JP2019104003A - Reaction method and reaction device - Google Patents

Abstract

To provide a reaction method and a reaction device, capable of suppressing load of devices and enhancing reaction efficiency.SOLUTION: In a reaction method using a reaction device 1, by changing a changing part 7 at a first position communicating a first flow pass 4 and a first column 3a, and communicating a second flow pass 5 and a second column 3b, and at a second position communicating the first flow pass 4 and the second column 3b and communicating the second flow pass 5 and the first column 3a alternatively, a raw material solution and a reaction gas flowing inside in the first column 3a and second column 3b constitute a layer shape alternatively to flow directions thereof. As a result, in a boundary of each layer, the raw material solution and the reaction gas are contacted. Thereby the boundary of each layer becomes a reaction surface, area of a reaction surface of the whole first column 3a and second column 3b increases, and reaction efficiency can be enhanced.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a reaction method and a reaction apparatus in which a raw material solution and a reaction gas are caused to flow through a column packed with an immobilized catalyst to cause a chemical reaction.

  Generally, a reaction method using a trickle bed reactor in which a raw material solution and a reaction gas are supplied to a column packed with an immobilized catalyst to cause a chemical reaction, and a reaction apparatus used for the method are known (for example, , Patent Document 1). Conventionally, as shown in FIG. 4, the reactor 101 controls at least one column 102 packed with an immobilized catalyst, a pump 104 for feeding the raw material solution 103 into the column 102, and the flow rate of the reaction gas 105. A mass flow controller 106 and a channel 107 for supplying the raw material solution 103 and the reaction gas 105 to the column 102 are provided. The reaction apparatus 101 simultaneously supplies the raw material solution 103 and the reaction gas 105 from the flow path 107 to one column 102, and chemically reacts the raw material solution 103 and the reaction gas 105 in the column 102 to obtain a product. ing.

Unexamined-Japanese-Patent No. 2017-113658

However, the conventional reactor 101 (see FIG. 4) has the following problems.
When the raw material solution 103 and the reaction gas 105 are simultaneously supplied to the column 102 from the flow path 107, the inner diameter of the column 102 needs to be as large as possible in order to enhance the reaction efficiency. In the column 102, a partial flow of the raw material solution 103 and the reaction gas 105 occurs, which causes a problem that the reaction efficiency is largely reduced.

  Also, a method has been proposed for alternately supplying the raw material solution and the reaction gas to the column in the conventional reaction apparatus 101. In this case, the raw material solution 103 is used to control the supply of the raw material solution 103 and the reaction gas 105. It is necessary to repeat ON / OFF control of the pump 104 for feeding. In addition, it is necessary to repeat ON / OFF control of a drive power source for driving a control valve (not shown) of the mass flow controller 106. Therefore, the pump 104 and the mass flow controller 106 may be loaded.

  This invention is made in view of the said subject, The place made into the objective is to provide the reaction method and reaction apparatus which can suppress the load of an apparatus and can improve reaction efficiency.

(Aspects of the Invention)
The following aspects of the invention illustrate aspects of the invention and are divided into sections to facilitate understanding of the various components of the invention. The following sections do not limit the technical scope of the present invention, and while taking into consideration the best mode for carrying out the present invention, some of the components of each section may be replaced, deleted, or further The aspect to which other components are added is also one aspect of the present invention.

  (1) A reaction method using a trickle bed reactor in which a raw material solution and a reaction gas are caused to flow through a column packed with an immobilized catalyst to cause a chemical reaction, and the first column and the second column are arranged in parallel. A reaction method comprising: arranging each of the first column and the second column to alternately supply a raw material solution or a reaction gas at predetermined time intervals (claim 1).

  In the reaction method according to this item, by arranging the first column and the second column in parallel, it is possible to prevent the occurrence of the partial flow of the raw material solution and the reaction gas generated by enlarging the inner diameter of each column, By the column and the second column, products resulting from the chemical reaction of the raw material solution and the reaction gas are obtained. Further, in the reaction method, the raw material solution and the reaction gas are alternately switched at predetermined time intervals for each of the first column and the second column, whereby the raw material solution and the reaction gas become the first column and the second column. The flow alternately in the two columns, so that in each column, the raw material solution and reaction gas flowing inside are alternately layered with respect to the flow direction, and the raw material solution and reaction gas come into contact at the boundary of each layer. It becomes. Therefore, the boundary of each layer becomes a reaction surface, and a chemical reaction of the raw material solution and the reaction gas occurs.

  (2) In the above (1), the first flow path for supplying the raw material solution to the first column and the second column via the switching unit, and the second flow path for supplying the reaction gas are respectively provided. A first position for connecting the first flow path and the first column and for causing the second flow path and the second column to communicate with each other; A second position communicating the two columns and communicating the second flow path and the first column; alternately switching the first position and the second position; And a reaction method of supplying a raw material solution or a reaction gas to each of the second columns (claim 2).

