Reaction device and method for producing oxidation reaction product

Abstract

The present invention provides a reaction device that makes it possible to make products separately.　Provided is a reaction device 1 that generates a product by subjecting a raw material to an oxidation reaction in a solution containing the raw material and an oxidizing agent, wherein the raw material includes a hydrocarbon or a derivative of the hydrocarbon, the oxidizing agent includes a chlorine dioxide radical, and the reaction device is provided with: a reaction container 10 that has formed therein a first liquid phase capable of dissolving the product and a second liquid phase including the raw material and the oxidizing agent; an irradiation device 12 that irradiates the interior of the reaction container 10 with light to subject the raw material to the oxidation reaction; a first liquid phase preparation device 30 (product collection device) that collects, from the first liquid phase, the product generated by the oxidation reaction of the raw material; and a second liquid phase preparation device 40 (solvent supply device) that is capable of supplying, into the reaction container 10, fluorous solvents having different compositions as solvents constituting the second liquid phase.

Description

Reactor and method for producing oxidation reaction products

[0001] The present invention relates to a reaction apparatus for carrying out a chemical reaction on a reactant and a technique for producing an oxidation reaction product.

[0002] Conventionally, techniques for carrying out chemical reactions on reactants have been publicly known. For example, Patent Document 1 discloses a method for producing a product at room temperature and atmospheric pressure by a chemical reaction using two liquid phases.

[0003] The invention described in Patent Document 1 above describes a production method in which a reaction system including an aqueous phase and an organic phase is irradiated with light in the presence of a raw material and chlorine dioxide radicals to produce an oxidation reaction product of the raw material. Patent Document 1 describes that when methane is used as the raw material, methanol and formic acid are produced as oxidation reaction products.

[0004] However, in the prior art, it has not been possible to produce different products using the same reaction apparatus.

[0005] Patent No. 6080281

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a reaction apparatus capable of producing different products.

[0007] The problem to be solved by the present invention is as described above, and the means for solving this problem will now be described.

[0008] That is, the reaction apparatus of the present invention is a reaction apparatus that produces a product by subjecting a raw material to an oxidation reaction in a solution containing the raw material and an oxidizing agent, wherein the raw material contains a hydrocarbon or a derivative of the hydrocarbon, and the oxidizing agent contains a chlorine dioxide radical. The reaction apparatus comprises a reaction vessel in which a first liquid phase capable of dissolving the product and a second liquid phase containing the raw material and the oxidizing agent are formed; an irradiation device that irradiates the interior of the reaction vessel with light to cause an oxidation reaction of the raw material; a product recovery device that recovers the product produced by the oxidation reaction of the raw material from the first liquid phase; and a solvent supply device that can supply a fluorous solvent of a different composition into the reaction vessel as a solvent that constitutes the second liquid phase.

[0009] In the reaction apparatus of the present invention, the product contains at least one of formic acid and methanol.

[0010] In the reaction apparatus of the present invention, the solvent constituting the second liquid phase is the fluorous solvent having a composition of C8F13OH3.

[0011] In the reaction apparatus of the present invention, the solvent constituting the second liquid phase is the fluorous solvent having a composition of C3F3H2Cl.

[0012] In the reaction apparatus of the present invention, the fluorous solvent having the composition C3F3H2Cl has the structure CF3CH=CHCl.

[0013] In the reaction apparatus of the present invention, the fluorous solvent having the composition C3F3H2Cl has the structure CHF2CF=CHCl.

[0014] Furthermore, the method for producing an oxidation reaction product of the present invention includes a reaction step of irradiating a solution containing a raw material and chlorine dioxide radicals with light, wherein the raw material includes a hydrocarbon or a derivative of the hydrocarbon, the solution includes an organic phase, and the organic phase includes the raw material and the chlorine dioxide radicals, and in the reaction step, the raw material is oxidized by the light irradiation to produce an oxidation reaction product of the raw material, and the organic phase includes a fluorous solvent having a composition of C8F13OH3 or C3F3H2Cl.

[0015] The present invention has the following effects.

[0016] In the reaction apparatus of the present invention, different products can be produced depending on the purpose.

[0017] Furthermore, in the reaction apparatus of the present invention, formic acid and methanol can be produced separately.

[0018] Furthermore, in the reactor of the present invention, the production rate of methanol can be improved.

[0019] Furthermore, in the reaction apparatus of the present invention, the production rate of formic acid can be improved.

[0020] Furthermore, in the reaction apparatus of the present invention, the production rate of formic acid can be improved.

[0021] Furthermore, in the reaction apparatus of the present invention, the production rate of formic acid can be improved.

[0022] Furthermore, in the method for producing an oxidation reaction product of the present invention, formic acid and methanol can be separately produced.

