration of unreacted co, oo, and so on is lower than in (2) above. It is.

In other words, the reactor shown in Figure 89 has a problem in that the reaction load distribution in the tube length direction is significantly different, and the load near the catalyst layer inlet is extremely large (too large).

On the other hand, the reactor (2) proposed by the present inventors exhibits a behavior similar to that shown in FIG. 9, although there is a significant improvement over that shown in FIG. 9 due to heat transfer through the central tube.

As mentioned above, this temperature increase is undesirable in terms of deactivation of the catalyst and increase in undesirable side reaction products, and becomes an obstacle in reducing the space velocity.

The present invention proposes a reactor that does not have the above drawbacks.

[Means for solving problems]

The present invention fixes a plurality of reaction tubes positioned in the vertical direction to upper and lower tube plates, and also positions a center tube in the center of the reaction tubes, so that granular particles are formed in an annular space constituted by the reaction tubes and the center tube. A methanol synthesis reaction is carried out by filling a solid catalyst and contacting the catalyst with a pressurized mixed gas containing hydrogen, carbon monoxide, and carbon dioxide as significant substances, and the reaction heat is located outside the reaction tube at a saturation temperature. In the reactor, steam is obtained by transferring pressurized water to water, and from the upper end of the annular space filled with granular solid catalyst in each reaction tube, gas separated by gas-liquid separation is pressurized by a circulating gas compressor and flows into the reactor. In addition to doing so,
Makeup gas produced by a method such as steam reforming is allowed to flow into each center tube, and a plurality of gas inflows penetrate the wall of the center tube from any position in the longitudinal direction of the center tube. The present invention relates to a reactor characterized in that the supplementary gas is allowed to flow through the holes into the catalyst layer in which a catalytic reaction is occurring, thereby preventing an excessive rise in the catalytic reaction temperature.

As an example of the reactor of the present invention is shown in FIG. 1 (4), similar to the reactor (2) above, a plurality of reactors [in FIG. 1 (4), one
[Only shown] A central tube 19 is located at the center of the reaction tube 11. However, this center tube 19 does not need to be provided over the entire length of the reaction tube 11, and as shown in FIG.
The gas outlet hole 20 may be provided at an arbitrary position of the central tube 19 as shown in FIG. The plurality of reaction tubes 11 are arranged on upper and lower tube plates iA, 15.
mounted on. Each central tube 19 has an upper end attached to the partition plate 18 and a lower end closed by an end cap 21. A granular solid catalyst 12 is filled in the reaction tube 11 . The catalyst 12 in the reaction tube 11 is packed in the form shown in Figure 1 (q(2)). FIG. 1 is a cross-sectional view at the 0 point in FIG. 1 (8).

A gas produced by steam reforming or the like is allowed to flow into the central pipe 19 as the supplementary gas 1 for the reactor 7. On the other hand, as shown in Fig. 5, the circulating gas 4 after the methanol (containing water and a small amount of side reaction products and dissolved gas) liquid has been separated in the gas-liquid separator 3, or a small amount of new replenishment to this The gas to which gas 1 has been added is preheated by a heat exchanger 8 and supplied from the circulating gas nozzle of the reactor 7, so as to flow into the reaction tube 11.

As mentioned above, the log gas 4 output from the gas-liquid separator 5 is (:!0,
00. /H, ratio is small, for example, the ratio of the coating 1, in other words, the concentration of the substance with significant reaction is small.

That is, in the present invention, the unreacted gas 4 in a state where the degree of methanol is low is
co, co, 7 when in contact with the catalyst 12 in the reaction tube 11
The first feature is that the reactor has a structure in which the ratio of m and m can be made smaller than that of the conventional reactor shown in FIGS. 6 and 7.8.

It is a matter of course that even if the difference from the reaction equilibrium concentration is large, the reaction rate cannot be increased if the concentration of the reaction significant substance is small.

Further, the present invention provides co, oo! /4 ratio reactor make-up gas 1 is added, i.e. CO.

The second feature is that the reactor has a structure that allows the partial pressure to be raised to zero. This reactor supply gas 1 moves in the center pipe 19 as shown in FIG.
From the gas outlet holes 20 (plurality) provided in the tube hole of the catalyst layer 12
The gas inside is replenished.

Note that if the methanol concentration in the gas is a significant value, the co
, co, it is a matter of course that the reaction rate cannot become excessive even if the partial pressure is increased.

Furthermore, the present invention includes providing the gas flowing in the central tube 19 with the role of a refrigerant, as in the reactor (2) above.

The supplementary gas 1 to be supplied into the center pipe 19 can be supplied by preheating the discharge gas of the compressor 2 via a gas preheater (not shown), and on the other hand, the temperature is lower than the contact reaction temperature 40
It is also possible to introduce gas at ~150° C. and use it for a timed contact reaction.