  In the reaction method according to the present paragraph, the first channel for supplying the raw material solution and the second channel for supplying the reaction gas are connected to the first column and the second column via the switching section, and the switching section And a first position connecting the first flow path and the first column and connecting the second flow path and the second column, and connecting the first flow path and the second column and the second flow path And a second position for communicating with the first column, and alternately switching the first position and the second position. According to this configuration, while supplying the raw material solution to the first column, the reaction gas is supplied to the second column, and while the reaction gas is supplied to the first column, the reaction to the second column is performed. It becomes what supplies a raw material solution. In addition, by switching the supply state of these simultaneously by switching the first position and the second position in the switching unit, in each column, the raw material solution and the reaction gas flowing to the inside are in the flow direction thereof. Layered alternately, the raw material solution and the reaction gas come into contact at the boundary of each layer. Therefore, the boundary of each layer becomes the reaction surface, and the area of the reaction surface in the entire column increases. Also, since the switching section is switched between the first position and the second position to control the flow direction of the raw material solution and the reaction gas, the pump can be operated at all times, and the load due to ON / OFF of the pump can be suppressed. It becomes.

  (3) The reaction method according to (2), wherein the switching unit includes control means for switching between the first position and the second position every predetermined time.

  In the reaction method according to the present item, by providing control means for switching the switching unit between the first position and the second position every predetermined time, the time for supplying the raw material solution and the reaction gas to the first column and the second column Control the dynamic span. Then, by setting the time span of switching of the first position and the second position in the switching section appropriately short, in each column, the raw material solution and reaction gas flowing inside are switched with respect to their flow directions. In response to the time span of (1), the raw solution and the reaction gas come into contact at the boundary of each layer. Therefore, the boundary of each fine layer becomes the reaction surface, and the area of the reaction surface in the entire column increases.

  (4) The reaction method according to (2) or (3), wherein a four-port two-position directional control valve is used in the switching unit.

  In the reaction method according to this item, by using the 4-port 2-position directional control valve, the flow directions of the raw material solution and the reaction gas with respect to the first column and the second column can be simultaneously switched.

  (5) In any one of the above (1) to (4), the first and second columns are packed with an immobilized catalyst in which a catalyst is supported on a carrier having an average particle diameter of 20 μm to 3 mm. Reaction method (claim 5).

  In the reaction method according to the present item, the raw material solution and the raw material solution in each column are packed by filling the first column and the second column with the immobilized catalyst having the catalyst supported on the carrier having an average particle diameter of 20 μm to 3 mm. The catalyst functions on the reaction surface of the raw material solution flowing inside each column and the reactive gas without causing the flow of the reactive gas to cause a chemical reaction between the raw material solution and the reactive gas.

  (6) A reaction apparatus comprising a trickle bed reactor in which a raw material solution and a reaction gas are allowed to flow through a column packed with an immobilized catalyst to cause a chemical reaction, and the first column and the second column arranged in parallel A first flow path for supplying a raw material solution to the first column and the second column, a second flow path for supplying a reaction gas to the first column and the second column, and the first flow path and The second flow path is disposed between the first column and the second column, and the first flow path and the first column are in communication with each other, and the second flow path and the second column are A first position for communication, or a second position for communication between the first flow path and the second column and between the second flow path and the first column, the first position And a switching unit capable of alternately switching the second position Ku and reactor also comprises (Claim 6).

  (7) The reaction device according to (6), further comprising: control means for switching the switching portion between the first position and the second position at predetermined time intervals (claim 7).

  (8) The reaction device according to (6) or (7), wherein the switching unit is a 4-port 2-position directional control valve (claim 8).

  (9) In any one of the above (6) to (8), in the immobilized catalysts packed in the first column and the second column, the catalysts are supported on a carrier having an average particle diameter of 20 μm to 3 mm. A reactor (claim 9) that is

  By using the reaction devices of the above items (6) to (9), the same effects as those obtained by the respective reaction methods of the above items (2) to (5) can be exhibited.

  ADVANTAGE OF THE INVENTION this invention can provide the reaction method and reaction apparatus which can suppress the load of an apparatus and can improve reaction efficiency by having comprised as mentioned above.

It is the schematic of the process flow of the trickle bed reactor which concerns on this embodiment. It is the description which showed typically the switching part shown in FIG. 1, (a) is a figure which shows the 1st position of a switching part, (b) is a figure which shows the 2nd position of a switching part. It is explanatory drawing which showed typically the flow aspect of the raw material solution in the inside of the 1st column shown in FIG. 1, and a 2nd column, and reaction gas. FIG. 1 is a schematic view of the process flow of a prior art trickle bed reactor.

Hereinafter, the structure of the reaction apparatus which concerns on one Embodiment of this invention is demonstrated in detail based on FIGS. 1-3.
As shown in FIGS. 1 and 3, the reaction apparatus 1 according to an embodiment of the present invention allows the raw material solution 18 and the reaction gas 19 to flow through the column 3 filled with the immobilized catalyst 2 to cause a chemical reaction. The product is obtained. The reaction apparatus 1 includes a column 3, a first channel 4, a second channel 5, a third channel 6, a switching unit 7, a control unit 8, a raw material solution storage unit 11, and a reaction gas. A storage unit 12, a pump 13, a mass flow controller 14, a gas-liquid separation tank 15, a liquid discharge flow path 16, and a gas discharge flow path 17 are provided.

  The column 3 is formed by arranging in parallel cylindrical first columns 3a and second columns 3b formed of a glass material (see FIG. 1). The immobilized catalyst 2 (see FIG. 3) is packed in the first column 3a and the second column 3b. Further, in the first column 3a and the second column 3b, a first flow path 4 and a second flow path 5 described later are connected to the upper portion, and a third flow path 6 described later is connected to the lower portion. The immobilized catalyst 2 is a catalyst in which palladium is supported on a spherical alumina carrier having a polysilane coating layer and having an average particle diameter of 20 μm to 3 mm.

