JPWO2014157343A1 - Method and apparatus for producing organic compounds using solid-phase oxidation reaction method - Google Patents

Abstract

[Problem] The technical problem was to develop a method and apparatus for producing an organic compound using a novel solid-phase oxidation reaction method, which can industrially realize the solid-phase oxidation reaction method. [Solution] A mixture preparation step in which a powder of a solid catalyst and a powder of a solid dispersed phase are mixed to prepare a powder mixture, a mixing step of adding a raw material organic compound to the mixture, and processing in the mixing step are performed. An impregnation step of impregnating the mixed mixture with an oxidizing agent, an oxidation reaction step of reacting a raw material organic compound and an oxidizing agent in the mixture subjected to the treatment in the impregnation step, and an organic compound generated in the oxidation reaction step as a solvent In the method for producing an organic compound, the organic compound is obtained by sequentially performing a recovery step of recovering in a dissolved state, wherein at least the impregnation step, the oxidation reaction step, and the recovery step are performed in the same container body. Become.

Description

  The present invention relates to a method for producing an organic compound and an apparatus therefor, and particularly uses a solid-phase oxidation reaction method that can industrially realize a solid-phase oxidation reaction method established at a laboratory level. The present invention relates to a method for manufacturing an organic compound and an apparatus therefor.

One of the present applicants mixes an organic compound as a raw material (hereinafter referred to as a raw material organic compound) with a mixture of a powder composed of a solid catalyst powder and a solid dispersed phase powder, and further contains an excess as an oxidizing agent. It was found that a high-purity oxidation reaction product (hereinafter referred to as an organic compound) can be obtained from a raw material organic compound by impregnating with hydrogen oxide water to make a mixture in an apparent powder state and allowing this mixture to stand at room temperature. Have already filed patent applications (see Patent Document 1).
Such a solid-phase oxidation reaction method is an organic compound oxidation reaction system, which is a mixture (powder) of a powder of a solid dispersed phase and a powder of a solid catalyst, a raw material organic compound, and a concentration of 5% or more. Less than 35% or more than 35% and less than 60% hydrogen peroxide solution (oxidant), and dispersed in the mixture so that the raw material organic compound, the solid catalyst and the hydrogen peroxide solution are in contact with each other. It is characterized by this.
The solid-phase oxidation reaction method does not require an organic solvent that adversely affects the global environment, and has a high conversion rate and high selectivity (that is, a high product yield). Further, the catalyst can be reused. It has advantages such as being possible, and does not require a process that complicates the reaction operation, has a high reaction rate, and can be easily isolated and recovered with a high industrial value. It is expected to be possible.

  However, such a solid-phase oxidation reaction method has been verified at the laboratory stage using beakers and test tubes at present, but industrial production has not yet been realized. .

WO2008 / 093711

  The present invention has been made from such a background. An organic compound production method using a novel solid-phase oxidation reaction method and an apparatus thereof capable of industrially realizing the solid-phase oxidation reaction method are provided. Development is a technical issue.

  That is, the method for producing an organic compound using the solid-phase oxidation reaction method according to claim 1 comprises a mixture preparation step of preparing a powder mixture by mixing a solid catalyst powder and a solid dispersed phase powder. A mixing step of adding a raw material organic compound to the mixture, an impregnation step of impregnating the mixture subjected to the treatment in the mixing step with an oxidizing agent, and an oxidation of the raw material organic compound in the mixture subjected to the treatment in the impregnation step In the method for producing an organic compound, an organic compound is obtained by sequentially performing an oxidation reaction step in which an agent is reacted and a recovery step in which the organic compound generated in the oxidation reaction step is recovered in a state of being dissolved in a solvent. , At least the impregnation step, the oxidation reaction step, and the recovery step are performed in the same container body.

  In addition to the above requirements, the method for producing an organic compound using the solid-phase oxidation reaction method according to claim 2 includes a solid catalyst powder and a solid dispersed phase powder after the recovery step is performed. A regeneration step for reusing the mixture containing the mixture is carried out, and the mixture step, the impregnation step, the oxidation reaction step, the recovery step, and the regeneration step are repeated using the mixture regenerated by the regeneration step. It is characterized by what it does.

  Furthermore, the method for producing an organic compound using the solid-phase oxidation reaction method according to claim 3 is not only the requirements of claim 2, but also the impregnation step, oxidation reaction step and recovery step, and the mixture preparation step. Any one step or a plurality of steps among the mixing step and the regeneration step is performed in the same container body.

  An apparatus for producing an organic compound using the solid-phase oxidation reaction method according to claim 4 includes: a sealable container body; a filter provided in the container body; and a device for supplying gas into the container body. A mixture of a powder of a solid catalyst and a powder of a solid dispersed phase to prepare a mixture of powders in an apparatus comprising a temperature adjusting mechanism for bringing the inside of the container body to a desired temperature A preparation step, a mixing step of adding a raw material organic compound to the mixture, an impregnation step of impregnating the mixture subjected to the treatment in the mixing step with an oxidizing agent, and a raw material organic in the mixture subjected to the treatment in the impregnation step An organic compound can be obtained by sequentially performing an oxidation reaction step in which a compound and an oxidizing agent are reacted, and a recovery step in which the organic compound generated in the oxidation reaction step is recovered in a state of being dissolved in a solvent. In the manufacturing apparatus of kill organic compounds are those comprising as characterized by being configured to perform at least the impregnation step, the oxidation reaction step and the same container body of the recovery process.

