JP4440862B2 - Methyl iodide production equipment - Google Patents

Description

  The present invention relates to an apparatus for producing methyl iodide.

Conventionally, as a production apparatus for methyl iodide ( ¹¹ CH ₃ I), which is a radiopharmaceutical labeling precursor, ¹¹ CH ₄ is added in the circulation path, ¹¹ CH ₄ is reacted with iodine and ¹¹ CH ₃ is reacted. A reactor for generating I and a collector for collecting the generated ¹¹ CH ₃ I are provided in this order, and an unreacted ¹¹ CH ₄ is reused while circulating an inert gas serving as a carrier gas by a pump means. An apparatus that generates ¹¹ CH ₃ I is known (see, for example, Patent Document 1).
Japanese National Patent Publication No. 10-509449

  However, in the conventional apparatus, since the gas is circulated by the pump means which is a movable member, iodine or the like is deposited on the pump means and causes a failure.

The present invention has been made in view of the above problems, without using the pump means, and an object of the invention to provide a methyl iodide manufacturing apparatus can be effectively utilized ¹¹ CH _4.

Methyl iodide manufacturing apparatus according to the present invention, the inert gas flow path to which the inert gas is supplied from the inert gas source, and capable of supplying methane supply the ¹¹ CH ₄ in an inert gas flow path, ¹¹ , CH _4, methyl iodide generator for generating a ^{11 CH} 3 _I by reacting iodine, methyl iodide collector for collecting the ^{11 CH} 3 _I, and can accommodate chamber gas, an inert gas A first state in which a flow path, a methyl iodide generator, a methyl iodide collector, and a chamber are connected in series in this order, an inert gas flow path, a chamber, a methyl iodide generator, and a methyl iodide collection And a flow path switch that selectively switches between the second states in which the devices are connected in series in this order.

According to the present invention, first, set the flow channel switching device in the first state, when supplying ¹¹ CH ₄ in an inert gas flow path from methane feeder, ¹¹ CH ₄ and inert gas as a carrier gas is not ¹¹ CH ₃ I is supplied to the methyl iodide generator from the active gas flow path, and the generated ¹¹ CH ₃ I is adsorbed to the methyl iodide collector, while unreacted. ¹¹ CH ₄ passes through the methyl iodide collector and is accommodated in the chamber.

Subsequently, when the flow path switch is switched to the second state, the gas in the chamber, that is, unreacted ¹¹ CH ₄ is iodinated again by the inert gas as the carrier gas supplied from the inert gas flow path. It is supplied to the methyl generator, and ¹¹ CH ₃ I is further generated in the methyl iodide generator, and the generated ¹¹ CH ₃ I is adsorbed to the methyl iodide collector.

Therefore, unreacted ¹¹ CH ₄ discharged from the methyl iodide generator can be returned from the chamber to the methyl iodide generator and reused without using a pump means.

Here, the methane feeder preferably includes a methane adsorption column filled with an adsorbent that adsorbs ¹¹ CH ₄ and a heater that heats the methane adsorption column and desorbs ¹¹ CH ₄ from the adsorbent.

According to this, by using a highly selective adsorbents for ¹¹ CH _4, it is easy to supply the high purity ¹¹ CH ₄ in an inert gas flow path.

The methane generator further includes a methane generator that reacts ¹¹ CO ₂ and H ₂ to generate ¹¹ CH ₄ , the methane generator is connected to the methane adsorption column, and the inert gas from the inert gas supply source to the methane generator. Is preferably supplied.

According to this, ¹¹ CH ₄ can be generated from ¹¹ CO ₂ on the spot, and the generated ¹¹ CH ₄ can be transferred by the inert gas and adsorbed on the adsorbent of the methane adsorption column.

  Moreover, it is preferable that an inert gas flow path further has a bypass line which bypasses a methane feeder.

  According to this, when the flow path switching device is in the second state and it is not necessary to supply methane from the methane supply device, the inert gas flows from the inert gas flow channel bypassing the methane supply device. Therefore, the cleanliness of the inert gas is improved, which is preferable.