  The first flow path 4 is a flow path for supplying the raw material solution 18 to the first column 3a and the second column 3b, and the raw material solution storage unit 11 containing the raw material solution 18, the first column 3a and the second column 3b Connect between The second flow path 5 is a flow path for supplying the reaction gas 19 to the first column 3a and the second column 3b, and the reaction gas storage unit 12 storing the reaction gas 19, the first column 3a and the second column 3b Connect between The third flow path 6 is a flow path for supplying gas / liquid obtained from the chemical reaction of the raw material solution 18 and the reaction gas 19 to the gas / liquid separation tank 15, and the first column 3a and the second column 3b It connects between the liquid separation tank 15.

  The switching unit 7 is disposed between the first flow path 4 and the second flow path 5 and the first column 3a and the second column 3b, and connects the first flow path 4 and the first column 3a to a first connection. A first position (see FIG. 2A) in which the second channel 5 and the second column 3b are in communication via the second connection channel 10 and in communication via the channel 9; The first channel 4 and the second column 3b are communicated via the second connection channel 10, and the second channel 5 and the first column 3a are communicated via the first connection channel 9. And a second position (see FIG. 2B). The switching unit 7 electrically switches between the first position and the second position in response to an operation command from the control means 8 described later, and in the present embodiment, it is an electromagnetic four-port two-position directional control valve. is there.

  The control means 8 is provided in the switching unit 7 and switches the first position and the second position in the switching unit 7 every predetermined time, and the raw material solution 18 and the reaction gas 19 are arranged in the first column 3a and the second column 3b. Control the time span supplied to the As the control means 8, a suitable control device such as a general purpose or dedicated computer, PLC, etc. is used.

  The pump 13 feeds the raw material solution 18 to the first column 3 a and the second column 3 b, and is provided in the first flow path 4. The mass flow controller 14 controls the flow rate of the reaction gas 19 and is provided in the second flow path 5.

  The gas-liquid separation tank 15 stores gas-liquid obtained by causing a chemical reaction of the raw material solution 18 and the reaction gas 19, and is connected to the third flow path 6. Further, the gas-liquid separation tank 15 is connected to the liquid discharge flow path 16 for discharging the liquid (product), and is connected to the gas discharge flow path 17 for discharging the waste gas. The liquid discharge flow path 16 is provided with a needle valve 20. A back pressure valve 21 is provided in the gas discharge passage 17.

Next, a reaction method using the reaction apparatus 1 according to an embodiment of the present invention will be described below.
The raw material solution 18 is supplied from above the first column 3 a by the pump 13 via the first flow path 4. At the same time, the reaction gas 19 is supplied from above the second column 3 b via the second flow path 5. At this time, the flow rate of the raw material solution 18 is controlled to a constant amount by the pump 13. Further, the mass flow controller 11 controls the flow rate of the reaction gas 19 to a constant amount. Further, the control unit 8 causes the switching unit 7 to flow through the first flow passage 4 and the first column 3a, and causes the second flow passage 5 and the second column 3b to flow (see FIG. 2 (a). ))). First, the switching unit 7 is set to the first position, the raw material solution 18 is supplied to the first column 3a, and the reaction gas 19 is supplied to the second column 3b. The reaction gas 19 may be supplied to the first column 3a, and the raw material solution 18 may be supplied to the second column 3b.

  Then, after supplying the raw material solution 18 and the reaction gas 19 for a predetermined time, the control means 8 causes the first flow path 4 and the second column 3b to flow from the first position, and the second flow path 5 and the first column It switches to the 2nd position (refer FIG.2 (b)) which distribute | circulates with 3a. Thus, the raw material solution 18 supplied to the first column 3a is supplied to the second column 3b, and the reaction gas 19 supplied to the second column 3b is supplied to the first column 3a. Thereafter, the switching unit 7 is switched between the first position and the second position every predetermined time to alternately supply the raw material solution 18 and the reaction gas 19 to the first column 3a and the second column 3b (see FIG. 3).

  Then, the raw material solution 18 and the reaction gas 19 are chemically reacted via the immobilized catalyst 2 packed in the first column 3a and the second column 3b. At this time, the raw material solution 18 and the reaction gas 19 are layered in the first column 3a and the second column 3b (see FIG. 3), and at the boundary 22 (reaction surface) of each layer, the raw material solution 18 and the reaction gas 19 comes in contact and a chemical reaction occurs.

  Then, the gas and liquid obtained by the chemical reaction flow to the gas and liquid separation tank 15 through the third flow path 6. Thereafter, the liquid is sent to the outside through the liquid discharge flow path 16, and the waste gas is discharged through the gas discharge flow path 17.