  Furthermore, an apparatus for producing an organic compound using the solid-phase oxidation reaction method according to claim 5 adds the requirements of claim 4 and the solid catalyst powder and solid after the recovery step is performed. It is configured to be able to carry out a regeneration process for reusing a mixture containing dispersed phase powder, and using the mixture regenerated by the regeneration process, the mixing process, impregnation process Further, the present invention is characterized in that the oxidation reaction process, the recovery process, and the regeneration process can be repeated.

Furthermore, the organic compound production apparatus using the solid-phase oxidation reaction method according to claim 6 includes the mixture preparation step in addition to the impregnation step, oxidation reaction step, and recovery step in addition to the requirements of claim 5. In addition, any one step or a plurality of steps among the mixing step and the regeneration step can be performed in the same container body.
The above-described problems can be solved by using the inventions described in these claims as means.

  First, since the solid-phase oxidation reaction method can be industrially realized, the organic compound produced by the solid-phase oxidation reaction method can be provided to the market. .

  Further, according to the invention described in claim 2, since the regenerated mixture can be used repeatedly for the mixing step, the impregnation step, the oxidation reaction step, the recovery step and the regeneration step, Can greatly contribute to realization.

Furthermore, according to the invention described in claim 3, impurities can be reduced by performing any one step or a plurality of steps in the same container body among the mixture preparation step, the mixing step or the regeneration step. can do. In particular, the mixing process, the impregnation process, the oxidation reaction process, the recovery process and the regeneration process are all the same from the mixture preparation process in which the powder of the solid catalyst and the powder of the solid dispersed phase are mixed to prepare the powder mixture. Impurities are greatly reduced by repeatedly performing the mixing, impregnation, oxidation, recovery, and regeneration processes while leaving the regenerated mixture in the same container body in the container body. And a high-purity organic compound can be produced.
Moreover, compared with the case where a mixture preparation process, a mixing process, or a reproduction | regeneration process is performed with the apparatus different from a container main body, simplification of processes, such as material conveyance, and reduction of an apparatus space can be aimed at.

  According to the invention described in claim 4, since the solid-phase oxidation reaction method can be industrially realized, it is possible to provide the market with an organic compound produced by the solid-phase oxidation reaction method. .

  Furthermore, according to the invention described in claim 5, since it is possible to repeatedly perform the mixing step, the impregnation step, the oxidation reaction step, the recovery step, and the regeneration step using the regenerated mixture, as a resource-saving production method It can greatly contribute to industrial realization.

Furthermore, according to the invention described in claim 6, impurities can be mixed by performing any one step or a plurality of steps of the mixture preparation step, the mixing step, or the regeneration step in the same container body. Can be reduced. In particular, the mixing process, the impregnation process, the oxidation reaction process, the recovery process and the regeneration process are all the same from the mixture preparation process in which the powder of the solid catalyst and the powder of the solid dispersed phase are mixed to prepare the powder mixture. Impurities are greatly reduced by repeatedly performing the mixing, impregnation, oxidation, recovery, and regeneration processes while leaving the regenerated mixture in the same container body in the container body. And a high-purity organic compound can be produced.
Moreover, compared with the case where a mixture preparation process, a mixing process, or a reproduction | regeneration process is performed with the apparatus different from a container main body, simplification of processes, such as material conveyance, and reduction of an apparatus space can be aimed at.

1 is a skeleton diagram showing an organic compound production apparatus using the solid-phase oxidation reaction method of the present invention. FIG. It is a flowchart which shows the manufacturing method of the organic compound using a solid-phase-type oxidation reaction method. It is process drawing which shows the manufacturing method of the organic compound using a solid-phase-type oxidation reaction method in frame. It is a skeleton figure which shows the other Example of the manufacturing apparatus of the organic compound using the solid-phase-type oxidation reaction method of this invention.

  One of the best modes of the “method for producing an organic compound using a solid-phase oxidation reaction method and its apparatus” according to the present invention is as shown in the following examples. First, the solid-phase oxidation reaction of the present invention An example of the configuration of an organic compound manufacturing apparatus 1 (hereinafter referred to as manufacturing apparatus 1) using a method is described, and then the solid-phase oxidation reaction method of the present invention is used in conjunction with the operation mode of the manufacturing apparatus 1. An example of a method for producing an organic compound will be described. It should be noted that this embodiment can be appropriately modified within the scope of the technical idea of the present invention.

FIG. 1 schematically shows a manufacturing apparatus 1 according to the present invention, which can perform mixing, temperature adjustment, filtration, and drying of an object to be processed fed into a sealable container body 2. Device.
First, the container body 2 is a hollow cylindrical member having an upper portion tapered, and an opening 20 and a material supply port 21 are formed on the upper portion, and the lower opening is closed by a lid 24 that can be opened and closed. It is configured as follows. A shutoff valve 22 is connected to the opening 20.
The raw material supply port 21 is provided with a supply pipe 26 so that the discharge part is inserted into the container body 2. The pipe connected to the supply pipe 26 branches into two paths. The shut-off valves 23 and 25 are connected to each other, and the interior space of the container body 2 is sealed.
A filtrate discharge port 24 a is formed in the lower part of the lid 24, a filter support member 27 is provided between the lid 24 and the container body 2, and a filter 27 a is provided on the upper surface of the filter support member 27. Yes.

  Further, a jacket 3 is provided so as to cover the outer peripheral portion of the container body 2, and by circulating and supplying a heat medium to the inside of the jacket 3, the container body 2 is temperature-controlled from the outside and the internal temperature is desired. It is comprised so that it can be set as the value of. Such a heat medium supply means will be described later.