  Furthermore, it is preferable to have a so-called six-way valve as the flow path switching device, thereby reducing the cost and simplifying the operation.

According to the present invention, an apparatus for producing methyl iodide that does not use pump means and can effectively use ¹¹ CH ₄ is realized.

  Hereinafter, a preferred embodiment of a methyl iodide production apparatus according to the present invention will be described with reference to FIG. FIG. 1 is a schematic configuration diagram showing an apparatus for producing methyl iodide according to an embodiment of the present invention. In the following description of the drawings, the same or equivalent elements will be denoted by the same reference numerals, and redundant description will be omitted.

As shown in FIG. 1, the methyl iodide production apparatus 100 of the present embodiment includes ¹¹ CH ₃ I, which is a radiopharmaceutical label precursor used in, for example, a PET examination (positron emission tomography examination) in a hospital or the like. This is an apparatus for producing methyl iodide. If necessary, ¹¹ CH ₃ OTf can be further generated from the generated ¹¹ CH ₃ I.

This methyl iodide production apparatus 100 is roughly composed of an inert gas flow path 1 to which an inert gas is supplied, a methane feeder 2 for supplying ¹¹ CH ₄ to the inert gas flow path 1, ¹¹ CH ₄ and iodine. with methyl iodide generator 3 for generating a ^{11 CH} 3 _I by reacting, with methyl iodide collector 4 for collecting the synthesized ^{11 CH} 3 _I, and can accommodate chamber 5 gas, flow of gas And a six-way valve 80 for switching the path.

The inert gas flow path 1 has a line L1 having one end connected to a helium supply source S1 (for example, He cylinder) as an inert gas and the other end connected to the opening a of the six-way valve 80. It is. The pressure gauge 20, the mass flow controller 10, the valve V7, the CO ₂ adsorption column 72, the methane feeder 2, the three-way valve V9, and the three-way valve V10 are connected to the line L1 in this order from the upstream side. .

As the CO ₂ adsorption column, a column filled with a filler mainly composed of alkali such as caustic soda or soda lime such as Ascarite II can be used.

The methane feeder 2 has a methane adsorption column 44 and a temperature controller (heater) 46 that can heat and cool the methane adsorption column 44. As the temperature controller, for example, an electric heater and preferably one having an air cooling fan can be used. The adsorbent in the methane adsorption column 44 is not particularly limited as long as it selectively adsorbs ¹¹ CH _4. For example, 60-80 mesh Carbosphere (registered trademark) can be used. For example, when the adsorbent in the methane adsorption column 44 is brought to room temperature by the temperature controller 46, ¹¹ CH ₄ is selectively adsorbed to the adsorbent, while, for example, when the adsorbent is brought to a high temperature of about 120 to 130 ° C. since the adsorbent ¹¹ CH ₄ is released, the inert gas flow path 1 can supply the ¹¹ CH ₄ into a high purity.

  An exhaust gas line L8 is connected to the other opening of the three-way valve V9.

  A bypass line L7 that bypasses the methane feeder 2 is branched from the mass flow controller 10 and the valve V7 in the line L1, and the bypass line L7 is connected to another opening of the three-way valve V10. A valve V8 is connected to the line L7. In the present embodiment, the line L1 and the bypass line L7 constitute the inert gas flow path 1.

  In addition, a radiation sensor RI3 that measures radiation intensity emitted from the substance flowing through the line L1 is installed between the three-way valve V9 and the three-way valve V10 in the line L1.

A line L2 branches from between the valve V7 and the CO ₂ adsorption column 72 in the line L1, and this line L2 is connected to a part upstream of the pressure gauge 20 in the line L1. A pressure gauge 16, a flow meter 12, a valve V1, a valve V4, a methane generator 6, a valve V5, and a three-way valve V6 are connected to the line L2 in order from the upstream side.