  According to the reactor 1 of the embodiment having the above configuration, the following effects can be obtained. That is, the reaction apparatus 1 arranges the first column 3a and the second column 3b in parallel to expand the inner diameter of the first column 3a and the second column 3b, thereby generating the raw material solution 18 and the reaction gas 19 In the first column 3a and the second column 3b, it is possible to obtain the product of the chemical reaction between the raw material solution 18 and the reaction gas 19, while preventing the occurrence of the uneven flow of

  Further, according to the reaction device 1, the first flow path 4 for supplying the raw material solution 18 to the first column 3 a and the second column 3 b via the switching unit 7, and the second flow for supplying the reaction gas 19. A first position for connecting the passage 5 and connecting the switching unit 7 with the first passage 4 and the first column 3a and with the second passage 5 and the second column 3b; And the second position where the second flow path 5 and the first column 3a are in communication with each other. With this configuration, the reaction gas 19 is supplied to the second column 3b while the raw material solution 18 is supplied to the first column 3a, and the reaction gas 19 is supplied to the first column 3a. The raw material solution 18 can be supplied to the second column 3b. Moreover, by switching the supply state of these simultaneously by switching the first position and the second position in the switching unit 7, the raw material solution 18 flowing inside and the reaction gas flow in the first column 3a and the second column 3b. 19 alternate in layers with respect to their flow direction, and at the boundary 22 of each layer, the feed solution 18 and the reaction gas 19 contact. As a result, the boundary 22 of each layer becomes a reaction surface, the area of the reaction surface in the entire first column 3a and the second column 3b increases, and the reaction efficiency can be increased.

  Furthermore, according to the reaction device 1, since the switching unit 7 is switched to the first position and the second position to control the flowing direction of the raw material solution 18 and the reaction gas 19, the pump 13 can be always operated. It is possible to suppress the load due to the ON / OFF of the pump 13.

  According to the reaction apparatus 1, the raw material solution 18 and the reaction gas 19 are provided in the first column 3 a and the second column by providing the control unit 8 that switches the switching unit 7 between the first position and the second position every predetermined time. It is possible to control the time span supplied to 3b. Then, by setting the time span of switching of the first position and the second position in the switching unit 7 appropriately short, in the first column 3a and the second column 3b, the raw material solution 18 and the reaction gas 19 flowing inside are set. In the direction of their flow, they are alternately finely stratified in response to the temporal span of switching, and the feed solution 18 and the reaction gas 19 contact at the boundary 22 of each layer. As a result, the boundary 22 of the fine layers becomes the reaction surface, and the area of the reaction surface in the entire first column 3a and the second column 3b increases, so that the reaction efficiency between the raw material solution 18 and the reaction gas 19 is increased. It is possible to make it higher.

  According to the reaction apparatus 1, the switching unit 7 can simultaneously switch the flow directions of the raw material solution 18 and the reaction gas 19 with respect to the first column 3a and the second column 3b by using the 4-port 2-position directional control valve. It becomes.

  According to the reactor 1, the first column 3a and the second column 3b are filled with the immobilized catalyst 2 in which the catalyst (palladium) is supported on a spherical carrier (alumina carrier) having an average particle diameter of 20 μm to 3 mm. , Reaction of the raw material solution 18 and the reaction gas 19 flowing inside the first column 3a and the second column 3b without blocking the flow of the raw material solution 18 and the reaction gas 19 in the first column 3a and the second column 3b. In terms of surface, the catalyst can function to cause a chemical reaction between the feed solution 18 and the reaction gas 19.

  In the reaction apparatus 1 according to one embodiment, the switching unit 7 is an electromagnetic four-port two-position directional control valve. However, the raw material solution 18 may be formed using other valves such as a solenoid valve, a pinch valve, and a rotary valve. The flow direction of the reaction gas 19 may be switched.

  In the reaction method using the reactor 1 according to one embodiment, the raw material solution 18 and the reaction gas 19 are supplied from above the first column 3a and the second column 3b. It may be supplied from the lower side of the two columns 3b.

  In addition, although the internal diameter of the 1st column 3a and the 2nd column 3b is 32 mm in the reaction method using the reaction apparatus 1 which concerns on the Example demonstrated below, you may use that whose internal diameter is 15 mm-100 mm.

  In addition, in the reaction method using the reaction apparatus 1 according to the embodiment described below, the immobilized catalyst 2 is one in which palladium is supported on a spherical alumina carrier having an average particle diameter of 80 μm having a polysilane coating layer, The catalyst is not particularly limited as long as it is an immobilized catalyst having an average particle diameter of 20 μm to 3 mm for smoothly advancing the desired reaction, and may be a mixture with solid particles that do not affect the reaction such as celite or glass beads.

  Hereinafter, the reaction method using the reaction device 1 according to an embodiment of the present invention will be described by way of examples.

Example 1
The conditions of Example 1 are as follows. The first column 3a and the second column 3b have an inner diameter of 32 mm, and have a column temperature of 20.degree. The immobilized catalyst 2 is a palladium catalyst in which palladium is supported on a spherical alumina carrier having an average particle diameter of 80 μm and having a polysilane coating layer in the first column 3a and the second column 3b (JPG catalysis, trade name PPD -200A80) Charge 84.0 g. The raw material solution 18 uses a 0.4 mol / L benzonitrile solution in which 123.7 g of benzonitrile, 2164 g of methanol, and 162.6 g of 35% by mass hydrochloric acid are mixed. Also, hydrogen gas is used as the reaction gas 19. Furthermore, the benzonitrile solution is passed through the reactor 1 at 100 mL per minute (100 mL / min). Further, hydrogen gas is allowed to flow through the reactor 1 at 2.87 mL per minute (0 ° C., converted to 1 atm). The switching interval of the switching unit 7 by the control means 8 is 5 seconds.