[0023] 1 is a schematic diagram showing a reaction apparatus according to one embodiment of the present invention; a block diagram showing a reaction apparatus; a flowchart showing a process performed by the reaction apparatus; a flowchart showing a continuation of the process shown in FIG. 3; a diagram showing a schematic diagram of an example of a reaction process; a table showing the production ratios of methanol and formic acid when each solvent is used as the solvent for the second liquid phase;

[0024] The configuration of a reaction apparatus 1 according to one embodiment of the present invention will be described below with reference to FIGS. 1 and 2. FIG.

[0025] The reactor 1 generates a product through a chemical reaction of a raw material gas in a liquid contained in a reaction vessel 10. Specifically, the reactor 1 irradiates light onto a liquid containing the raw material gas and chlorine dioxide radicals as an oxidant, thereby oxidizing the raw material gas and generating a product (oxidation reaction product).

[0026] The source gas may be a hydrocarbon or a derivative thereof. The hydrocarbon may be a saturated hydrocarbon. The saturated hydrocarbon may be, for example, methane, ethane, or cyclohexane. The hydrocarbon may also be a non-aromatic unsaturated hydrocarbon. The hydrocarbon may also be an aromatic hydrocarbon. The aromatic hydrocarbon may be, for example, benzene. In this embodiment, methane is used as the source gas.

[0027] The liquid (reaction system) used in the reaction includes a first solution and a second solution, which are two types of liquids with different specific gravities. The solvent for the first solution can be a solvent capable of dissolving the product, such as water. The solvent for the second solution can be an organic solvent capable of dissolving the raw material gas, such as a fluorous solvent. Types of fluorous solvents will be described later.

[0028] The second solution contains chlorine dioxide radicals. In the reaction system, the first solution contains a source of an oxidant such as chlorine dioxide radicals, and chlorine dioxide radicals are generated in the first solution (first liquid phase), and the generated chlorine dioxide radicals can be extracted from the first solution (first liquid phase) in the second solution (second liquid phase). In this embodiment, sodium chlorite is used as the source of chlorine dioxide radicals.

[0029] The second solution has a larger specific gravity than the first solution, and therefore the first solution (first liquid phase) and the second solution (second liquid phase) are separated in the reaction vessel 10 as shown in FIG.

[0030] The reaction apparatus 1 according to this embodiment can obtain products by oxidizing a raw material gas in a reaction vessel 10. The reaction apparatus 1 can produce alcohols, carboxylic acids, aldehydes, ketones, percarboxylic acids, and hydroperoxides as products. In this embodiment, the reaction apparatus 1 produces methanol and formic acid as products. A detailed description of the chemical reaction in the reaction vessel 10 will be given later. The reaction apparatus 1 includes a reaction vessel 10, a gas phase preparation device 20, a first liquid phase preparation device 30, a second liquid phase preparation device 40, and a control unit 50.

[0031] The reaction vessel 10 is used to chemically react the source gas. The reaction vessel 10 is formed in a substantially cylindrical shape capable of accommodating the source gas, the first solution, and the second solution therein. The reaction vessel 10 is formed with a relatively large depth (vertical dimension) so that the separated first solution and second solution can be easily collected, as will be described later. The reaction vessel 10 is formed of a material that is resistant to the solvent and source gas.

[0032] As shown in FIG. 1 , inside a reaction vessel 10 containing a raw material gas, a first solution, and a second solution, a "gas phase," a "first liquid phase," and a "second liquid phase" are formed, in that order from top to bottom. The "gas phase" is a phase consisting of a mixture of the raw material gas and other gases (gas evaporated from the liquid phase, air inside the reaction vessel 10, etc.). The "first liquid phase" is a phase (aqueous phase) consisting of the first solution. The "second liquid phase" is a phase (solvent phase) consisting of the second solution. The reaction vessel 10 is equipped with a stirring device 11 and an irradiation device 12.

[0033] The agitator 11 agitates the first and second solutions in the reaction vessel 10. The agitator 11 is provided inside the reaction vessel 10. The agitator 11 is equipped with a propeller or the like that rotates around a rotation axis whose axis is oriented in the vertical direction. Note that the agitator 11 is not limited to one equipped with a propeller, and various configurations that can agitate the first and second solutions can be employed. By operating the agitator 11 to mix the first and second solutions, the contact area between the first and second solutions can be increased, thereby promoting the reaction. Note that the mixed first and second solutions will separate again when a predetermined time has elapsed after agitation has stopped.