Further, a line L3 and a line L4 branch from between the valve V1 and the valve V4 in the line L2, and are connected to the hydrogen supply source S2 and the ¹¹ CO ₂ supply source S3, respectively. The hydrogen supply source S2 is connected to, for example, a hydrogen cylinder, and the supply source S3 is connected to a target container that produces ¹¹ CO ₂ by, for example, a cyclotron (not shown).

  A pressure gauge 18, a flow meter 14, and a valve V2 are connected to the line L3 in this order from the upstream side. A valve V3 is connected to the line L4.

The methane generator 6 includes a methane generation column 40 filled with a reduction catalyst, and a temperature controller 42 that can heat and cool the methane generation column 40. At room temperature on a reducing catalyst to adsorb ¹¹ CO _2, then, by heating the reduced catalyst in order 440-460 ° C. in the presence of ^hydrogen, it is possible to react the 11 CO ₂ and hydrogen ¹¹ CH ₄ Produces. As the reduction catalyst, for example, 50-80 mesh Shimalite Ni can be used.

  The methane generator 6 is provided with a radiation sensor RI <b> 1 that measures the radiation intensity radiated from the reduction catalyst in the methane generation column 40.

An exhaust gas line L5 is connected to the other end of the three-way valve V6, and a CO ₂ adsorption column 70 is connected to the exhaust gas line L5.

  Subsequently, the six-way valve 80 will be described. The six-way valve 80 is a valve having openings a to f, and is in a first state in which the opening b and the opening c are communicated, the opening d and the opening e are communicated, and the opening a and the opening f are communicated. And a second state in which the opening a and the opening b communicate with each other, the opening c and the opening d communicate with each other, and the opening e and the opening f communicate with each other.

  As described above, the other end of the line L1 is connected to the opening a of the six-way valve 80. One end of a line L12 is connected to the opening b of the six-way valve 80, and the other end of the line L12 is connected to the opening e.

The chamber 5 is connected to the line L12. The chamber 5 is an empty column having a predetermined capacity and capable of storing gas. In the present embodiment, a tube having a diameter larger than that of the line L12 is adopted as the chamber 5, but it is only necessary to have a predetermined capacity. For example, even if the line L12 itself is sufficiently long, the chamber 5 Can function. The capacity of the chamber 5 is preferably about 1 to 2 times the total volume of the iodine vaporizing column 50 and the methyl iodide generating column 52 as a necessary volume for obtaining the switching time of the six-way valve 80. The chamber 5 may be filled with an adsorbent that adsorbs ¹¹ CH ₄ . In this case, the capacity of the chamber 5 is smaller than that in the case of using an empty column, but it is necessary to provide a temperature controller 82 for heating the chamber 5 in order to desorb ¹¹ CH ₄ from the adsorbent after adsorption. is there. In addition, a radiation sensor RI2 that measures the radiation intensity emitted from the portion of the line L12 closer to the opening e than the chamber 5 is provided.

One end of the line L10 is connected to the opening c of the six-way valve 80, and the other end of the line L10 is connected to the opening f. The methyl iodide generator 3, the CO ₂ adsorption column 74, and the methyl iodide collector 4 are connected to the line L10 in order from the opening f to the opening c.

  The methyl iodide generator 3 includes an iodine vaporization column 50 provided on the upstream side (opening f side), a methyl iodide production column 52 provided on the downstream side (opening c side) from the iodine vaporization column 50, A temperature controller 51 for heating and cooling the iodine vaporizing column 50 and a temperature controller 54 for heating and cooling the methyl iodide generation column 52 are provided.

  The iodine vaporization column 50 is filled with solid iodine in advance, and iodine gas is supplied into the line L10 by heating the iodine vaporization column 50 to about 70 to 95 ° C. by the temperature controller 51.

The methyl iodide production column 52 is a reaction tube made of glass or the like. For example, by heating the methyl iodide generation column 52 to about 650 to 750 ° C. by the temperature controller 54, iodine and ¹¹ CH ₄ are reacted in the methyl iodide generation column 52 to generate ¹¹ CH ₃ I.