In the present invention, when the center tube 19 is extended to the middle of the length of the reaction tube 11 as in the first device, the filling state of the catalyst 12 is as shown in FIG. It is different as shown in tcqol18. Therefore, reaction tube 1
1 diameter is the same, the space velocity will differ depending on the presence or absence of the center tube 19, but this is because in the region where the reaction rate is small, that is, in the region where the methanol concentration in the gas increases, the contact reaction time will be different. This has the advantage that the amount of methanol produced increases (the concentration of methanol output from the reactor 7 increases), and the pressure drop decreases because the flow resistance of the gas decreases, which is the third aspect of the present invention. It is a characteristic.

However, there may also be a case as shown in FIG. 4 as an embodiment of the present invention, in which case the fifth feature is compromised.

[Function] [Example] In the present invention, as shown in FIG. To separate. The gas-liquid separator 3
A portion of the separated gas 4 is purged 10, and the remaining gas is pressurized by a circulating gas compressor 5, preheated by a heat exchanger 8, and then sent to a reactor 7. A small amount of supplementary gas 1 may be added to adjust the co, cot/4 ratio.O New supplementary gas 1 produced by means such as steam reforming (not shown) has a large co, co, lz ratio. , all (or most) of this gas is fed into the reactor 7 without mixing with the recycle gas 4. In order to adjust the temperature, preheating may be performed using a heat exchanger (not shown).

Incidentally, the fifth case corresponds to the reactor having the structure shown in FIGS. 1 and 4, and in the case of the reactor having the structure shown in FIG. 2, the gas feeding point needs to be corrected.

In addition, in FIG. 1 (4), the circulating gas 4 is
and the space ■ separated by the upper tube plate 14, and the space ■
It flows into the upper end of each reaction tube 11 in a dispersed manner, and moves from top to bottom of the catalyst 12 layer while producing methanol through a catalytic reaction. New supplementary gas produced by steam reforming etc. 1
flows into the space (2) divided by the upper mirror 15 and the partition plate 18, enters the upper end of each center pipe 19 from the space, and enters the outflow hole 20.
and then dispersedly flows into the 12 catalyst layers.

As shown in FIG. 1 (6), the central pipe 19 plays the role of a connecting pipe with respect to the pipe length (2) between the partition plate [18 of the first device] and the upper end of the catalyst 12 layer. The pipe length (2) from the upper end of the catalyst layer 12 to the gas outlet hole 20 area is a supplementary gas preheating area (role of heat exchanger). In other words, the supplementary gas 1 functions as a refrigerant and suppresses an excessive rise in the contact reaction temperature. In this section of the pipe length (■), methanol is produced by the contact reaction between ao and ao in the circulating gas 4.

The pipe length of the central pipe 19 is 0.00. Co, /E, make-up gas 1 with a large ratio
This is the area where . This is done by a plurality of small holes (gas outflow holes) 20 provided in the wall of the central tube 19. There are no restrictions on the diameter, number, position, distribution, or differential pressure of the sous outlet holes 20.

Pipe length ■ is the area where the space velocity is maintained high.

There are no restrictions on the pipe lengths of (1), (2), (2), and (2) and the diameter of the central tube 19.

In the first stage, the gas flowing down while reacting in the catalyst 12 layer flows into the space ◎ formed by the lower tube plate 15 and the lower mirror 16, and is taken out of the reactor 7. Upper and lower tube plates 14, 15
Pressurized water at a saturated temperature is placed in a space (2) partitioned by a body 17 and a body 17. Naturally, the temperature is maintained below the appropriate catalytic reaction temperature.

In a second device other than another embodiment of the reactor of the present invention,
The circulating gas 4 is introduced into the upper end of each reactor 11 from a space 1 separated by an upper part 1S and a partition plate 1B. The supplementary gas 1 flows into the upper end of each central tube 19 from a space defined by the partition plate 18 and the upper tube plate 14.

The structure in Fig. 2 is different from that in Fig. 1 between the upper tube plate 14 and the partition plate 18, and as shown in ) in Fig. 2, the structure between the upper tube plate 14 and the partition plate 18 is different from that in Fig. 1. Central tube 1? is bent, and the central tube 19 is positioned by penetrating the tube wall of the connecting tube 22. The upper end of the connecting pipe 22 is connected to the partition plate 1B (Fig. 2 (4)
) is opened to the space ■ consisting of 15) inside.

The one in Figure 2 has a partition plate 18 and an upper value 1 for the upper part.
There is no center pipe 19, connecting pipe 22, etc. in the space ◎ between the lower tube plate 15 and the lower mirror 16, and compared to the reactor in It also has the advantage that the extraction work becomes much easier.

There is also a reactor in which FIG. 2 is turned upside down, which is more advantageous from the point of view of catalyst loading operations, in which case the gas flow in the catalyst bed is from bottom to top.

The reactor shown in FIG. 4 is one in which the length of the center tube 19 of the reactor in FIG. ■The length of the central canal in the area is increased. In this case, the 12 layers of catalyst packed have an annular shape over the entire length.

The extension of the length of the central tube 19 shown in FIG. 4 can also be applied to the reactor shown in FIG. 2.