The benzonitrile solution is supplied from above the first column 3 a by the pump 13 via the first flow path 4. At the same time, hydrogen gas is supplied from above the second column 3 b via the second flow path 5. Further, the control unit 8 sets the switching unit 7 to the first position. Then, after the benzonitrile solution and the hydrogen gas are supplied for a predetermined time, the control means 8 switches from the first position to the second position. Thereafter, the switching unit 7 is switched between the first position and the second position every 5 seconds to alternately supply the benzonitrile solution and the hydrogen gas to the first column 3a and the second column 3b. Then, benzonitrile solution and hydrogen gas are brought into contact and chemically reacted at the boundary 22 (reaction surface) of each layer via the palladium catalyst packed in the first column 3a and the second column 3b. Then, gas and liquid obtained by causing a chemical reaction flow to the gas and liquid separation tank 15 through the third flow path 6. Thereafter, the liquid obtained from the gas-liquid separation tank 15 is collected via the liquid discharge channel 16 for 5 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol for high performance liquid chromatography (hereinafter referred to as As a result of performing quantitative analysis by HPLC), the collection rate of benzylamine was 88%.
The details of the quantitative analysis conditions by HPLC are described below.
Equipment used: 1290 Infinity Technology by Agilent Technology
Injection volume: 0.5 μL
Eluent: 0.2% by volume aqueous acetic acid / methanol = 60/40
Flow rate: 0.50 mL / min Column: Kinetex F5 (2.6 μm, 100 mm × 2.1 mm) Phenomenex Column temperature: 40 ° C.
Detector: UV 254 nm
Holding time: benzylamine 0.53 min, benzonitrile 1.45 min
A reagent special grade (B0406) manufactured by Tokyo Chemical Industry Co., Ltd. was used as a standard product of benzylamine.

[Reference Example 1]
Hereinafter, a reaction method using the reaction apparatus 101 shown in FIG. 4 will be described with reference to Reference Example 1. The conditions of Reference Example 1 are as follows.
The column 102 has an inner diameter of 32 mm and a column temperature of 20 ° C. The immobilized catalyst is packed in a column 102 with 84.0 g of a palladium catalyst (Nikko catalysis, trade name PPD-200A80) having palladium supported on a spherical alumina support having an average particle diameter of 80 μm having a polysilane coating layer. Do. The raw material solution 103 uses a 0.4 mol / L benzonitrile solution in which 123.7 g of benzonitrile, 2164 g of methanol, and 162.6 g of 35 mass% hydrochloric acid are mixed. Also, as the reaction gas 105, hydrogen gas is used. Furthermore, the benzonitrile solution is passed through the reactor 1 at 50 mL (50 mL / min) per minute. Further, hydrogen gas is circulated in the reactor 1 at a rate of 1.43 mL (0 ° C., 1 atm. State conversion) per minute. The benzonitrile solution is passed through the column 102 at 50 mL / min and hydrogen gas at 1.43 L / min.

  The benzonitrile solution and hydrogen gas are simultaneously supplied from above the column 102 through the flow path 107 by the pump 104 and the mass flow controller 106. Then, a benzonitrile solution and hydrogen gas are brought into contact with each other via a palladium catalyst packed in the first column 3a and the second column 3b to cause a chemical reaction. Then, gas and liquid obtained by causing a chemical reaction flow into the gas and liquid separation tank 109. Thereafter, the liquid obtained from the gas-liquid separation tank 109 is collected for 5 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol and quantitative analysis is performed by HPLC. As a result, the collection rate of benzylamine is It was 60%. The conditions for quantitative analysis by HPLC were the same as those described in Example 1 above.

  As apparent from the comparison of Example 1 and Reference Example 1 described above, in Example 1, the collection rate of benzylamine was 88%, and in Reference Example 1, the collection rate of benzylamine was 60%. Thus, according to Example 1 of the present invention, it has become clear that the reaction efficiency between the benzonitrile solution and hydrogen gas becomes high.

Example 2
The conditions of Example 2 are as follows. The first column 3a and the second column 3b have an inner diameter of 32 mm, and have a column temperature of 100.degree. The immobilized catalyst 2 is a palladium catalyst in which palladium is supported on a spherical alumina carrier having an average particle diameter of 80 μm and having a polysilane coating layer in the first column 3a and the second column 3b (JPG catalysis, trade name PPD -200A80) Charge 28.0 g. Raw material solution 18 is 0.7 mol / L prepared by mixing 875.7 g of N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide, 3196 g of methanol, and 474.0 g of 35 mass% hydrochloric acid. A solution of N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide is used. Also, hydrogen gas is used as the reaction gas 19. Furthermore, the N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution is circulated to the reaction device 1 at 33.3 mL (33.3 mL / min) per minute. Further, hydrogen gas is allowed to flow through the reactor 1 at a rate of 1.67 L per minute (0 ° C., converted to 1 atm). The switching interval of the switching unit 7 by the control means 8 is 10 seconds.