[0034] In this embodiment, the agitator 11 is disposed at a position eccentric to the center of the reaction vessel 10 in a plan view. This facilitates sufficient mixing of the first and second solutions and promotes separation of the liquid phases after agitation is stopped. That is, when agitation is performed using the agitator 11, vortices and bubbles are formed within the reaction vessel 10, improving the agitation effect. Furthermore, if the agitator 11 is disposed near the inner wall of the reaction vessel 10, the liquid phases are more likely to separate after agitation is stopped. Therefore, by disposing the agitator 11 eccentrically to the center of the reaction vessel 10 in a plan view and relatively close to the inner wall, the generation of vortices and the like is promoted, improving the agitation effect, and promoting separation of the liquid phases after agitation is stopped.

[0035] In this embodiment, as shown by the two-dot chain line in FIG. 1 , baffles 11a that obstruct the flow of each stirred solution are provided on the inner wall of the reaction vessel 10. The baffles 11a are formed in the shape of long plates extending in the vertical direction. A plurality of baffles 11a (for example, four) are provided along the circumferential direction of the reaction vessel 10. By obstructing the flow of each solution with the baffles 11a, turbulence (upstream and downstream) is generated during stirring, promoting the generation of vortices and improving the stirring effect. Furthermore, the baffles 11a can promote separation of each liquid phase after stirring is stopped.

[0036] The irradiation device 12 irradiates light into the inside of the reaction vessel 10. In this embodiment, a photoreaction is caused by irradiating the first solution and the second solution stirred in the reaction vessel 10 with light. The irradiation device 12 is equipped with a light source that emits light of a wavelength required for the reaction. An LED, halogen, or the like can be used as the light source. Various light sources that can irradiate light of a wavelength required for the reaction can be used as the light source. Note that while FIG. 1 shows an example in which light is irradiated from above by the irradiation device 12, the installation position of the irradiation device 12 is not limited to the above position, and various installation positions, such as the side or bottom of the reaction vessel 10, can be used.

[0037] The gas phase preparation device 20 prepares the raw material gas that constitutes the gas phase in the reaction vessel 10. The gas phase preparation device 20 supplies the raw material gas to the reaction vessel 10 and recovers the raw material gas (gas phase gas) from the reaction vessel 10. The gas phase preparation device 20 also removes impurities and by-products contained in the recovered gas. The raw material gas is supplied to the gas phase preparation device 20 from a supply source such as a raw material tank. The gas phase preparation device 20 can also supply not only the raw material gas but also other gases (e.g., air, oxygen, etc.) used in the reaction.

[0038] As shown in FIG. 1 , the gas phase preparation apparatus 20 includes a gas phase supply path 21, which is a path capable of supplying a raw material gas into the reaction vessel 10, and a gas phase recovery path 22, which is a path capable of recovering the raw material gas in the gas phase within the reaction vessel 10. The gas phase supply path 21 is connected to a position within the reaction vessel 10 corresponding to the separated second liquid phase (a position lower than the height position of the upper end of the second liquid phase). The gas phase recovery path 22 is connected to a position within the reaction vessel 10 corresponding to the gas phase (a position above the first liquid phase). The gas phase preparation apparatus 20 is provided with an appropriate pump (not shown) for circulating the raw material gas. The gas phase preparation apparatus 20 is also provided with valves (not shown) capable of opening and closing the gas phase supply path 21 and the gas phase recovery path 22.

[0039] The raw material gas from the gas phase preparation device 20 is supplied to the reaction vessel 10 via the gas phase supply path 21 by the operation of a pump and is blown into the second liquid phase (second solution). At this time, bubbles of the raw material gas are formed in the second solution, and the raw material gas dissolves in the second solution. Note that finer the bubbles, the easier it is for the raw material gas to remain and dissolve in the second solution. For this reason, a mechanism for generating fine bubbles may be provided in the reaction vessel 10, etc.

[0040] The gas phase in the reaction vessel 10 contains the source gas that remains undissolved. The gas in the gas phase is recovered into the reaction vessel 10 via the gas phase recovery path 22 by the operation of a pump. The recovered gas is subjected to removal of impurities and by-products by the gas phase preparation device 20, and then supplied again to the reaction vessel 10. In this way, in this embodiment, the source gas is recycled.

[0041] The first liquid phase preparation device 30 prepares a first solution that constitutes the first liquid phase in the reaction vessel 10. The first liquid phase preparation device 30 can adjust the amount, concentration, and pH of the first solution. The first liquid phase preparation device 30 can also separate products contained in the first solution. The first liquid phase preparation device 30 is supplied with the first solution from a predetermined supply source.

[0042] 1 , the first liquid phase preparation device 30 includes a first liquid phase path 31, which is a path through which the first solution can flow. The first liquid phase path 31 is connected to the reaction vessel 10 at a position corresponding to the separated first liquid phase (a position lower than the height position of the upper end of the first liquid phase).

