WO2014157343A1 - Process for producing organic compound using solid-phase oxidation method, and device therefor - Google Patents
Process for producing organic compound using solid-phase oxidation method, and device therefor Download PDFInfo
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- WO2014157343A1 WO2014157343A1 PCT/JP2014/058554 JP2014058554W WO2014157343A1 WO 2014157343 A1 WO2014157343 A1 WO 2014157343A1 JP 2014058554 W JP2014058554 W JP 2014058554W WO 2014157343 A1 WO2014157343 A1 WO 2014157343A1
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- organic compound
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- oxidation reaction
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- powder
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- 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.
- a raw material organic compound a high-purity oxidation reaction product
- 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.
- 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.
- 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
- 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.
- 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.
- 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 includes: a sealable container body; a filter provided in the container body; and a device for supplying gas into the container body.
- 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 Obtaining an organic compound 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 solvent state
- the manufacturing apparatus of an organic compound which can, those comprising as
- 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.
- 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.
- 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 organic compound produced by the solid-phase oxidation reaction method can be provided to the market. .
- 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.
- 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.
- 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.
- simplification of processes, such as material conveyance, and reduction of an apparatus space can be aimed at.
- 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.
- 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.
- simplification of processes, such as material conveyance, and reduction of an apparatus space can be aimed at.
- FIG. 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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
- 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.
- a raw material organic compound O and an example of an oxidizing agent are used in the powder of the mixture M.
- 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.
- an oxidation reaction has been performed in a liquid phase using a solvent.
- a solid-phase oxidation reaction method a solid dispersed phase is used as a medium instead of a solvent.
- 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).
- an organic compound raw material organic compound O
- an oxidizing agent hydrogen peroxide water H
- 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.
- the mode in which the liquid raw material organic compound O is impregnated into the mixture M is described.
- the raw material organic compound O may be in a liquid state or in a powder state.
- 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.
- stimulates oxidation reaction is employ
- 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.
- a solid dispersed phase selected from phosphates, diatomaceous earth, silica, alumina, white clay, silica alumina and calcium fluoride 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.
- 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.
- Diatomaceous earth is preferably porous and has a high porosity and a cake bulk density of about 0.2 to 0.45.
- 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
- 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.
- 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.
- 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 such as NH 4 VO 3
- 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.)
- 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.
- 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.
- 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.
- 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.
- oxides, halides, and sulfates of elements selected from the group consisting of iron, manganese, and ruthenium include FeCl 3 , MnSO 4 , and RuCl 3 .
- the solid catalyst C does not need to be immobilized on the solid dispersed phase S, and the solid catalyst C powder and the solid dispersed phase S powder may be simply mixed.
- 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 a powder having a particle size of about 5 to 100 ⁇ m, which is easily available, can be used, and a high yield of the product is realized. can do.
- the raw material organic compound O for example, cyclooctene, 1-decene, 2-octen1-ol, allylbenzene, dicyclopentadiene, 1,5-cyclooctadiene, (R)-(+)-limonene Benzyl alcohol, ⁇ -phenethyl alcohol, paratrimethyl sulfide, ⁇ -picoline and the like.
- 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.
- 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.
- 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.
- 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.
- 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.
- the container main body 2 is connected by connecting the raw material organic compound O supply device (not shown) and the shut-off 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 body 2, supply is appropriately performed by the feeding device (not shown), or the rocking is stopped intermittently, so that the container body 2 is appropriately
- 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.
- 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.
- 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.
- 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.
- 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.
- the hydrogen peroxide solution H is supplied while the container body 2 is swung continuously or intermittently.
- 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.
- 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.
- 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.
- 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.
- the oxidation reaction process can also be performed while rotating the container body 2.
- the temperature control that causes the optimum reaction over time can be performed efficiently so that the oxidation reaction process can proceed efficiently.
- 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.
- 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.
- the shutoff valves 25 and 28 are closed.
- the solvent R can be appropriately recovered and reused.
- the epoxy compound E in the mixture M is also collect
- the vacuum pump P is activated, the shutoff valve 29 is opened, the motor 40 is activated, and the container body 2 is rotated.
- 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.
- the present regeneration step can be performed by swinging as described in the impregnation 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 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.
- 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.
- 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.
- 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).
- 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.
- 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
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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
- 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.
- 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.
- the mixture M can be discharged
- 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.
- the filter cake of the mixture M is discharged
- 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.
- 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.
- 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.
- a mixer separately prepared as a component device of the manufacturing apparatuses 1 and 9. is there.