The N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution is supplied from above the first column 3 a by the pump 13 via the first flow path 4. At the same time, hydrogen gas is supplied from above the second column 3 b via the second flow path 5. Further, the control unit 8 sets the switching unit 7 to the first position. Then, after the N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution and hydrogen gas are supplied for a predetermined time, the control means 8 switches from the first position to the second position. Thereafter, the switching unit 7 is switched between the first position and the second position every 10 seconds, and the N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfone is applied to the first column 3a and the second column 3b. The amide solution and hydrogen gas are alternately supplied. Then, N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide is formed at the boundary 22 (reaction surface) of each layer via the palladium catalyst packed in the first column 3a and the second column 3b. The solution and hydrogen gas are brought into contact and chemically reacted. Then, gas and liquid obtained by causing a chemical reaction flow to the gas and liquid separation tank 15 through the third flow path 6. Thereafter, the liquid obtained from the gas-liquid separation tank 15 is collected via the liquid discharge flow path 16 for 9 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol and quantitative analysis is performed by HPLC. As a result, the collection rate of N- [2- (aminomethyl) phenyl] -1,1,1-trifluoromethanesulfonamide was 97%.
The details of the quantitative analysis conditions by HPLC are described below.
Equipment used: 1290 Infinity Technology by Agilent Technology
Injection volume: 0.5 μL
Eluent: 0.2% by volume aqueous acetic acid / methanol = 60/40
Flow rate: 0.50 mL / min Column: Kinetex F5 (2.6 μm, 100 mm × 2.1 mm) Phenomenex Column temperature: 40 ° C.
Detector: UV 254 nm
Retention time: N- [2- (aminomethyl) phenyl] -1,1,1-trifluoromethanesulfonamide 0.78 min, N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide 1. 00 min
The standard product of N- [2- (aminomethyl) phenyl] -1,1,1-trifluoromethanesulfonamide is synthesized according to any of the methods described in Reference Examples 7 to 9 of WO 2015/060402. Used.

[Reference Example 2]
Hereinafter, a reaction method using the reaction apparatus 101 shown in FIG. 4 will be described with reference to Reference Example 2. The conditions of Reference Example 2 are as follows.
The column 102 has an inner diameter of 32 mm and a column temperature of 100 ° C. In the column 102, the immobilized catalyst is packed with 28.0 g of a palladium catalyst (Nikko catalysis, trade name: PPD-200A80) having palladium supported on a spherical alumina carrier having an average particle diameter of 80 μm having a polysilane coating layer. Do. 0.7 mol / L N- (2-) obtained by mixing 875.7 g of N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide, 3196 g of methanol, and 474.0 g of 35 mass% hydrochloric acid A cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution is used. Also, as the reaction gas 105, hydrogen gas is used. Furthermore, the N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution is passed through the reactor 1 at 16.7 mL (16.7 mL / min) per minute. Further, hydrogen gas is allowed to flow through the reactor 1 at a rate of 0.84 L (0 ° C., converted to one atmospheric pressure) per minute. The solution of N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide is passed through the column 102 at 16.7 mL / min and hydrogen gas at 0.84 L / min.

  The N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution and hydrogen gas are simultaneously supplied from the upper side of the column 102 through the flow path 107 by the pump 104 and the mass flow controller 106. Then, N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution and hydrogen gas are brought into contact with each other through the palladium catalyst packed in the first column 3a and the second column 3b, and the chemical reaction is caused. Let Then, gas and liquid obtained by causing a chemical reaction flow into the gas and liquid separation tank 109. Thereafter, the liquid obtained from the gas-liquid separation tank 109 is collected for 9 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol and quantitative analysis is performed by HPLC. The collection rate of aminomethyl) phenyl] -1,1,1-trifluoromethanesulfonamide was 68%. The conditions for quantitative analysis by HPLC were the same as those described in Example 2 above.

  As is clear from the comparison of Example 2 and Reference Example 2 described above, in Example 2, the collection rate of N- [2- (aminomethyl) phenyl] -1,1,1-trifluoromethanesulfonamide is 97%. In Reference Example 2, the collection rate of N- [2- (aminomethyl) phenyl] -1,1,1-trifluoromethanesulfonamide was 68%. Thus, according to Example 2 of the present invention, it has become clear that the reaction efficiency of the N- (2-cyanophenyl) -1,1,1-trifluoromethanesulfonamide solution with hydrogen gas becomes high.

[Example 3]
The conditions of Example 3 are as follows. The first column 3a and the second column 3b have an inner diameter of 35 mm, and have a column temperature of 25.degree. The immobilized catalyst 2 is a palladium catalyst in which palladium is supported on a spherical alumina carrier having an average particle diameter of 40 μm having a polysilane coating layer in the first column 3a and the second column 3b (JPG catalysis, trade name PPD -60) Charge 29.8 g. The raw material solution 18 uses a 0.7 mol / L styrene solution in which 109.4 g of styrene and 1191 g of toluene are mixed. Also, hydrogen gas is used as the reaction gas 19. Furthermore, the styrene solution is passed through the reactor 1 at 45.3 mL (45.3 mL / min) per minute. Further, hydrogen gas is allowed to flow through the reactor 1 at 920 mL per minute (0 ° C., converted to 1 atm). The switching interval of the switching unit 7 by the control means 8 is 9 seconds.