[0043] The first liquid phase preparation device 30 is provided with an appropriate pump (not shown) for circulating the first solution. The first liquid phase preparation device 30 is also provided with a valve (not shown) that can open and close the first liquid phase path 31, and a sensor (not shown) that can measure the amount of the first solution supplied to the reaction vessel 10.

[0044] By operating the pump of the first liquid phase preparation device 30, a first solution whose concentration and the like have been adjusted can be supplied from the first liquid phase preparation device 30 into the reaction vessel 10. Furthermore, by operating the pump, the first solution from the first liquid phase can be discharged from the reaction vessel 10 to the first liquid phase preparation device 30. The first liquid phase preparation device 30 can separate products contained in the discharged first solution and discharge the products to a predetermined discharge destination. Note that, in the illustrated example, an example is shown in which the first solution is supplied and discharged using one first liquid phase path 31, but separate paths for supplying and discharging the first solution may be provided.

[0045] The second liquid phase preparation device 40 prepares a second solution that constitutes the second liquid phase in the reaction vessel 10. The second liquid phase preparation device 40 can adjust and regenerate the amount of solvent in the second solution. The second liquid phase preparation device 40 can also remove by-products from the second liquid phase (second solution). The second liquid phase preparation device 40 is supplied with the second solution from a predetermined supply source.

[0046] The second liquid phase preparation device 40 can supply fluorous solvents having different compositions as the second solution to the reaction vessel 10. For example, the second liquid phase preparation device 40 may be connected to a plurality of supply sources each capable of supplying fluorous solvents having different compositions, and may be able to supply fluorous solvents having different compositions to the reaction vessel 10 by switching the supply sources. Alternatively, the second liquid phase preparation device 40 may be able to supply fluorous solvents having different compositions to the reaction vessel 10 by having the user prepare the fluorous solvents to be supplied to the second liquid phase preparation device 40.

[0047] The second liquid phase preparation device 40 can supply a fluorous solvent having a composition of C3F3H2Cl to the reaction vessel 10 as the second solution. The fluorous solvent having a composition of C3F3H2Cl may have a structure of CF3CH=CHCl. ​​Furthermore, the fluorous solvent having a composition of C3F3H2Cl may have a structure of CHF2CF=CHCl. ​​Furthermore, the second liquid phase preparation device 40 can supply a fluorous solvent having a composition of C8F13OH3 to the reaction vessel 10 as the second solution. The fluorous solvent having a composition of C8F13OH3 may have a structure of C7F13OCH3.

[0048] 1, the second liquid phase preparation device 40 includes a second liquid phase path 41, which is a path through which the second solution can flow. The second liquid phase path 41 is connected to the reaction vessel 10 at a position corresponding to the separated second liquid phase (a position lower than the height position of the upper end of the second liquid phase).

[0049] An appropriate pump (not shown) for circulating the second solution is provided in the second liquid phase preparation device 40 or the second liquid phase path 41. In addition, the second liquid phase preparation device 40 is provided with a valve (not shown) that can open and close the second liquid phase path 41 and a sensor (not shown) that can measure the amount of the second solution supplied to the reaction vessel 10.

[0050] By operating the pump of the second liquid phase preparation device 40, the second solution, the amount of solvent, etc. of which has been adjusted, can be supplied from the second liquid phase preparation device 40 into the reaction vessel 10. Furthermore, by operating the pump, the second solution from the second liquid phase can be discharged from the reaction vessel 10 to the second liquid phase preparation device 40. Note that, although the illustrated example shows an example in which the second solution is supplied and discharged using one second liquid phase path 41, separate paths for supplying and discharging the second solution may also be provided.

[0051] The control unit 50 shown in FIG. 2 is capable of processing various types of information. The control unit 50 includes a CPU, a memory, and the like. As shown in FIG. 2, the control unit 50 is electrically connected to the reaction vessel 10 (stirring device 11 and irradiation device 12), the gas phase preparation device 20, the first liquid phase preparation device 30, and the second liquid phase preparation device 40 of the reaction apparatus 1. The control unit 50 can control the operation of the gas phase preparation device 20, the first liquid phase preparation device 30, and the second liquid phase preparation device 40, as well as the valves and pumps provided in each of the above-mentioned devices. The control unit 50 can also acquire measurement results from sensors provided in each device of the reaction apparatus 1.

[0052] The operation of the reactor 1 will be described below. The reactor 1 (controller 50) produces a product by controlling each process shown in the flowcharts of Figures 3 and 4. The reactor 1 can produce the product at room temperature and atmospheric pressure. At the start of the following control, the inside of the reaction vessel 10 is empty and all valves of the reactor 1 are closed.