  The methyl iodide collector 4 includes a methyl iodide adsorption column 56 and a temperature controller 58 that heats and cools the methyl iodide adsorption column 56.

The methyl iodide adsorption column 56 is a column filled with an adsorbent that selectively adsorbs ¹¹ CH ₃ I from a mixture of ¹¹ CH ₃ I and unreacted ¹¹ CH ₄ . The adsorbent is not particularly limited, and for example, 50-80 mesh Porapack N can be used. Then, for example, the methyl iodide adsorption column 56 is brought to room temperature by the temperature controller 62 and ¹¹ CH ₃ I is selectively adsorbed on the adsorbent from the mixed gas, and then the methyl iodide adsorption column by the temperature controller 58. For example, ¹¹ CH ₃ I can be desorbed from the adsorbent by heating 56 to 180 to 200 ° C.

  The methyl iodide adsorption column 56 is provided with a radiation sensor RI4 that detects the intensity of radiation emitted from the adsorbed substance.

  A line L14 is connected to the opening d of the six-way valve 80. A three-way valve V11, a three-way valve V12, and a valve V14 are connected to the line L14 in order from the opening d side. Both ends of the bypass line L16 are connected to the other end of the three-way valve V11 and the other end of the three-way valve V12. A triflate generator 8 is connected to the bypass line L16.

The triflate generator 8 includes a triflate production column 60 filled with AgOTf (Silver trifluoromethanesulfonate), and a temperature controller 62 that can heat and cool the triflate production column 60. If the upstream from the ¹¹ CH ₃ I is supplied, the triflate product column 60 by the temperature controller 62 for example, when heated to about 200-230 ° ^C., a 11 CH ₃ I methyl triflate ⁽¹¹ _CH 3 OTf) Can be converted.

^Thus, 11 CH ₃ so as not to flow gas to the bypass line L16 if you want the I the final product, ^whereas, when it ^is desired to the final product 11 CH ₃ I is not ¹¹ CH ₃ OTf, the bypass line The gas flowing in the line L14 may be made to flow to the triflate generator 8 by L16.

  An exhaust gas line L18 branches from between the valve V12 and the valve V14 in the line L14. The exhaust gas line L18 has a valve V13.

  In summary, the six-way valve 80 forms a first flow path that connects the inert gas flow path 1, the methyl iodide generator 3, the methyl iodide collector 4, and the chamber 5 in series in this order. And a second state that forms a second flow path that connects the inert gas flow path 1, the chamber 5, the methyl iodide generator 3, and the methyl iodide collector 4 in series in this order. It is a flow path switching device that switches automatically.

Next, a method of synthesizing ¹¹ CH ₃ I or ¹¹ CH ₃ OTf using the thus configured methyl iodide production apparatus 100 will be described with reference to FIGS. It should be noted that a black portion in the valve means a closed state, and a white portion in the valve means an open state.

This methyl iodide production method is roughly composed of an ¹¹ CH ₄ production step for producing ¹¹ CH ₄ from ¹¹ CO _2, an ¹¹ CH ₄ purification step for purifying the produced ¹¹ CH ₄ by adsorption, and a purified ¹¹ CH ₄ and supplies the methyl iodide generator generates a ¹¹ CH ₃ I, the resulting ¹¹ CH ₃ I is adsorbed methyl iodide adsorber, the ¹¹ CH ₄ and unreacted first reaction step to be accommodated in the chamber 5 a second reaction step of adsorbing is supplied to the re-methyl iodide generator ¹¹ CH ₄ unreacted chamber 5 generates a ¹¹ CH ₃ I, the resulting ¹¹ CH ₃ I methyl iodide adsorber Then, ¹¹ CH ₃ I is desorbed from the methyl iodide adsorber, and if necessary, ¹¹ CH ₃ I is converted to ¹¹ CH ₃ OTf and then discharged out of the system.