The styrene solution is supplied from above the first column 3 a by the pump 13 via the first flow path 4. At the same time, hydrogen gas is supplied from above the second column 3 b via the second flow path 5. Further, the control unit 8 sets the switching unit 7 to the first position. Then, after supplying a styrene solution and hydrogen gas for a predetermined time, the control means 8 switches from the first position to the second position. Thereafter, the switching unit 7 is switched between the first position and the second position every 9 seconds to alternately supply the styrene solution and the hydrogen gas to the first column 3a and the second column 3b. Then, a styrene solution and hydrogen gas are brought into contact and chemically reacted at the boundary 22 (reaction surface) of each layer via the palladium catalyst packed in the first column 3a and the second column 3b. Then, gas and liquid obtained by causing a chemical reaction flow to the gas and liquid separation tank 15 through the third flow path 6. Thereafter, the liquid obtained from the gas-liquid separation tank 15 is collected via the liquid discharge channel 16 for 5 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol for gas chromatography (hereinafter referred to as GC) As a result of area percentage analysis, the area percentage of ethylbenzene is 100% (solvent toluene, dilution solvent other than methanol).
The details of analysis conditions by GC are described below.
Equipment used: 7890B manufactured by Agilent Technology
Injection volume: 0.5 μL
Injection temperature: 250 ° C
He linear velocity: 31 cm / sec Column: ZB-5MS plus (0.18 μm, 0.18 mm × 20 m) Phenomenex column temperature: 50 ° C. (5 min) → 30 ° C./min→160° C. (0 min)
Detector: FID
Detector temperature: 300 ° C
Holding time: Ethyl benzene 4.66 min, styrene 5.50 min
A reagent special grade (E0064) manufactured by Tokyo Chemical Industry Co., Ltd. was used as a standard product of ethylbenzene.

[Reference Example 3]
Hereinafter, a reaction method using the reaction device 101 shown in FIG. 4 will be described with reference to Reference Example 3. The conditions of Reference Example 3 are as follows.
The column 102 has an inner diameter of 35 mm and a column temperature of 25 ° C. In the column 102, the immobilized catalyst is packed with 29.8 g of a palladium catalyst (JGC catalyst formation, trade name: PPD-60) having palladium supported on a spherical alumina carrier having an average particle diameter of 40 μm having a polysilane coating layer. Do. The raw material solution 103 uses a 0.7 mol / L styrene solution in which 109.4 g of styrene and 1191 g of toluene are mixed. Also, as the reaction gas 105, hydrogen gas is used. Furthermore, the styrene solution is passed through the reactor 1 at a rate of 22.6 mL (22.6 mL / min) per minute. Further, hydrogen gas is allowed to flow through the reactor 1 at a rate of 460 mL (0 ° C., 1 atm. State conversion) per minute. The styrene solution is allowed to flow through the column 102 at 22.6 mL / min and hydrogen gas at 460 mL / min.

  The styrene solution and hydrogen gas are simultaneously supplied from above the column 102 through the flow path 107 by the pump 104 and the mass flow controller 106. Then, a styrene solution and hydrogen gas are brought into contact with each other via a palladium catalyst packed in the first column 3a and the second column 3b to cause a chemical reaction. Then, gas and liquid obtained by causing a chemical reaction flow into the gas and liquid separation tank 109. Thereafter, the liquid obtained from the gas-liquid separation tank 109 is collected for 6 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol and area percentage analysis is performed by GC. It was 86.3% (solvent toluene, diluted solvent other than methanol). When the flow was continued after 6 minutes, the pressure increased to 0.9 MPa, and the flow could not be continued continuously. The area percentage analysis conditions by GC were the same as the conditions described in Example 3 above.

  As apparent from the comparison of Example 3 and Reference Example 3 described above, in Example 3, the area percentage of ethylbenzene was 100%, and in Reference Example 3, the area percentage of ethylbenzene was 86.3%. Thus, according to Example 3 of the present invention, it has become clear that the reaction efficiency between the styrene solution and hydrogen gas becomes high.

Example 4
The conditions of Example 4 are as follows. The first column 3a and the second column 3b have an inner diameter of 35 mm, and have a column temperature of 25.degree. The immobilized catalyst 2 is a palladium catalyst in which palladium is supported on a spherical alumina carrier having an average particle diameter of 40 μm having a polysilane coating layer in the first column 3a and the second column 3b (JPG catalysis, trade name PPD -60) Charge 29.8 g. The raw material solution 18 uses a 0.7 mol / L nitrobenzene solution in which 38.79 g of nitrobenzene and 361.0 g of toluene are mixed. Also, hydrogen gas is used as the reaction gas 19. Furthermore, the nitrobenzene solution is passed through the reactor 1 at 20.0 mL (20.0 mL / min) per minute. Further, hydrogen gas is allowed to flow through the reactor 1 at a rate of 1.22 L per minute (0 ° C., converted to 1 atm). The switching interval of the switching unit 7 by the control means 8 is 20 seconds.

The nitrobenzene solution is supplied from above the first column 3 a by the pump 13 via the first flow path 4. At the same time, hydrogen gas is supplied from above the second column 3 b via the second flow path 5. Further, the control unit 8 sets the switching unit 7 to the first position. Then, after the nitrobenzene solution and the hydrogen gas are supplied for a predetermined time, the control means 8 switches from the first position to the second position. Thereafter, the switching unit 7 is switched between the first position and the second position every 20 seconds to alternately supply the nitrobenzene solution and the hydrogen gas to the first column 3a and the second column 3b. Then, a nitrobenzene solution and hydrogen gas are brought into contact and chemically reacted at the boundary 22 (reaction surface) of each layer via the palladium catalyst packed in the first column 3a and the second column 3b. Then, gas and liquid obtained by causing a chemical reaction flow to the gas and liquid separation tank 15 through the third flow path 6. Thereafter, the liquid obtained from the gas-liquid separation tank 15 is collected via the liquid discharge channel 16 for 7 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol for quantitative analysis by HPLC. As a result, the collection rate of aniline was 75%.
The details of analytical conditions by HPLC are described below.
Equipment used: 1290 Infinity II manufactured by Agilent Technology
Injection volume: 0.5 μL
Eluent: 0.2% by volume aqueous acetic acid / methanol = 30/70
Flow rate: 0.50 mL / min Column: YMC-Triart C18 (1.9 μm, 100 mm × 2.1 mm) YMC column temperature: 40 ° C.
Detector: UV 254 nm
Holding time: aniline 0.68 min, nitrobenzene 1.14 min
As a standard product of aniline, a special grade reagent (019-03996) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used.