The container body 2 is rotationally driven about a horizontal axis, and support shafts 4 and 5 for this purpose are provided to the side periphery of the container body 2, and these are bearings 41, 51. In addition, a sprocket (not shown) is provided on one support shaft 4 and the output shaft of the motor 40, and a chain 42 is wound between them. With such a configuration, the container body 2 can be turned upside down and rotated. The container body 2 can be continuously rotated in one or both directions, can be swung at an appropriate angle, or can be rotated at an appropriate angle by a motor 40 having a brake function. Operations such as stopping and stopping can also be performed. Further, as will be described later in detail, it is possible to stop (rotate) the position by stopping the rotation at a preferred position in order to promote mixing, impregnation, or oxidation reaction necessary for each step.
The support shaft 4 has a forward path and a return path formed therein, and is connected to the heat medium generator 6 using a rotary joint 43, and circulates and supplies the heat medium to the inside of the jacket 3. It is configured to be able to.
Further, the support shaft 5 has a hollow shape and is connected to a separation device 7 for solid-gas separation, and thereafter, a condenser 8 provided with a refrigerator 8a and a vacuum pump P are sequentially connected. The pipe connected to the filtrate outlet 24a is branched into two paths, and shut-off valves 28 and 29 are connected to each, and the shut-off valve 29 is communicated with the hollow space of the support shaft 5.
The production apparatus 1 of the present invention is configured as described above as an example, and hereinafter, a method for producing an organic compound using the solid-phase oxidation reaction method of the present invention, which is performed using the production apparatus 1 However, prior to this description, the solid phase oxidation reaction method and various substances used in the solid phase oxidation reaction method will be described.

The solid phase oxidation reaction method uses a mixture M of a powder of a solid dispersion phase S and a powder of a solid catalyst C. In the powder of the mixture M, a raw material organic compound O and an example of an oxidizing agent are used. An epoxy compound E which is an example of an organic compound as a product is obtained by impregnating with a certain hydrogen peroxide solution H, bringing them into contact with each other, and oxidizing the raw organic compound O.
Conventionally, in such an oxidation reaction in a two-phase heterogeneous system, an oxidation reaction has been performed in a liquid phase using a solvent. In a solid-phase oxidation reaction method, a solid dispersed phase is used as a medium instead of a solvent. For example, the solid dispersed phase powder is mixed with the powder of the solid catalyst C and impregnated with an organic compound (raw material organic compound O) as a reaction reagent and an oxidizing agent (hydrogen peroxide water H). Thus, the oxidation reaction is apparently performed in the powder state.
For this reason, it is not necessary to mix and stir the reaction system during the oxidation reaction, and the oxidation reaction can be performed in a stationary state.

As the mixing or impregnation mode of the solid dispersed phase S, the solid catalyst C, the raw material organic compound O, and the hydrogen peroxide solution H, in addition to the above-described mode, the powder of the solid catalyst C is contained in the powder of the solid dispersed phase S. It is also possible to adopt a mode in which the body is mixed, and the material impregnated with the raw material organic compound O and the powder of another solid dispersed phase S impregnated with the hydrogen peroxide solution H are mixed. Furthermore, after impregnating the raw material organic compound O and the hydrogen peroxide solution H separately in the powder of the solid dispersed phase S, the powder of the solid dispersed phase S and the powder of the solid catalyst C are mixed. The embodiment is not particularly limited as long as the oxidation reaction can be performed with the powder state apparently.
In the above description, the mode in which the liquid raw material organic compound O is impregnated into the mixture M is described. However, the raw material organic compound O may be in a liquid state or in a powder state. Added the raw material organic compound O to the mixture M as mixing (mixing step) in the meaning including the aspect of impregnation.

Here, the solid dispersion phase S is preferably a solid catalyst C, a raw material organic compound O, and a hydrogen peroxide solution H dispersed therein, which have the property of not deteriorating and inhibiting the oxidation reaction. The powder of the substance which has the property which accelerates | stimulates oxidation reaction is employ | adopted.
Specifically, phosphates such as apatite, diatomaceous earth (main component: silica), white ceramics (main component: silica alumina), clays such as hydrotalcite, fluorides such as calcium fluoride, silica, titania, alumina, etc. These oxides can be used. Among these, it is preferable to employ a solid dispersed phase selected from phosphates, diatomaceous earth, silica, alumina, white clay, silica alumina and calcium fluoride, and a high yield can be achieved. In particular, when a solid dispersed phase selected from apatite, diatomaceous earth and calcium fluoride is employed, a higher yield can be achieved.

  The apatite is a kind of calcium phosphate, and fluorapatite, chlorapatite, carbonate apatite, hydroxyapatite, etc. are present as apatite minerals, and fluorapatite is particularly preferred in the solid-phase oxidation reaction method. Used for.

The diatomaceous earth is a soft rock or soil mainly composed of diatom shell, which is mainly composed of silica, but includes alumina, iron oxide, oxides of alkali metals, etc. in addition to silica. There are many. Diatomaceous earth is preferably porous and has a high porosity and a cake bulk density of about 0.2 to 0.45. Further, among the diatomaceous earth, a fired product is preferred, and freshwater diatomaceous earth is preferred, but other diatomaceous earth can also be adopted.
Specific examples of such diatomaceous earth include Celite (registered trademark) manufactured by Celite and Ceratom (trade name) manufactured by Eagle Pitcher Minerals. Moreover, what baked these with sodium carbonate etc. can also be employ | adopted.