- an efficient mixer or dryer is used.
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Abstract
[Problem] To develop: a novel process for producing an organic compound using a solid-phase oxidation method, the process making it possible to industrially practice the solid-phase oxidation method; and a device for the production process.
[Solution] A process for producing an organic compound by successively conducting the following steps: a mixture preparation step in which a powder of a solid catalyst is mixed with a powder of a solid dispersing phase to prepare a powdery mixture; a mixing step in which a starting-material organic compound is added to the mixture; an impregnation step in which the mixture obtained in the mixing step is impregnated with an oxidizing agent; an oxidation step in which the starting-material organic compound and the oxidizing agent in the mixture obtained in the impregnation step are reacted with each other; and a recovery step in which the organic compound yielded in the oxidation step is recovered in the state of having been dissolved in a solvent. The process is characterized in that at least the impregnation step, oxidation step, and recovery step are conducted in the main body of the same vessel.
Description
本発明は有機化合物の製造方法並びにその装置に関するものであって、特に実験室レベルで確立されている固相系酸化反応法を工業的に実現することのできる、固相系酸化反応法を用いた有機化合物の製造方法並びにその装置に係るものである。
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.
本出願人の一方は、固体触媒の粉体と固体分散相の粉体から成る粉体の混合物に、原料としての有機化合物(以下、原料有機化合物と呼ぶ)を混合し、更に酸化剤として過酸化水素水を含浸させ、見かけ上粉体状態の混合物とし、これを常温で静置することにより、原料有機化合物から高純度の酸化反応物(以下、有機化合物と呼ぶ)が得られることを見出し、既に特許出願に及んでいる(特許文献1参照)。
このような固相系酸化反応法は、有機化合物の酸化反応システムであって、固体分散相の粉体と固体触媒の粉体との混合物(粉体)、原料有機化合物、濃度が5%以上で35%未満あるいは35%以上で60%未満の過酸化水素水(酸化剤)からなり、原料有機化合物、固体触媒及び過酸化水素水が互いに接触するように、前記混合物内に分散されていることを特徴とするものである。
そして上記固相系酸化反応法によって、地球環境に悪影響を与える有機溶媒を必要とすることなく、且つ転化率や選択率が高く(すなわち生成物の収率が高く)、更に触媒の再使用が可能である等の利点を有するとともに、反応操作を複雑にする工程を必要とすることなく、且つ反応速度が高く、更に製造物の単離や回収操作が容易な、工業的価値の高い製造が可能となることが期待されている。 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.
このような固相系酸化反応法は、有機化合物の酸化反応システムであって、固体分散相の粉体と固体触媒の粉体との混合物(粉体)、原料有機化合物、濃度が5%以上で35%未満あるいは35%以上で60%未満の過酸化水素水(酸化剤)からなり、原料有機化合物、固体触媒及び過酸化水素水が互いに接触するように、前記混合物内に分散されていることを特徴とするものである。
そして上記固相系酸化反応法によって、地球環境に悪影響を与える有機溶媒を必要とすることなく、且つ転化率や選択率が高く(すなわち生成物の収率が高く)、更に触媒の再使用が可能である等の利点を有するとともに、反応操作を複雑にする工程を必要とすることなく、且つ反応速度が高く、更に製造物の単離や回収操作が容易な、工業的価値の高い製造が可能となることが期待されている。 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.
しかしながらこのような固相系酸化反応法は、現状ではあくまでもビーカ、試験管等を用いた実験室段階での実証が成されているものの、工業的な生産が実現されるには至っていなかった。
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. .
本発明はこのような背景からなされたものであり、固相系酸化反応法を工業的に実現することのできる、新規な固相系酸化反応法を用いた有機化合物の製造方法並びにその装置を開発することを技術課題としたものである。
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.
すなわち請求項1記載の固相系酸化反応法を用いた有機化合物の製造方法は、固体触媒の粉体と固体分散相の粉体とを混合して粉体の混合物を調製する混合物調製工程と、前記混合物に原料有機化合物を加える混合工程と、前記混合工程における処理が行われた混合物に酸化剤を含浸させる含浸工程と、前記含浸工程における処理が行われた混合物中の原料有機化合物と酸化剤とを反応させる酸化反応工程と、前記酸化反応工程で生成された有機化合物を溶剤に溶解させた状態で回収する回収工程と、を順次実施することにより有機化合物を得る有機化合物の製造方法において、少なくとも前記含浸工程、酸化反応工程及び回収工程を同一の容器本体内において行うことを特徴として成るものである。
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.