  First, all the valves are closed in advance, and the six-way valve 80 is set to the first state. Further, in advance, solid iodine is filled in the iodine vaporization column 50, and AgOTf is filled in the triflate production column 60. Further, the adsorbent in each column is aged and cleaned, and the temperature of the adsorbent is set to room temperature.

First, as shown in FIG. 2, the opening valve V3, V4, V5, communicates the upstream side of the line L2 by operating the valves V6 and (helium supply source side S1) and a line ^L5, 11 CO ¹¹ CO ₂ from the ₂ supply source S 3 is supplied to the methane generator 6, and ¹¹ CO ₂ is adsorbed to the reduction catalyst in the methane generation column 40. The ¹¹ CO _{2 that} has not been adsorbed is collected by the CO ₂ adsorption column 70 and is not discharged out of the system.

Then, after confirming that the ¹¹ CO ₂ adsorption amount in the methane generation column 40 has reached a predetermined value by the radiation sensor RI1, the supply of the raw material gas is stopped, and the valve V3 is closed.

  Next, as shown in FIG. 3, the valve V <b> 2 is opened and the flow meter 14 is adjusted to supply a predetermined amount of hydrogen gas from the hydrogen supply source S <b> 2 to the methane generation column 40. Then, the inside of the methanation column 40 is filled with hydrogen.

  In parallel with this, the valve V8 is opened, and the line L7 and the portion of the line L1 on the 6-way valve 80 side are communicated by the 3-way valve V10. The six-way valve is in the first state, that is, the state where the opening a and the opening f communicate with each other, the opening b and the opening c communicate with each other, and the opening d and the opening e communicate with each other. Further, the three-way valves V11 and V12 are operated so that the lines L14 communicate with each other, and the valve V13 is opened. Then, the mass flow controller 10 is operated to supply a predetermined amount of helium from the helium supply source S1 in the order of line L1, line L7, line L1, line L10, line L12, line L14, and line L18. Keep in an inert gas atmosphere. Here, the temperature controllers 51, 54, 58, and 62 maintain each column at a constant temperature.

Thereafter, as shown in FIG. 4, the valves V2, V4, and V5 are closed, and the methane generation column 40 is heated by the temperature controller 42 to react ¹¹ CO ₂ and hydrogen to generate ¹¹ CH ₄ .

  Subsequently, as shown in FIG. 5, the valves V1, V4, V5 are opened, the lines L2 are communicated with each other by the three-way valve V6, and the portion on the methane adsorption column 44 side in the line L1 and the line L8 are connected by the three-way valve V9. To communicate. Further, a predetermined amount of helium is supplied from the flow meter 12 in the order of the line L2, the line L1, and the line L8.

As a result, ¹¹ CH ₄ , unreacted hydrogen, and unreacted ¹¹ CO ₂ generated in the methane generation column 40 using helium gas as a carrier gas flow downstream. Unreacted ¹¹ CO ₂ is adsorbed by the CO ₂ adsorption column 72, ¹¹ CH ₄ is adsorbed by the methane adsorption column 44, and unreacted hydrogen is discharged out of the system from the line L 8.

  Subsequently, as shown in FIG. 6, the valves V1, V4, V5, V6, and V8 are closed, the valve V7 is opened, and the three-way valves V9 and V10 are operated so that the lines L1 communicate with each other. A predetermined amount of helium gas is allowed to flow from the controller 10 in the order of line L1, line L10, line L12, line L14, and line L18.

After a while, the methane adsorption column 44 is heated by the temperature controller 46 of the methane supplier 2, ¹¹ CH ₄ is desorbed from the adsorbent, and ¹¹ CH ₄ is supplied into the inert gas flow path 1.

Then, the ¹¹ CH ₄ flows down using helium gas as a carrier gas and flows into the line L10 via the 6-way valve 80. ^It can be confirmed by the radiation sensor RI3 that ¹¹ CH ₄ has flowed to the line L10.