The hydrotalcites are (M ²⁺ ) _{1 -x} (M ³⁺ ) _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · aH ₂ O (where M ²⁺ is a divalent metal) indicates ion, M ³⁺ is a trivalent metal ion, a ^n-represents an n-valent anion, and x and a indicates a range 0 <x <0.5,0 ≦ a < 1 , respectively. ) consists of at least one member selected from the group consisting of, Mg as M ^2+, Ca or Zn is, the Al or Fe as M ^3+, as A ^n- is _{^{OH -, ClO 4 -, NO}} 3 - , SO ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻ , PO ₄ ³⁻ or CH ₃ COO ⁻ can be mentioned.

  Next, as the solid catalyst C, an oxide of a metal selected from the group consisting of tungsten, molybdenum and vanadium, an oxyacid containing a metal selected from the group consisting of tungsten, molybdenum and vanadium and salts thereof, and iron Oxides, halides and sulfates of elements selected from the group consisting of manganese and ruthenium are employed.

Examples of the metal oxide selected from the group consisting of tungsten, molybdenum, and vanadium include WO ₃ , MoO ₃ , and V ₂ O ₅ . Examples of oxyacids and salts thereof containing a metal selected from the group consisting of tungsten, molybdenum and vanadium include tungstic acid (H ₂ WO ₄ ), tungstates such as Na ₂ WO ₄ , molybdic acid (H ₂ MoO _4). ), Molybdate such as Na ₂ MoO ₄ , vanadic acid, vanadate such as NH ₄ VO ₃ , isopolyacids containing tungsten, molybdenum or vanadium and salts thereof, heteropolyacids containing tungsten, molybdenum or vanadium and Examples thereof include salts thereof. The isopolyacids and heteropolyacids containing tungsten, molybdenum or vanadium are hybrids represented by (Q ₃ [PW ₆ Mo ₆ O _{4 0} ], Q ₇ [PV ₄ Mo ₈ O _{4 0} ], etc.) Or a peroxo type compound represented by Q ₃ {PO ₄ [W (O) (O ₂ )] ₄ }, Q ₂ [W ₂ O ₃ (O ₂ ) ₄ ], etc. Q represents a counter cation.)

Examples of the heteroatoms of the heteropolyacids include phosphorus, boron, silicon, germanium, lanthanoid elements, manganese, nickel, iron, cobalt, and ruthenium. The counter cation of the isopolyacid salt or heteropolyacid salt includes tetrabutylammonium, butylammonium, benzyltrimethylammonium, cetylpyridinium organic cations, and inorganic cations such as ammonium, potassium, sodium, and calcium. Can be mentioned.
More specifically, the iso polytungstic acids containing _{tungsten, (NH 4) 6 W 7} O 2 4, (NH 4) 1 0 [H 2 W 1 2 O 4 2], (CetylPy) 1 0 [H ₂ W _{1 2} O _{4 2} ], (CetylPy) ₄ [W _{1 0} O _{3 2} ], K ₄ [W _{1 0} O _{3 2} ] and the like can be mentioned. Examples of the heteropolytungstic acids containing tungsten include , (CetylPy) ₃ [PW _{1 2} O _{4 0} ], (CetylPy) ₅ H ₂ [PW _{1 1} O _{3 9} ], Na ₉ [PW ₉ O _{3 4} ] and the like, and the heteropolytungsten described above. Examples include those in which phosphorus (P) in acids is replaced with boron (B), silicon (Si), germanium (Ge), or the like. In the formula, CetylPy represents cetylpyridinium.

  Examples of the oxygen acid containing molybdenum and salts thereof include compounds in which tungsten in the compounds exemplified as the oxygen acid containing tungsten and salts thereof is substituted with molybdenum. Examples of the oxygen acid containing vanadium and salts thereof include compounds in which tungsten in the compounds exemplified as the oxygen acid containing tungsten and salts thereof is substituted with vanadium.

  Furthermore, among the solid catalysts C, a catalyst selected from the group consisting of oxides of tungsten or molybdenum, isopolyacids containing tungsten or molybdenum, and heteropolyacids containing tungsten or molybdenum is preferred, and in particular contains tungsten. A catalyst selected from the group consisting of isopolyacids or heteropolyacids is preferred because high selectivity can be obtained.

Examples of oxides, halides, and sulfates of elements selected from the group consisting of iron, manganese, and ruthenium include FeCl ₃ , MnSO ₄ , and RuCl ₃ .

  In the solid-phase oxidation reaction method, the solid catalyst C does not need to be fixed to the solid dispersed phase S, and the solid catalyst C powder and the solid dispersed phase S powder may be simply mixed. For example, a mixture that becomes a solid phase of the oxidation reaction system can be obtained by a method in which the powder of the solid catalyst C is added to the powder of the solid dispersion phase S in advance and the powders are stirred and mixed. The particle size of the powder of the solid catalyst C and the powder of the solid dispersed phase S is not particularly limited, but easily available powder with a particle size of about 5 to 100 μm can be used to achieve a high yield of the product. can do.

  Next, as the raw material organic compound O, for example, cyclooctene, 1-decene, 2-octen1-ol, allylbenzene, dicyclopentadiene, 1,5-cyclooctadiene, (R)-(+)-limonene Benzyl alcohol, α-phenethyl alcohol, paratrimethyl sulfide, γ-picoline, and the like.