また請求項2記載の固相系酸化反応法を用いた有機化合物の製造方法は、前記要件に加え、前記回収工程が実施された後の、固体触媒の粉体と固体分散相の粉体とを含む混合物を再利用するための再生工程が実施されるものであり、前記再生工程により再生された混合物を用いて、前記混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を繰り返して行うことを特徴として成るものである。
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.
更にまた請求項3記載の固相系酸化反応法を用いた有機化合物の製造方法は、前記請求項2記載の要件に加え、前記含浸工程、酸化反応工程及び回収工程に加え、前記混合物調製工程、混合工程あるいは再生工程の内、いずれか一つの工程あるいは複数の工程を、前記同一の容器本体内において行うことを特徴として成るものである。
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.
また請求項4記載の固相系酸化反応法を用いた有機化合物の製造装置は、密閉可能な容器本体と、この容器本体内に設けられたフィルタと、容器本体内に気体を供給する装置と、容器本体内を所望の温度とするための温度調整機構とを具えて構成された装置において、固体触媒の粉体と固体分散相の粉体とを混合して粉体の混合物を調製する混合物調製工程と、前記混合物に原料有機化合物を加える混合工程と、前記混合工程における処理が行われた混合物に酸化剤を含浸させる含浸工程と、前記含浸工程における処理が行われた混合物中の原料有機化合物と酸化剤とを反応させる酸化反応工程と、前記酸化反応工程で生成された有機化合物を溶剤に溶解させた状態で回収する回収工程と、を順次実施することにより有機化合物を得ることができる有機化合物の製造装置において、少なくとも前記含浸工程、酸化反応工程及び回収工程を同一の容器本体内において行うことができるように構成されていることを特徴として成るものである。
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 Obtaining an organic compound 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 solvent state In the manufacturing apparatus of an organic compound which can, 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.
更にまた請求項5記載の固相系酸化反応法を用いた有機化合物の製造装置は、前記請求項4記載の要件に加え、前記回収工程が実施された後の、固体触媒の粉体と固体分散相の粉体とを含む混合物を再利用するための再生工程を実施することができるように構成されるものであり、前記再生工程により再生された混合物を用いて、前記混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を繰り返して行うことができるように構成されていることを特徴として成るものである。
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.
更にまた請求項6記載の固相系酸化反応法を用いた有機化合物の製造装置は、前記請求項5記載の要件に加え、前記含浸工程、酸化反応工程及び回収工程に加え、前記混合物調製工程、混合工程あるいは再生工程の内、いずれか一つの工程あるいは複数の工程を、前記同一の容器本体内において行うことができるように構成されていることを特徴として成るものである。
そしてこれら各請求項記載の発明を手段として、前記課題の解決が図られる。 Furthermore, the organic compound production apparatus using the solid-phase oxidation reaction method according toclaim 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.
そしてこれら各請求項記載の発明を手段として、前記課題の解決が図られる。 Furthermore, the organic compound production apparatus using the solid-phase oxidation reaction method according to
The above-described problems can be solved by using the inventions described in these claims as means.
まず請求項1記載の発明によれば、固相系酸化反応法を工業的に実現することができるため、固相系酸化反応法によって製造された有機化合物を市場に提供することが可能となる。
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. .
また請求項2記載の発明によれば、再生された混合物を用いて、混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を繰り返し行うことが可能なため、省資源な製造方法として工業的実現に大きく貢献できるものである。
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.
更にまた請求項3記載の発明によれば、混合物調製工程、混合工程あるいは再生工程の内、いずれか一つの工程あるいは複数の工程を、同一の容器本体内で行うことにより、不純物の混入を低減することができる。特に、固体触媒の粉体と固体分散相の粉体を混合して粉体の混合物を調製する混合物調製工程から、続く混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を全て同一の容器本体内で行い、再生された混合物を同一の容器本体内に残したままで繰り返して混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を行うことにより、不純物の混入を大幅に低減することができ、高純度の有機化合物を製造することができる。
また、混合物調製工程、混合工程あるいは再生工程を、容器本体とは別の機器で行う場合に比べ、マテリアル搬送などの工程の簡略化、装置スペースの低減が図れる。 Furthermore, according to the invention described inclaim 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.
また、混合物調製工程、混合工程あるいは再生工程を、容器本体とは別の機器で行う場合に比べ、マテリアル搬送などの工程の簡略化、装置スペースの低減が図れる。 Furthermore, according to the invention described in
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.