[Reference Example 4]
Hereinafter, a reaction method using the reaction device 101 shown in FIG. 4 will be described with reference to Reference Example 4. The conditions of Reference Example 4 are as follows.
The column 102 has an inner diameter of 35 mm and a column temperature of 25 ° C. In the column 102, the immobilized catalyst is packed with 29.8 g of a palladium catalyst (JGC catalyst formation, trade name: PPD-60) having palladium supported on a spherical alumina carrier having an average particle diameter of 40 μm having a polysilane coating layer. Do. The raw material solution 103 uses a 0.7 mol / L styrene solution in which 109.4 g of styrene and 1191 g of toluene are mixed. Also, as the reaction gas 105, hydrogen gas is used. Further, the styrene solution is passed through the reactor 1 at 10.0 mL per minute (10.0 mL / min). Further, hydrogen gas is allowed to flow through the reactor 1 at a rate of 0.61 L per minute (0 ° C., converted to 1 atm). The styrene solution is allowed to flow through the column 102 at 10.0 mL / min and hydrogen gas at 0.61 L / min.

  The nitrobenzene solution and hydrogen gas are simultaneously supplied from above the column 102 through the flow path 107 by the pump 104 and the mass flow controller 106. Then, a nitrobenzene solution and hydrogen gas are brought into contact with each other via a palladium catalyst packed in the first column 3a and the second column 3b to cause a chemical reaction. Then, gas and liquid obtained by causing a chemical reaction flow into the gas and liquid separation tank 109. Thereafter, the liquid obtained from the gas-liquid separation tank 109 is collected for 12 minutes after reaching equilibrium, and about 10 μL is diluted in 1 mL of methanol and quantitative analysis is performed by HPLC. As a result, the collection rate of aniline is 32 %Met. The conditions for quantitative analysis by HPLC were the same as those described in Example 4 above.

  As is clear from the comparison of Example 4 and Reference Example 4 described above, in Example 4, the collection rate of aniline was 75%, and in Reference Example 4, the collection rate of aniline was 32%. Thus, according to Example 4 of the present invention, it has become clear that the reaction efficiency between the nitrobenzene solution and hydrogen gas becomes high.

  DESCRIPTION OF SYMBOLS 1 ... Reaction apparatus, 2 ... Immobilization catalyst, 3 ... Column, 3a ... 1st column, 3b ... 2nd column, 4 ... 1st flow path, 5 ... 2nd flow path, 7 ... Switching part, 18 ... Raw material solution , 19 ... reactive gas

Claims (9)

A reaction method using a trickle bed reactor in which a raw material solution and a reaction gas are caused to flow through a column packed with an immobilized catalyst to cause a chemical reaction,
Place the first and second columns in parallel,
A reaction method characterized in that supply of a raw material solution or reaction gas is alternately performed at predetermined time intervals to each of the first column and the second column. A first flow path for supplying a raw material solution and a second flow path for supplying a reaction gas are connected to the first column and the second column via a switching unit,
The switching portion communicates a first flow path with the first column and communicates a second flow path with the second column, the first flow path, and the second column. And a second position for communicating the second flow path and the first column, and alternately switching the first position and the second position to form the first column and the second position. The reaction method according to claim 1, wherein a raw material solution or a reaction gas is supplied to each of the two columns.   The reaction method according to claim 2, wherein the switching unit comprises control means for switching between the first position and the second position every predetermined time.   The reaction method according to claim 2 or 3, wherein a four-port two-position directional control valve is used for the switching unit.   The reaction according to any one of claims 1 to 4, wherein an immobilized catalyst having a catalyst supported on a carrier having an average particle diameter of 20 m to 3 mm is packed into the first column and the second column. Method. A reactor comprising a trickle bed reactor in which a raw material solution and a reaction gas are caused to flow through a column packed with an immobilized catalyst to cause a chemical reaction,
First and second columns arranged in parallel,
A first flow path for supplying a raw material solution to the first column and the second column;
A second flow path for supplying a reaction gas to the first column and the second column;
The first flow channel and the second flow channel are disposed between the first column and the second column, and the first flow channel and the first column are in communication with each other and the second flow channel. It has a first position communicating the second column, or a second position communicating the first channel and the second column and communicating the second channel and the first column. A reaction apparatus comprising at least a switching unit capable of alternately switching between the first position and the second position.   The reaction device according to claim 6, further comprising: control means for switching the switching unit between the first position and the second position every predetermined time.   The reaction device according to claim 6 or 7, wherein the switching unit is a four-port two-position directional control valve.   9. The immobilized catalyst packed in the first column and the second column, wherein the catalyst is supported on a carrier having an average particle diameter of 20 μm to 3 mm. Reactor as described in paragraph.