Hereinafter, the manufacturing method of the organic compound using the solid-phase oxidation reaction method of the present invention will be described together with the operation mode of the manufacturing apparatus 1 of the present invention. In this embodiment, as an example, the raw material organic compound O is oxidized with hydrogen peroxide H to obtain an epoxy compound E as an organic compound.
[Mixture preparation step] (see FIG. 2S1, FIG. 3 (a), (b))
First, with the shut-off valves 22, 23, 25 closed and the shut-off valves 28, 29 open, the motor 40 is started to invert the container body 2 upside down as shown in FIG. Next, the lid 24 is opened, and the powder of the solid catalyst C and the powder of the solid dispersed phase S are put into the container body 2. Next, the lid 24 is closed so that the filter support member 27 and the filter 27a are sandwiched between the container body 2 and the lid body 24. In this state, the motor 40 is activated to rotate the container body 2. The mixture M is prepared by mixing the powder of the solid catalyst C and the powder of the solid dispersed phase S.
In addition to the above-described method, the filter support 27 and the filter 27 are sandwiched between the container main body 2 and the shutoff valve 22 is opened, and the solid catalyst C and the solid dispersed phase S are mixed outside the container main body 2. The mixture M can also be prepared by, for example, charging the container body 2 through the shutoff valve 22.

[Mixing step] (see FIG. 2S2, FIG. 3C)
Next, the shutoff valves 28 and 29 are closed, the shutoff valve 23 is opened, and the liquid raw material organic compound O is supplied from the supply device (not shown) into the container body 2 through the supply pipe 26 to impregnate the mixture M. The mixture M impregnated with the raw material organic compound O is apparently in a powder state. Note that the shutoff valve 28 is slightly opened, and the container body 2 is evacuated so as not to be pressurized by supplying the raw material organic compound O. When exhaust is completed, the shutoff valve 28 is closed.
Furthermore, if necessary, the raw material organic compound O can be spread over the entire area of the mixture M by starting the motor 40 and rotating the container body 2. Moreover, in order to absorb more uniformly, the container main body 2 is connected by connecting the supply device (not shown) of the raw material organic compound O and the shutoff valve 23 with a flexible tube (not shown). The raw material organic compound O is supplied while rocking continuously or intermittently.
Then, according to the flow state due to the rocking of the mixture M in the container main body 2, the supply device (not shown) is appropriately supplied, or the rocking is stopped intermittently, so that the container main body 2 is The supply pipe 26 may be directed toward the mixture M that is deposited in an inclined state. Even during this swinging, a slight exhaust is performed as described above.

[Impregnation step] (see FIG. 2S3, FIG. 3C)
Next, the shut-off valve 23 is opened, and the hydrogen peroxide solution H is supplied from the supply device (not shown) into the container body 2 through the supply pipe 26 to further impregnate the mixture M impregnated with the raw material organic compound O. The mixture M impregnated with the raw material organic compound O and the hydrogen peroxide solution H is apparently in a powder state.
As in the above mixing step, the shutoff valve 28 is slightly opened, and the container body 2 is evacuated so as not to be pressurized by the supply of the hydrogen peroxide solution H. When exhaust is completed, the shutoff valve 28 is closed. Similarly to the above mixing step, if necessary, the motor 40 is started and the container body 2 is rotated, so that the hydrogen peroxide solution H can be uniformly distributed over the entire area of the mixture M. Furthermore, as in the above mixing step, the hydrogen peroxide solution H supply device (not shown) and the shutoff valve 23 are connected by a flexible tube (not shown) in order to absorb more uniformly. Thus, the hydrogen peroxide solution H is supplied while the container body 2 is swung continuously or intermittently.

[Oxidation reaction step (see FIG. 2S4, FIG. 3 (d))
Next, hot water as a heating medium is supplied from the heating medium generator 6 into the jacket 3. In this embodiment, the inside of the container body 2 is kept at 25 ° C. as an example. The heat medium whose temperature is adjusted (heated or cooled) for the container body 2 is discharged from the jacket 3.
The mixture M impregnated with the organic compound O and the hydrogen peroxide solution H is deposited on the upper surface of the filter 27a so as to have a substantially uniform layer thickness as shown in FIG. For 6 hours (here, 6 hours as an example). At this time, the powder surface of the mixture M becomes a special reaction field. Apparently, epoxidation proceeds gently in the powder state, and a high-purity epoxy compound E (oxide) is obtained. At this time, the deterioration of the solid catalyst C is extremely small, and water is the only byproduct produced by this reaction.
Although not specifically shown, the temperature sensor (not shown) is positioned at a position where it is buried in the mixture M and near the center of the filter 27a in plan view, that is, a position farthest from the jacket 3 to oxidize. You may make it measure the temperature in a reaction process and adjust the temperature or supply amount of the hot water supplied to the jacket 3 from the heat-medium generator 6 according to a temperature rise.

In consideration of adjusting the temperature or supply amount of hot water based on such temperature measurement, the mixture M is deposited on the inner surface of the container body 2 in a wide contact state, and in this state, the oxidation reaction step is performed. Implementing is also one of the preferred embodiments.
For this reason, the attitude of the manufacturing apparatus 1 during the oxidation reaction process is not the state shown in FIG. 3D, but the container body 2 is rotated 180 ° so that the shutoff valve 22 is positioned downward. The mixture M is accumulated, or the container body 2 is rotated 90 ° from this state so that the shutoff valve 22 is in a horizontal position, and the mixture M is deposited mainly on the inner surface of the container body 2. It is also possible to adopt a form that makes it in a state of being allowed to enter. Even when these forms are adopted, the sensing position of a temperature sensor (not shown) is buried in the mixture M.

Regarding the adjustment of hot water supplied into the jacket 3, for example, when the heat radiation from the container body 2 is large and the mixture M is at a temperature lower than a predetermined temperature, the hot water is set so that the mixture M has a predetermined temperature. Adjust the temperature and supply. Moreover, the temperature of the hot water discharged from the jacket 3 is measured by a temperature sensor (not shown), and the temperature of the hot water supplied from the heat medium generator 6 to the jacket 3 is adjusted according to the temperature rise or temperature drop. You may do it.
Then, when the above-described oxidation reaction step is completed, the supply of hot water to the jacket 3 is stopped.