[0053] First, the control unit 50 executes a "reaction preparation step" shown in steps S101 to S106 in Fig. 3. The reaction preparation step is a step for making preparations before starting a reaction in the reaction vessel 10.

[0054] In the processes from step S101 to step S103, the control unit 50 fills a preset amount (specified amount) of the first solution into the reaction vessel 10. More specifically, the control unit 50 opens the valve of the first liquid phase path 31 and operates the pump of the first liquid phase preparation device 30 to start filling the first solution (aqueous solution containing sodium chlorite) into the reaction vessel 10 (step S101). Furthermore, the control unit 50 determines whether the specified amount of the first solution has been filled into the reaction vessel 10 based on the measurement result of the sensor of the first liquid phase preparation device 30 (step S102).

[0055] When the control unit 50 determines that the reaction vessel 10 has been filled with a specified amount of the first solution (step S102: YES), it stops the pump of the first liquid phase preparation device 30 and closes the valve of the first liquid phase path 31 to stop filling of the first solution into the reaction vessel 10 (step S103). After executing the process of step S103, the control unit 50 proceeds to the process of step S104. On the other hand, when the control unit 50 determines that the reaction vessel 10 has not been filled with a specified amount of the first solution (step S102: NO), it proceeds to the process of step S101 (continues filling of the first solution).

[0056] In the processes from step S104 to step S106, the control unit 50 fills a preset amount (specified amount) of the second solution into the reaction vessel 10. More specifically, the control unit 50 opens the valve of the second liquid phase path 41 and operates the pump of the second liquid phase preparation device 40 to start filling the reaction vessel 10 with the second solution (fluorous solvent) (step S104). Furthermore, the control unit 50 determines whether the specified amount of the second solution has been filled into the reaction vessel 10 based on the measurement results of the sensor of the second liquid phase preparation device 40 (step S105).

[0057] When the control unit 50 determines that the reaction vessel 10 has been filled with a specified amount of the second solution (step S105: YES), it stops the pump of the second liquid phase preparation device 40 and closes the valve of the second liquid phase path 41 to stop filling of the second solution into the reaction vessel 10 (step S106). After executing the process of step S106, the control unit 50 proceeds to the process of step S107. On the other hand, when the control unit 50 determines that the reaction vessel 10 has not been filled with a specified amount of the second solution (step S105: NO), it proceeds to the process of step S104 (continues filling of the second solution).

[0058] By carrying out the above reaction preparation step, a first liquid phase and a second liquid phase are formed in the reaction vessel 10 .

[0059] Next, the control unit 50 executes the "reaction step" shown in steps S107 to S110 in Fig. 3. The reaction step is a step of causing a chemical reaction using the source gas, the first solution, and the second solution in the reaction vessel 10.

[0060] In the processes from step S107 to step S109, the control unit 50 operates each device used in the chemical reaction. More specifically, the control unit 50 operates the agitator 11 of the reaction vessel 10 to start agitating the first solution and the second solution in the reaction vessel 10 (step S107). The control unit 50 also opens the valves of the gas phase preparation device 20 (gas phase supply path 21 and gas phase recovery path 22) and operates the pump of the gas phase preparation device 20 to start supplying the source gas (methane gas) into the reaction vessel 10 (step S108). The control unit 50 also operates the gas phase preparation device 20 to prepare the source gas and circulate the source gas. The control unit 50 also operates the irradiation device 12 of the reaction vessel 10 to start irradiating light inside the reaction vessel 10 (step S109). After executing the process of step S109, the control unit 50 proceeds to the process of step S110.

[0061] In the process of step S110, the control unit 50 determines whether a specified time has elapsed. The specified time can be a time (period) during which the chemical reaction in the reaction vessel 10 is estimated to have progressed sufficiently. The specified time can be set based on, for example, the amounts of the first solution and the second solution filled in the reaction preparation step. If the control unit 50 determines that the specified time has elapsed (step S110: YES), the control unit 50 proceeds to the process of step S111. On the other hand, if the control unit 50 determines that the specified time has not elapsed (step S110: NO), the control unit 50 proceeds to the process of step S119 (continuing the irradiation of light, etc.).

[0062] By carrying out the above reaction step, a chemical reaction using the raw material gas, the first solution, and the second solution occurs in the reaction vessel 10. More specifically, in the reaction step, the raw material gas is blown into the first solution and the second solution stirred in the reaction vessel 10. As a result, the raw material gas (methane gas), chlorine dioxide (chlorine dioxide gas) generated from the first solution, and oxygen in the reaction vessel 10 are dissolved in the second solution (fluorous solvent), which is a solvent. In this state, by irradiating the reaction vessel 10 with light from the irradiation device 12, a reaction occurs in the reaction vessel 10 to convert the raw material gas methane into methanol and formic acid. The product generated in the reaction vessel 10 does not dissolve in the second solution, but moves to the first liquid phase after the liquid phases are separated.