Subsequently, the iodine vaporizing column 50 is heated by the temperature controller 51 of the methyl iodide generator 3 to vaporize iodine in the iodine vaporizing column 50, and iodine and ¹¹ CH ₄ are mixed. Further, when the methyl iodide production column 52 is heated by the temperature controller 54, iodine in the mixed gas reacts with ¹¹ CH ₄ to produce ¹¹ CH ₃ I.

The produced ¹¹ CH ₃ I and unreacted ¹¹ CH ₄ flow down the line L10 using helium as a carrier gas, while ¹¹ CH ₃ I is adsorbed to the methyl iodide adsorption column 56 of the methyl iodide collector 4, Unreacted ¹¹ CH ₄ further flows down and reaches the chamber 5. A part of the acidic component generated by the reaction is adsorbed by the CO ₂ adsorption column 74.

Then, the radiation sensor RI2 monitor, continue this process from the chamber 5 to ¹¹ CH ₄ unreacted starts to be discharged. The amount of ¹¹ CH ₃ I adsorbed in the methyl iodide adsorption column 56 can be confirmed by the radiation sensor RI4.

Subsequently, when unreacted ¹¹ CH ₄ starts to be discharged from the chamber 5, as shown in FIG. 7, the valves V7 and V9 are closed, and the line L7 and the opening a side portion of the line L1 are connected by the three-way valve V10. The helium gas is supplied to the six-way valve via the line L7, and the six-way valve 80 is in the second state, that is, the opening a and the opening b are connected, and the opening c and the opening d are connected, It switches to the state which connects the opening e and the opening f. Then, helium gas from the inert gas flow path 1 is supplied to the line L12, the gas in the chamber 5, that is, unreacted ¹¹ CH ₄ is pushed out, and the pushed ¹¹ CH ₄ is passed through the line L10. Reentering the methyl iodide generator 3 and reacting in the methyl iodide generating column 52, the produced ¹¹ CH ₃ I is adsorbed to the methyl iodide adsorbing column 56, while a small amount of unreacted ¹¹ CH. ₄ is discharged out of the system through a line L14 and a line L18 together with helium gas as a carrier gas.

Thereafter, as shown in FIG. 8, the valve V13 is closed, the valve V14 is opened, and the three-way valves V11 and V12 are operated so that the gas flowing through the line L14 flows through the line L16. The triflate production column 60 of the triflate generator 8 is heated by 62. Then, by heating the methyl iodide adsorption column 56 of methyl iodide collector 4 by a temperature controller 58, the ¹¹ CH ₃ I from the adsorbent to desorb, the ¹¹ CH ₃ I helium gas as a carrier gas line Push to L14 and line L16. Then, ¹¹ CH ₃ I flowing through the line L14 and the line L16 in the triflate generation column 60 reacts with AgOTf, and ¹¹ CH ₃ OTf is generated. The generated ¹¹ CH ₃ OTf is taken out through the line L16 and the line L14. In addition, when it is desired to take out ¹¹ CH ₃ I instead of ¹¹ CH ₃ OTf, the line L14 may flow through the line L16 without bypassing the gas. Then, after confirming that ¹¹ CH ₃ I has been sufficiently discharged from the methyl iodide collector 4 based on the radiation sensor RI4, the supply of helium is stopped and the manufacturing process is ended.

Thus, according to the present embodiment, first, the 6-way valve 80 as the flow path switch is set to the first state, and ¹¹ CH ₄ supplied from the methane supply device 2 using helium as the carrier gas, When the inert gas flow path 1, the methyl iodide generator 3, the methyl iodide collector 4, and the chamber 5 flow in series in this order, the transported ¹¹ CH ₄ is a methyl iodide generator. 3 becomes ¹¹ CH ₃ I, and this ¹¹ CH ₃ I is adsorbed by the methyl iodide collector 4, and unreacted ¹¹ CH ₄ passes through the methyl iodide collector 4 and is accommodated in the chamber 5. The

Subsequently, when the six-way valve 80 is switched to the second state and helium flows through the chamber 5, the methyl iodide generator 3, and the methyl iodide collector 4 in this order, the gas in the chamber 5, that is, , ¹¹ CH ₄ unreacted, extruded helium gas as a carrier gas, is again supplied to the methyl iodide generator 3, further ¹¹ CH ₃ I is produced in methyl iodide generator 3, resulting ¹¹ CH ₃ I is adsorbed by the methyl iodide collector 4.