  In the above description, the case where the oxidation reaction process is performed in a state where the container body 2 is left stationary without rotating is shown, but the oxidation reaction process can also be performed while rotating the container body 2. In other words, in the oxidation reaction process, the temperature control that causes the optimum reaction over time can be performed efficiently so that the oxidation reaction process can proceed efficiently. When it is actively performed, or when warming is actively performed to promote the oxidation reaction, the main body container 2 is gently rotated so as to exchange heat by making contact with hot water in the jacket 3 as much as possible. It is also preferable to perform an appropriate combination of rotation and stationary, that is, rotation and stationary state.

[Recovery Step] (See FIG. 2S5, FIG. 3 (e), (f))
Next, the epoxy compound E and water are taken out of the container body 2 by extraction or direct distillation under reduced pressure.
Here, an extraction method will be described as an example, and the shutoff valve 23 is opened, and as shown in FIG. 3E, the mixture M that has finished the oxidation reaction process is deposited on the upper surface of the filter 27a. In this state, solvent R (hexane, pentane, ethyl acetate, etc.) is injected from the supply pipe 26 into the container body 2, and if necessary, the shut-off valve 23 is closed to supply hot water from the heating medium generator 6 to the jacket 3. Then, while heating, the motor 40 is started to rotate the container body 2 and then left to stand for a certain period of time at the position where the lid 24 is down. Thereafter, the shutoff valve 28 is opened, then the shutoff valve 25 is opened to introduce air into the container body 2 (FIG. 3 (f)), and the liquid in the container body 2 is pressurized (˜0.01 MPaG). Filter. If necessary, the space below the filter 27a may be depressurized, or may be filtered without being pressurized or depressurized.
The solvent R (filtrate) in which the epoxy compound E is dissolved is taken out from the filtrate outlet 24a, and the epoxy compound E is obtained by concentration of the filtrate and precipitation operation from the filtrate. Will be recovered. When the filtrate is no longer discharged from the shutoff valve 28, the shutoff valves 25 and 28 are closed. The solvent R can be appropriately recovered and reused.
In addition, the epoxy compound E in the mixture M is also collect | recovered by repeating taking out to the exterior of the solvent R in which the epoxy compound E was melt | dissolved from injection | pouring of the solvent R mentioned above as needed.

[Regeneration process] (see FIG. 2S6, FIGS. 3G and 3H)
After the filtrate (solvent R in which the epoxy compound E is dissolved) is discharged as described above, the filter cake of the mixture M remains on the filter 27a. In addition to the above, a powder of the solid dispersion phase S is included, and in addition, a solvent R in which an epoxy compound E is dissolved and water are included. Therefore, by drying the filter cake, the solid catalyst C and the solid dispersed phase S are returned to a reusable dry powder state. First, hot water as a heat medium is supplied from the heat medium generator 6 into the jacket 3, the refrigerator 8 a is started, and the refrigerant is supplied from the refrigerator 8 a to the condenser 8. Next, the vacuum pump P is activated, the shutoff valve 29 is opened, the motor 40 is activated, and the container body 2 is rotated. By this rotation, the filter cake is peeled off from the filter 27a, etc., contacts the inner surface of the main body container 2 and is heated by the hot water supplied from the jacket 3 to evaporate the solvent R and water. The fine powder is removed by a filter (not shown) in the separation device 7 and then condensed and recovered in the condenser 8. This condensate is reused as appropriate. Condensation may also occur in the separation device 7, and the drain generated here is appropriately recovered and reused.
Further, instead of rotating the main body container 2, the present regeneration step can be performed by swinging as described in the impregnation step. In this case, instead of air in the above-described recovery step, the hot air generator (not shown) and the shutoff valve 25 are connected by a flexible tube (not shown), and the shutoff valve 25 is opened. The solvent R and water can be quickly evaporated by supplying warm air from the supply pipe 26 while the container body 2 is swung continuously or intermittently.

The completion of the removal of the solvent R from the filter cake is confirmed by the temperature change in the container body 2 or by the stop of the generation of the condensate in the condenser 8, and then the filter 27a is moved downward. The rotation is stopped at the position where the surface 27a becomes horizontal, the shutoff valve 29 is closed, and the vacuum pump P and the refrigerator 8a are stopped. Thereafter, the valve 28 is opened to return the inside of the main body container 2 to atmospheric pressure.
Thus, in the regeneration step, the filter cake is pulverized and pulverized by the above-mentioned rotation or swinging and drying, and a mixture of the powder containing the solid catalyst C powder and the solid dispersed phase S powder. Reuse as M is possible.
Then, as shown in FIG. 2, a decision to continue the production is made (S7), and if it is judged that the recycling is possible (S8), the mixing step, impregnation step, oxidation reaction without going through the mixture preparation step. A process, a recovery process, and a regeneration process are sequentially performed.
Whether or not recycling is possible is determined by collecting a part of the mixture M from the shutoff valve 22 and confirming its physical properties. When it is determined that it is unsuitable for reuse (S8), the main body container 2 is inverted 180 ° by the motor 40 and stopped with the shut-off valve 22 being lowered, the shut-off valve 22 is opened, and the mixture M is discharged (S9). Then, as described above, the production may be newly started from the mixture preparation step (S1).
Incidentally, it has been confirmed by the present applicant that the mixture M can be reused at least 25 times.