[0063] FIG. 5 is a schematic diagram illustrating an example of a reaction process for producing alcohol. As shown in FIG. 5, chlorite ions (ClO2-) in a first liquid phase (aqueous phase) react with an acid to generate chlorine dioxide radicals (ClO2.). The ClO2. dissolves in a second liquid phase (organic phase). Next, the second liquid phase (organic phase) containing the chlorine dioxide radicals (ClO2.) is irradiated with light to provide light energy hν (h is the Blank constant, ν is the light frequency), causing the chlorine dioxide radicals (ClO2.) in the second liquid phase (organic phase) to decompose, generating chlorine radicals (Cl.) and oxygen molecules (O2). As a result, the raw material (RH) in the second liquid phase (organic phase) is oxidized, generating an alcohol (R-OH) as an oxidation reaction product.

[0064] Next, the control unit 50 executes the "reaction field regeneration process" shown in steps S111 to S117 of Fig. 4. The reaction field regeneration process is a process of recovering the products produced in the reaction vessel 10 and preparing each liquid phase.

[0065] In the processes from step S111 to step S114, the control unit 50 stops each device operated in the reaction process and waits for a predetermined time. More specifically, the control unit 50 stops the light irradiation by the irradiation device 12 (step S111). The control unit 50 also closes the valve of the gas phase preparation device 20 and stops the pump to stop the supply of the raw material gas into the reaction vessel 10 (step S112). The control unit 50 also stops the stirring by the stirring device 11 (step S113) and waits in this state for a predetermined time (step S114). The predetermined time can be the time it is estimated that the first and second liquid phases mixed by stirring will separate. After executing the process of step S114, the control unit 50 proceeds to the process of step S115.

[0066] In the process of step S115, the control unit 50 determines whether the first liquid phase and the second liquid phase have separated. The control unit 50 makes this determination based on the measurement results of a sensor (not shown), such as an optical sensor, that is provided in the reaction vessel 10 and is capable of measuring the state of separation of the liquid phases. If the control unit 50 determines that the liquid phases have separated (step S115: YES), the control unit 50 proceeds to the process of step S116. On the other hand, if the control unit 50 determines that the liquid phases have not separated (step S115: NO), the control unit 50 proceeds to the process of step S114 (and further waits for a predetermined time).

[0067] In the above example, both the process of waiting for a predetermined time to separate the liquid phases (step S114) and the process of determining whether the liquid phases have been separated (step S115) are performed, but the present invention is not limited to the above. For example, only one of the processes may be performed.

[0068] In the processes of steps S116 and S117, the control unit 50 operates the first liquid phase preparation apparatus 30 and the second liquid phase preparation apparatus 40 to recover the product and prepare each liquid phase. More specifically, by operating the first liquid phase preparation apparatus 30, the control unit 50 extracts a portion of the first solution of the first liquid phase, adjusts the extracted first solution (adjusting the chlorine dioxide concentration, pH, etc.), and supplies it to the reaction vessel 10 (step S116). In this way, when the first liquid phase preparation apparatus 30 is operated, the first solution is circulated between the first liquid phase preparation apparatus 30 and the reaction vessel 10. In addition, the first liquid phase preparation apparatus 30 extracts the product (methanol) from the extracted first solution. The extracted product is discharged to an appropriate discharge destination (not shown).

[0069] Furthermore, the control unit 50 operates the second liquid phase preparation device 40 to extract a portion of the second solution in the second liquid phase, adjust the extracted second solution (adjust the amount of solvent, etc.), and supply it into the reaction vessel 10 (step S117). In this way, when the second liquid phase preparation device 40 is operated, the second solution is circulated between the second liquid phase preparation device 40 and the reaction vessel 10. Furthermore, the second liquid phase preparation device 40 recovers by-products (e.g., fixatives, etc.) contained in the extracted second solution. The recovered by-products are discharged to an appropriate discharge destination (not shown). After executing the process of step S117, the control unit 50 proceeds to the process of step S118.

[0070] By carrying out the above-mentioned reaction field regeneration process, the first liquid phase and the second liquid phase inside the reaction vessel 10 are restored to a state in which the reaction process can be carried out again. In addition, the control unit 50 counts the number of times the reaction field regeneration process and the reaction process have been carried out since the control was started.

[0071] In the processing of step S118, the control unit 50 determines whether the number of times the reaction field regeneration step (reaction step) has been performed is a specified number of cycles. The specified number of cycles is set in advance. If the control unit 50 determines that the number of times the reaction field regeneration step has been performed is the specified number of cycles, it terminates the processing of the reaction device 1. On the other hand, if the control unit 50 determines that the number of times the reaction field regeneration step has been performed is not the specified number of cycles, it proceeds to the processing of step S107 and performs the reaction step again.