Therefore, the unreacted ¹¹ CH ₄ discharged from the methyl iodide generator 3 can be returned to the methyl iodide generator 3 from the chamber 5 and reused, and efficient ¹¹ CH ₃ I can be produced. At the same time, since helium gas from the helium supply source S1 is used as a carrier gas for flowing unreacted ¹¹ CH ₄ , ¹¹ CH ₃ I can be manufactured without using pump means. .

  And since the pump means is not used, failure of the movable part due to precipitation of iodine or the like hardly occurs, and continuous use for a long time is possible.

In addition, when ¹¹ CH ₄ is circulated many times by a pump in the circulation path as in the past, although the utilization rate of iodine can be increased to some extent, there is a problem that solid iodine is excessively vaporized and consumed. In this embodiment, ¹¹ CH ₄ can be moved in a plug flow manner by switching the flow path, and the amount of useless iodine vaporization is reduced. Therefore, even if the amount of solid iodine preliminarily charged into the iodine vaporization column is the same, ¹¹ CH ₃ I can be produced in a larger amount than in the conventional case. For example, it is possible to reduce the consumption of iodine to 1/3 to 1/2 as compared with the conventional case, and the number of continuous synthesis obtained by filling with iodine once is, for example, 2 to 3 times. It is also possible.

Further, the methane supply device 2, and a heater 46 for ¹¹ CH ₄ from the adsorbent by heating the methane adsorption column 44 and the methane adsorption column 44 which adsorbent is filled to adsorb ¹¹ CH ₄ desorbed ing. Therefore, provided by the use of highly selective adsorbents for ¹¹ CH _4, in such a case that generated the ¹¹ CH ₄ in situ, high-purity ¹¹ CH ₄ removal of the hydrogen or the like in an inert gas flow path can do.

Further, ¹¹ CO ₂ and a and H ₂ are reacted further comprising a methane generator 6 to produce ¹¹ CH _4, methane generator 6 is connected to the methane adsorption column 44, the inert gas supply source to the methane generator 6 From ¹¹ CO _{2 having} a short half-life, ¹¹ CH ₄ is generated in situ, and the generated ¹¹ CH ₄ is transferred by the inert gas and adsorbed on the adsorbent of the methane adsorption column. be able to.

  Furthermore, since the flow path switch has a so-called six-way valve 80, the cost is reduced and the operation is simplified.

Moreover, in the said embodiment, helium gas is supplied to the 6-way valve 80 via the bypass line L7 in FIG.7, FIG.8. When the 6-way valve 80 is set to the second state and the unreacted ¹¹ CH ₄ in the chamber 5 is returned to the methyl iodide generator 3, it is not necessary to use the methane feeder 2. In this case, the bypass line L7 Is preferable because the cleanliness of helium gas is improved.

  As mentioned above, although this invention was concretely demonstrated based on the embodiment, this invention is not limited to the said embodiment.

For example, in the above-described embodiment, the methane adsorption column 44 having an adsorbent and the temperature controller 46 are employed as the methane feeder 2. For example, ¹¹ CH ₄ produced and purified in the target container is used. When supply is possible, instead of the methane adsorption column 44 and the temperature controller 46, a valve, piping or the like connected between the inert gas flow path 1 and the target container functions as a methane supply device.

  Moreover, in the said embodiment, although the methane adsorption column 44 and the temperature controller 46 are functioning as a methane generator, the aspect without the methane adsorption column 44 and the temperature controller 46 is also possible, and in this case, methane The generator 6 functions as a methane feeder, and the line L1, the line L7, and the line L2 function as an inert gas flow path.