As described above, according to the present invention, the mixture preparation step, the mixing step, the impregnation step, the oxidation reaction step, and the recovery step for carrying out the solid-phase oxidation reaction method are performed in the single container body 2. Furthermore, since the regeneration step can be carried out without taking out the mixture M from the container body 2, the second and subsequent mixture preparation steps can be omitted, and the organic phase can be obtained by a solid-phase oxidation reaction method. The compound can be produced very efficiently and at low cost.
Furthermore, since the capacity | capacitance of the container main body 2 can be 1000 liters or more, manufacture of the organic compound in an industrialization level is realizable.
Further, in the above-described embodiment, since it can be carried out without using a halide in all the steps, there is no need for a purification step for removing halogen, and a complete halogen-free organic compound (epoxy compound E) is obtained. Can be obtained.

[Other Examples]
The present invention is based on the above-described embodiment, but based on the technical idea of the present invention, the following embodiment can also be adopted.
First, the manufacturing apparatus 1 described above effectively mixes, impregnates, or drys powders by turning the container body 2 upside down or swinging, and the organic compound using the solid-phase oxidation reaction method of the present invention can be obtained. Although the manufacturing method was performed, for example, as shown in FIG. 4, mixing, impregnation, or drying was effectively performed using a manufacturing apparatus 9 including a stirring device 91, and the solidification of the present invention was performed. It is also possible to carry out a method for producing an organic compound using a phase-based oxidation reaction method.
Since the manufacturing method using the manufacturing apparatus 9 is substantially the same as the manufacturing method using the manufacturing apparatus 1, the main configuration of the manufacturing apparatus 9, the main part of the manufacturing method when using the manufacturing apparatus 9, and A different part from the manufacturing method when using the manufacturing apparatus 1 is demonstrated.

First, the stirring device 91 is configured to include, for example, a single ribbon blade 911 and is rotated in an inverted conical container body 93 in the manufacturing device 9 by a motor 90. The ribbon blade 911 is a spiral blade plate, which is continuous from directly above the filter 27 a provided at the bottom of the main body container 93 to the upper portion of the main body container 93, and a blade plate near the inner wall surface of the main body container 93. Is what rotates. Therefore, when the ribbon blade 911 rotates, the mixture M located at the bottom of the main body container 93 is lifted to the upper part of the main body container 93 along the inner wall surface of the main body container 93 and then falls to the center of the main body container 93. Therefore, the mixture M is vigorously stirred in the main body container 93.
The container main body 93 can be sealed in the same manner as the main body container 2 shown in the basic embodiment, and an appropriate sealing mechanism (not shown) is provided in a portion through which the rotation shaft of the stirring device 91 passes. It has been.

Next, a method for producing an organic compound using the solid-phase oxidation reaction method of the present invention using the production apparatus 9 will be described. This example is also performed in accordance with the flowchart shown in FIG. In the adjustment step, the solid catalyst C and the solid dispersed phase S are introduced into the container main body 93 from the charging port 92, and the solid catalyst C and the solid dispersed phase S are stirred and mixed by the rotation of the ribbon blade 911 of the stirrer 91. Mixture M.
Next, in the mixing step, the raw material organic compound O is uniformly mixed with the mixture M by supplying the raw material organic compound O from the supply pipe 26 while stirring the mixture M by the rotation of the ribbon blade 911.
Next, in the impregnation step, the hydrogen peroxide solution H is uniformly mixed with the mixture M by supplying the hydrogen peroxide solution H from the supply pipe 26 while stirring the mixture M by the rotation of the ribbon blade 911.
Next, in the oxidation reaction step, the rotation of the ribbon blade 911 is stopped, whereby the mixture M is allowed to stand, and the temperature is adjusted by the heat medium supplied from the heat medium generator 6 to the jacket 3 provided on the outer surface of the main body container 93. Oxidation reaction is performed in the state in which. In addition, the ribbon blade | wing 911 may be rotated as needed and the mixture M may be stirred and heat exchange with the heat medium in the jacket 3 can be accelerated | stimulated.
Next, in the recovery process, when the solvent R is injected from the supply pipe 26 in a state where the rotation of the ribbon blade 911 is stopped, the epoxy compound E generated in the mixture M in the oxidation reaction process is dissolved in the solvent R, and this solvent is filtered. 27a is taken out from the manufacturing apparatus 9 through the filtrate outlet 24a. In addition, melt | dissolution in the solvent R of the epoxy compound E can be accelerated | stimulated by inject | pouring the solvent R, rotating the ribbon blade | wing 911 as needed.
Next, in the regeneration step, the ribbon blade 911 is rotated, a heating medium is supplied to the jacket 3, and the solvent R and water that evaporate in the container body 93 are exhausted by the vacuum pump P, whereby the filter cake is dried solid. If it is regenerated as a mixture M of the powder of the catalyst C and the powder of the solid dispersed phase S, and it is judged that it can be reused thereafter, the mixing step, impregnation step, oxidation reaction step without going through the mixture preparation step The recovery process and the regeneration process are sequentially performed.
When it is necessary to take out the mixture M from the container main body 93, the damper 941 of the discharge device 94 provided near the bottom of the container main body 93 is opened, or the lid 24 is removed from the container main body 93. Furthermore, the mixture M can be discharged | emitted by opening the cover body 24 from the container main body 93 using the hinge mechanism which is not shown in figure.