[0072] By executing the control described above, the reaction apparatus 1 can continuously produce a product through a chemical reaction using two liquid phases. That is, by circulating the raw material gas, the first solution, and the second solution using the gas phase preparation apparatus 20, the first liquid phase preparation apparatus 30, and the second liquid phase preparation apparatus 40, the product can be continuously produced without discharging all of the solution, etc., in the reaction vessel 10. This allows the product to be produced more efficiently than, for example, a batch-type reaction system.

[0073] The above-described control mode is an example, and the content of each process can be changed as appropriate. For example, in the above example, the reaction process and the reaction field regeneration process are repeated until a predetermined number of cycles are reached (step S118), but this is not limited to this mode. For example, a configuration can be adopted in which a sensor capable of measuring the concentration of the product generated in the reaction process is provided in the reaction vessel 10, and when the measurement value of the sensor exceeds a predetermined threshold, the reaction process is terminated and the first liquid phase preparation device 30 is operated to recover the product.

[0074] Here, in step S104, as described above, the second liquid phase preparation apparatus 40 can supply a fluorous solvent having a different composition as the second solution to the reaction vessel 10. The second liquid phase preparation apparatus 40 can supply a fluorous solvent having a composition of C3F3H2Cl as the second solution (solvent) to the reaction vessel 10. Furthermore, the second liquid phase preparation apparatus 40 can supply a fluorous solvent having a composition of C8F13OH3 as the second solution to the reaction vessel 10.

[0075] By supplying a fluorous solvent having a composition of C3F3H2Cl (CF3CH=CHCl or CHF2CF=CHCl) to the reaction vessel 10 as the second solution, the production ratio of formic acid (the ratio of the amount of formic acid produced to the total amount of products produced) can be improved. Specifically, as shown in FIG. 6, when a solvent having a composition of C6F14 (current solvent) is used as the second solution, the production ratio of methanol is 24.7% and the production ratio of formic acid is 75.3%. However, when solvent A having a composition of C3F3H2Cl (CF3CH=CHCl) is used as the second solution, the production ratio of methanol can be 0% and the production ratio of formic acid can be 100%. Furthermore, by supplying solvent B having a composition of C3F3H2Cl (CHF2CF=CHCl) to the reaction vessel 10 as the second solution, the production ratio of methanol can be 1.8% and the production ratio of formic acid can be 98.2%.

[0076] On the other hand, by using a fluorous solvent having a composition of C8F13OH3 (C7F13OCH3) as the second solution, the methanol production ratio (the ratio of the amount of methanol produced to the total amount of products produced) can be improved. Specifically, as shown in Figure 6, by using solvent C having a composition of C8F13OH3 (C7F13OCH3) as the second solution, the methanol production ratio can be increased to 77.7% and the formic acid production ratio to 22.3%.

[0077] In this way, by changing the fluorous solvent of the second solution, it is possible to produce different products depending on the purpose. For example, if it is desired to increase the production ratio of formic acid, a fluorous solvent having a composition of C3F3H2Cl can be used as the second solution. On the other hand, if it is desired to increase the production ratio of methanol, a fluorous solvent having a composition of C8F13OH3 can be used as the second solution.

[0078] As described above, the reaction apparatus 1 according to this embodiment is a reaction apparatus 1 that produces a product by subjecting a raw material to an oxidation reaction in a solution containing the raw material and an oxidizing agent, wherein the raw material includes a hydrocarbon or a derivative of the hydrocarbon, and the oxidizing agent includes a chlorine dioxide radical. The reaction apparatus 1 comprises: a reaction vessel 10 in which a first liquid phase capable of dissolving the product and a second liquid phase containing the raw material and the oxidizing agent are formed; an irradiation device 12 that irradiates the interior of the reaction vessel 10 with light to cause an oxidation reaction of the raw material; a first liquid phase preparation device 30 (product recovery device) that recovers the product produced by the oxidation reaction of the raw material from the first liquid phase; and a second liquid phase preparation device 40 (solvent supply device) that can supply a fluorous solvent of a different composition into the reaction vessel 10 as a solvent that constitutes the second liquid phase.

[0079] By configuring in this way, it is possible to produce different products depending on the purpose.

[0080] The product contains at least one of formic acid and methanol.

[0081] By configuring in this way, formic acid and methanol can be produced separately.

[0082] The solvent constituting the second liquid phase is the fluorous solvent having a composition of C8F13OH3.

[0083] By configuring in this way, it is possible to improve the production ratio of methanol.