Further, in the above embodiment, it is arranged methane generator 6 for generating a pre-stage to the ¹¹ CO ₂ and _{H 2} Metropolitan from ¹¹ CH ₄ methane adsorption column 44, to produce a reaction by ¹¹ CH ₄ in addition to this A reactor may be arranged.

  Moreover, in the said embodiment, although the 6-way valve 80 is employ | adopted and the 1st state and the 2nd state are switched, for example, 6 three-way valves are employ | adopted and the same flow-path switching means is used. The first state and the second state may be switched by other means such as configuring.

In the above embodiment, after supplying methane feeder 2 ¹¹ CH _4, 7, 8, although supplying helium gas to the 6-way valve 80 through the bypass line L7, for example, As shown in FIG. 9, helium may be supplied to the six-way valve 80 via the methane supplier 2 without passing through the bypass line L7.

  Further, in the present invention, helium is employed as the inert gas, but other inert gases such as nitrogen and argon can be employed.

FIG. 1 is a schematic configuration diagram of a methyl iodide production apparatus according to the present embodiment. FIG. 2 is a flowchart showing the operation of the methyl iodide production apparatus of FIG. FIG. 3 is a flowchart following FIG. 2 showing the operation of the methyl iodide production apparatus of FIG. FIG. 4 is a flowchart following FIG. 3 showing the operation of the methyl iodide production apparatus of FIG. FIG. 5 is a flowchart following FIG. 4 showing the operation of the methyl iodide production apparatus of FIG. FIG. 6 is a flowchart following FIG. 5 showing the operation of the methyl iodide production apparatus of FIG. FIG. 7 is a flowchart following FIG. 6 showing the operation of the methyl iodide production apparatus of FIG. FIG. 8 is a flowchart subsequent to FIG. 7 showing the operation of the methyl iodide production apparatus of FIG. It is a flowchart which shows other operation | movement of the methyl iodide manufacturing apparatus of FIG.

Explanation of symbols

2 ... methane feeder, 3 ... methyl iodide generator, 4 ... methyl iodide collector, 5 ... chamber, 6 ... methane generator, 44 ... methane adsorption column, 46 ... temperature controller (heater), 80 ... 6-way valve (flow path switch), 100 ... Methyl iodide production apparatus, L1 ... Inert gas flow path, L7 ... Bypass line, S1 ... Inert gas source.

Claims (5)

An inert gas flow path through which an inert gas is supplied from an inert gas source;
A methane supplier capable of supplying ¹¹ CH ₄ into the inert gas flow path;
^A methyl iodide generator that reacts ¹¹ CH ₄ with iodine to produce ¹¹ CH ₃ I;
^A methyl iodide collector for collecting ¹¹ CH ₃ I;
A chamber capable of containing gas;
A first state in which the inert gas flow path, the methyl iodide generator, the methyl iodide collector, and the chamber are connected in series in this order, the inert gas flow path, the chamber, and the iodine A flow path switch that selectively switches between the methyl iodide generator and the second state in which the methyl iodide collector is connected in series in this order;
An apparatus for producing methyl iodide. The methane feeder includes a methane adsorption column filled with an adsorbent that adsorbs ¹¹ CH ₄ and a heater that heats the methane adsorption column and desorbs ¹¹ CH ₄ from the adsorbent. The methyl iodide manufacturing apparatus as described. A methane generator for reacting ¹¹ CO ₂ with H ₂ to produce ¹¹ CH ₄ , the methane generator being connected to the methane adsorption column, wherein the methane generator is inert from an inert gas source; The methyl iodide manufacturing apparatus according to claim 2, wherein gas is supplied.   The methyl iodide production apparatus according to claim 1, wherein the inert gas flow path further includes a bypass line that bypasses the methane feeder. The said flow path switch is a methyl iodide manufacturing apparatus in any one of Claims 1-4 which has a 6-way valve.

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