In the two embodiments described above, the mixture preparation process, the mixing process, the impregnation process, the oxidation reaction process, the recovery process, and the regeneration process are all performed in the same container body 2 and 93. You may make it perform a part or multiple in the exterior of the container main bodies 2 and 93. FIG.
First, an embodiment in which the regeneration step is performed outside the container bodies 2 and 93 will be described. Specifically, in the case of the manufacturing apparatus 1, after the collection step is finished, the filter cake of the mixture M located on the filter 27 a can be peeled off from the filter 27 a by the rotation of the container body 2 and discharged from the shutoff valve 22. After being crushed, it is discharged from the shutoff valve 22 to the outside. Moreover, in the case of the manufacturing apparatus 9, the filter cake of the mixture M is discharged | emitted from the container main body 93 as mentioned above.
Then, the filter cake is dried using a dryer (not shown) separately prepared as a component device of the manufacturing apparatuses 1 and 9, and the dried cake is crushed as necessary to be regenerated as a powder mixture M. Is.
The mixture M regenerated outside the container main bodies 2 and 93 is supplied into the main body containers 2 and 93 and impregnated or mixed with the raw material organic compound O in the same manner as the basic embodiment described above. A mixing step is performed, and subsequently, an impregnation step, an oxidation reaction step, and a recovery step are sequentially performed.

  Further, the mixture M regenerated outside the container bodies 2 and 93 as described above is impregnated with the raw material organic compound O using a mixer (not shown) separately prepared as a component device of the manufacturing apparatuses 1 and 9. Or after mixing, this thing is moved in the container main bodies 2 and 93, hydrogen peroxide solution H is supplied from the supply pipe 26, an impregnation process is performed, and then an oxidation reaction process and a recovery process are performed. Forms can also be taken.

Furthermore, the mixture preparation step for mixing the solid catalyst and the solid dispersed phase can also be performed outside the container bodies 2 and 93 by using a mixer separately prepared as a component device of the manufacturing apparatuses 1 and 9. is there.
Thus, when any one or more of the mixture preparation step, the mixing step, and the regeneration step are performed without using the container bodies 2 and 93, for example, an efficient mixer or dryer is used. Thus, there is an advantage that the manufacturing time can be shortened.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 2 Container body 20 Opening part 21 Raw material supply port 22 Shut-off valve 23 Shut-off valve 24 Lid 24a Filtrate discharge port 25 Shut-off valve 26 Supply pipe 27 Filter support material 27a Filter 28 Shut-off valve 29 Shut-off valve 3 Jacket 4 Support shaft 40 Motor 41 Bearing 42 Chain 43 Rotary joint 5 Support shaft 51 Bearing 6 Heat medium generator 7 Separating device 8 Condenser 8a Refrigerator 9 Manufacturing device 90 Motor 91 Stirrer 911 Ribbon blade 92 Input port 93 Container body 94 Discharge mechanism C Solid Catalyst E Epoxy compound H Hydrogen peroxide solution M Mixture O Raw material organic compound P Vacuum pump R Solvent S Solid dispersed phase

Claims (6)

A mixture preparation step of mixing a solid catalyst powder and a solid dispersed phase powder to prepare a powder mixture;
A mixing step of adding a raw organic compound to the mixture;
An impregnation step of impregnating the mixture subjected to the treatment in the mixing step with an oxidizing agent;
An oxidation reaction step of reacting the raw organic compound in the mixture subjected to the treatment in the impregnation step with an oxidizing agent;
A recovery step of recovering the organic compound produced in the oxidation reaction step in a state dissolved in a solvent;
In the method for producing an organic compound, an organic compound is obtained by sequentially performing
A method for producing an organic compound using a solid-phase oxidation reaction method, wherein at least the impregnation step, the oxidation reaction step, and the recovery step are performed in the same container body. A regeneration step for reusing the mixture containing the solid catalyst powder and the solid dispersed phase powder after the recovery step is carried out,
Using the mixture regenerated by the regeneration step,
The method for producing an organic compound using a solid-phase oxidation reaction method according to claim 1, wherein the mixing step, impregnation step, oxidation reaction step, recovery step and regeneration step are repeated. In addition to the impregnation step, oxidation reaction step and recovery step,
Of the mixture preparation process, mixing process or regeneration process,
Any one process or multiple processes,
The method for producing an organic compound using the solid phase oxidation reaction method according to claim 2, wherein the method is carried out in the same container body. A sealable container body;
A filter provided in the container body;
A device for supplying gas into the container body;
In an apparatus configured with a temperature adjustment mechanism for setting the inside of the container body to a desired temperature,
A mixture preparation step of mixing a solid catalyst powder and a solid dispersed phase powder to prepare a powder mixture;
A mixing step of adding a raw organic compound to the mixture;
An impregnation step of impregnating the mixture subjected to the treatment in the mixing step with an oxidizing agent;
An oxidation reaction step of reacting the raw organic compound in the mixture subjected to the treatment in the impregnation step with an oxidizing agent;
A recovery step of recovering the organic compound produced in the oxidation reaction step in a state dissolved in a solvent;
In an organic compound production apparatus capable of obtaining an organic compound by sequentially performing
An apparatus for producing an organic compound using a solid-phase oxidation reaction method, characterized in that at least the impregnation step, the oxidation reaction step, and the recovery step can be performed in the same container body. After the recovery step is performed, the regeneration step for reusing the mixture containing the solid catalyst powder and the solid dispersed phase powder can be performed,
Using the mixture regenerated by the regeneration step,
The organic compound using the solid-phase oxidation reaction method according to claim 4, wherein the mixing step, the impregnation step, the oxidation reaction step, the recovery step, and the regeneration step can be repeated. Manufacturing equipment. In addition to the impregnation step, oxidation reaction step and recovery step,
Of the mixture preparation process, mixing process or regeneration process,
Any one process or multiple processes,
The apparatus for producing an organic compound using a solid-phase oxidation reaction method according to claim 5, wherein the apparatus is configured to be performed in the same container body.

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