FIG. 5 schematically shows the distribution of the contact reaction temperature in the reaction tube of the reactor of the present invention in the tube length direction using the drawing method shown in FIG. 9.

In the conventional reactor 7 shown in FIGS. 7 and 8, a supplementary gas 1 is added to the circulating gas 4 to increase the co, co□/H, ratio, which is fed into the reactor 7, and this is fed into the catalyst layer. However, since the methanol concentration is substantially zero and the Go, CO, /4 ratio is large, the catalyst 12
The reaction rate is high above the layer, and the temperature rises due to the equilibrium between the heat transfer rate through the wall of the reaction tube 11 and the heat generation rate. As the temperature rises, the reaction rate also increases, υ, and the temperature reaches M. After reaching this point M, the methanol concentration increases and c
As the o, co, /4 ratio decreases, the reaction rate decreases and the temperature gradually decreases.

On the other hand, in the reactor of the present invention, 0.00. Since the cot/4 ratio is kept small, this temperature rise is small (point m in FIG. 5). In addition, the central tube 19 is positioned so that this area becomes the ■ area, and the central tube 1
The gas in the reaction tube 9 functions as a refrigerant, and the temperature rise at the point m is reduced by a combined effect with the refrigerant effect of pressurized water at a saturation temperature located outside the reaction tube 11.

In the region (■) from point n to point p, where the contact reaction temperature has slightly decreased after passing point m, supplementary gas 1 with a large co, cot/4 ratio is supplied from the center pipe 19 in a distributed manner to reduce the amount of c necessary for the contact reaction.
Replenish o, oo□. As a result, the temperature rises again, but since the supply is distributed, an excessive rise in temperature can be completely prevented.

Although the supplementary gas 1 is not supplied from the center pipe 19 in the region (2) from point p to the lower end of the catalyst layer 12, the co contained in the gas at point p moves while reacting with the bird. Note that as the reaction rate decreases due to the decrease in co, co, concentration, the temperature gradually decreases, but based on the known fact that the lower the contact reaction temperature near the outlet of the reaction tube 11, the higher the equilibrium methanol concentration becomes. The temperature of the region, the height of the catalyst layer, and the space velocity are important factors in reactor performance.

〔Effect of the invention〕

According to the present invention, various effects can be achieved, such as making the reaction load uniform over the entire length of the reaction tube, preventing an excessive rise in temperature, and facilitating the loading and unloading operations of the catalyst.

[Brief explanation of the drawing]

Fig. 1 (5) to (to) are diagrams showing one embodiment of the reactor of the present invention, Fig. 1 (6) is an overall view, Fig. 1 CBI is a partially enlarged sectional view, and Fig. 1 (C) is a cross-sectional view of point 0 in Figure 1 (1), the opening in Figure 1 is a cross-sectional view of point 0 in Figure 1 (4),
Figures (4) and (5) are diagrams showing other embodiments of the reactor of the present invention, where Figure 2 (6) is an overall view, Figure 2 (8) is a partially enlarged sectional view, and Figure 3. is a diagram showing the entire system of methanol synthesis to explain the action of the reactor of the present invention, Figure 4 is a diagram showing another embodiment of the reactor of the present invention, and Figure 5 is a diagram showing the effects of the reactor of the present invention. Figure 6 is a diagram showing the entire conventional methanol synthesis system, Figures 7 and 8 are diagrams showing the conventional reactor, and Figure 9 (B) is a diagram showing the conventional methanol synthesis system shown in Figure 7. It is a figure for explaining the drawback of a reactor. Sub-Agent 1) Meifuku Agent Ryo Hagiwara - Sub-Agent Atsuo Anzai Figure 1 (D) Box 4 817□-1'' Figure 6! Unreacted gas procedure amendment March 9, 1986

Claims (2)

[Claims] (1) A plurality of reaction tubes placed in the vertical direction are fixed to the upper and lower tube plates, and a center tube is positioned in the center of the reaction tubes, and granular solids are placed in the annular space composed of the reaction tubes and the center tube. A methanol synthesis reaction is carried out by filling a catalyst and contacting the catalyst with a pressurized mixed gas containing hydrogen, carbon monoxide, and carbon dioxide as significant substances, and the reaction heat is transferred to a saturated temperature chamber located outside the reaction tube. In a reactor in which steam is obtained by transferring pressurized water, the gas separated by gas-liquid separation is pressurized by a circulating gas compressor and flows into the upper end of the annular space filled with granular solid catalyst in each reaction tube. At the same time, the supplementary gas produced by a steam reforming method or the like is allowed to flow into the pipe of each central pipe, and the pipe wall of the central pipe is penetrated from any position in the longitudinal direction of the central pipe. A reactor characterized in that the supplementary gas is caused to flow into the catalyst layer in which a catalytic reaction is occurring through a plurality of gas inflow holes, thereby preventing an excessive rise in the catalytic reaction temperature. (2) The reactor according to claim (1), wherein a part of the supplementary gas is added to the gas separated by the gas-liquid separator.