[0084] The solvent constituting the second liquid phase is the fluorous solvent having a composition of C3F3H2Cl.

[0085] By configuring in this way, the production rate of formic acid can be improved.

[0086] Furthermore, the fluorous solvent having the composition C3F3H2Cl has the structure CF3CH=CHCl.

[0087] By configuring in this way, the production rate of formic acid can be improved.

[0088] Furthermore, the fluorous solvent having the composition C3F3H2Cl has the structure CHF2CF=CHCl.

[0089] By configuring in this way, the production rate of formic acid can be improved.

[0090] Furthermore, a method for producing an oxidation reaction product includes a reaction step of irradiating a solution containing a raw material and chlorine dioxide radicals with light, wherein the raw material includes a hydrocarbon or a derivative of the hydrocarbon, the solution includes an organic phase, and the organic phase includes the raw material and the chlorine dioxide radicals, and in the reaction step, the raw material is oxidized by the light irradiation to produce an oxidation reaction product of the raw material, and the organic phase includes a fluorous solvent having a composition of C8F13OH3 or C3F3H2Cl.

[0091] By configuring in this way, formic acid and methanol can be produced separately.

[0092] Although one embodiment of the present invention has been described above, the present invention is not limited to the above-described embodiments. For example, the configuration of each part constituting the reaction apparatus 1 is not limited to the above-described one, and can be appropriately changed.

[0093] In addition, in the above embodiment, an example is shown in which the stirring device 11 is provided at a position eccentric to the center of the reaction vessel 10 when viewed from above, but this is not limited to such an embodiment, and the stirring device 11 may also be provided at the center of the reaction vessel 10 when viewed from above.

[0094] Furthermore, in the above embodiment, an example was shown in which the baffle plate 11a was provided in the reaction vessel 10, but the present invention is not limited to this, and the baffle plate 11a may not be provided.

[0095] In addition, in the above embodiment, an example was shown in which a first liquid phase is formed on the upper side and a second liquid phase is formed on the lower side within the reaction vessel 10, but this is not limited to such an embodiment, and the first liquid phase may be formed on the lower side and the second liquid phase may be formed on the upper side.

[0096] In the above embodiment, the reaction step is performed at room temperature and normal pressure, but the present invention is not limited to this. For example, the reaction step may be performed by pressurizing the inside of the reaction vessel 10 with a source gas. Alternatively, the reaction step may be performed by heating or cooling the inside of the reaction vessel 10.

[0097] The present invention can be applied to a reactor for carrying out a chemical reaction on a reactant and to a method for producing an oxidation reaction product.

[0098] REFERENCE SIGNS LIST 1 Reaction device 10 Reaction vessel 20 Gas phase preparation device 30 First liquid phase preparation device 40 Second liquid phase preparation device 50 Control unit

Claims

1. A reaction apparatus for producing a product by oxidizing a raw material in a solution containing the raw material and an oxidizing agent, wherein the raw material includes a hydrocarbon or a derivative of the hydrocarbon, and the oxidizing agent includes a chlorine dioxide radical; the reaction apparatus comprising: a reaction vessel having formed therein a first liquid phase capable of dissolving the product and a second liquid phase containing the raw material and the oxidizing agent; an irradiation device that irradiates the interior of the reaction vessel with light to cause an oxidation reaction of the raw material; a product recovery device that recovers the product produced by the oxidation reaction of the raw material from the first liquid phase; and a solvent supply device that can supply a fluorous solvent of a different composition into the reaction vessel as a solvent for constituting the second liquid phase.

2. The reactor according to claim 1, wherein the product includes at least one of formic acid and methanol.

3. The reaction apparatus according to claim 2, wherein the solvent constituting the second liquid phase is the fluorous solvent having a composition of C8F13OH3.

4. The reaction apparatus according to claim 2, wherein the solvent constituting the second liquid phase is the fluorous solvent having a composition of C3F3H2Cl.

5. The reaction apparatus according to claim 4, wherein the fluorous solvent having a composition of C3F3H2Cl has a structure of CF3CH=CHCl.

6. The reaction apparatus according to claim 4, wherein the fluorous solvent having a composition of C3F3H2Cl has a structure of CHF2CF=CHCl.

7. A method for producing an oxidation reaction product, comprising a reaction step of irradiating a solution containing a raw material and chlorine dioxide radicals with light, wherein the raw material contains a hydrocarbon or a derivative of the hydrocarbon, the solution contains an organic phase, the organic phase contains the raw material and the chlorine dioxide radicals, and in the reaction step, the raw material is oxidized by the light irradiation to produce an oxidation reaction product of the raw material, and the organic phase contains a fluorous solvent having a composition of C8F13OH3 or C3F3H2Cl.

Images