また請求項4記載の発明によれば、固相系酸化反応法を工業的に実現することができるため、固相系酸化反応法によって製造された有機化合物を市場に提供することが可能となる。
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. .
更にまた請求項5記載の発明によれば、再生された混合物を用いて、混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を繰り返し行うことが可能なため、省資源な製造方法として工業的実現に大きく貢献できるものである。
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.
更にまた請求項6記載の発明によれば、混合物調製工程、混合工程、あるいは再生工程の内、いずれか一つの工程、あるいは複数の工程を、同一の容器本体内で行うことにより、不純物の混入を低減することができる。特に、固体触媒の粉体と固体分散相の粉体を混合して粉体の混合物を調製する混合物調製工程から、続く混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を全て同一の容器本体内で行い、再生された混合物を同一の容器本体内に残したままで繰り返して混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を行うことにより、不純物の混入を大幅に低減することができ、高純度の有機化合物を製造することができる。
また、混合物調製工程、混合工程あるいは再生工程を、容器本体とは別の機器で行う場合に比べ、マテリアル搬送などの工程の簡略化、装置スペースの低減が図れる。 Furthermore, according to the invention described inclaim 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.
また、混合物調製工程、混合工程あるいは再生工程を、容器本体とは別の機器で行う場合に比べ、マテリアル搬送などの工程の簡略化、装置スペースの低減が図れる。 Furthermore, according to the invention described in
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.
本発明の「固相系酸化反応法を用いた有機化合物の製造方法並びにその装置」の最良の形態の一つは以下の実施例に示すとおりであり、初めに本発明の固相系酸化反応法を用いた有機化合物の製造装置1(以下、製造装置1と称する。)の構成の一例について説明した後、この製造装置1の作動態様とあわせて本発明の固相系酸化反応法を用いた有機化合物の製造方法の一例について説明する。なおこの実施例に対して本発明の技術的思想の範囲内において適宜変更を加えることも可能である。
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.
図1に骨格的に示すのが本発明の製造装置1であり、このものは密閉可能な容器本体2内に供給された被処理物の、混合、温度調整、ろ過及び乾燥を行うことができる装置である。
まず前記容器本体2は、上部が先細り状に形成された中空円筒状の部材であり、その上部に開口部20及び原料供給口21が形成され、下部開口部を開閉可能な蓋体24によって塞ぐように構成されている。そして前記開口部20には遮断バルブ22が接続されている。
また前記原料供給口21には供給管26が、その排出部を容器本体2内に挿入状態となるように設けられており、この供給管26に接続された管路は二路に分岐するとともに、それぞれに遮断バルブ23、25が接続され、容器本体2の内部空間を密閉状態となるように構成されている。
また前記蓋体24の下部にはろ液排出口24aが形成され、蓋体24と容器本体2との間にフィルタ支持材27が設けられ、このフィルタ支持材27の上面にフィルタ27aが設けられている。 FIG. 1 schematically shows amanufacturing 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, thecontainer 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 rawmaterial 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.
Afiltrate 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.
まず前記容器本体2は、上部が先細り状に形成された中空円筒状の部材であり、その上部に開口部20及び原料供給口21が形成され、下部開口部を開閉可能な蓋体24によって塞ぐように構成されている。そして前記開口部20には遮断バルブ22が接続されている。
また前記原料供給口21には供給管26が、その排出部を容器本体2内に挿入状態となるように設けられており、この供給管26に接続された管路は二路に分岐するとともに、それぞれに遮断バルブ23、25が接続され、容器本体2の内部空間を密閉状態となるように構成されている。
また前記蓋体24の下部にはろ液排出口24aが形成され、蓋体24と容器本体2との間にフィルタ支持材27が設けられ、このフィルタ支持材27の上面にフィルタ27aが設けられている。 FIG. 1 schematically shows a
First, the
The raw
A
また容器本体2の外周部を覆うようにジャケット3が具えられるものであり、ジャケット3の内側に熱媒体を循環供給することにより、容器本体2を外側から調温してその内部の温度を所望の値とすることができるように構成されている。なおこのような熱媒体の供給手段については後述する。
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.
そして前記容器本体2は、水平軸を中心として回転駆動されるものであり、このための支持軸4、5が容器本体2の側周部に対して具えられており、これらは軸受41、51に軸支されるとともに、一方の支持軸4とモータ40の出力軸にスプロケット(図示省略)が具えられ、これらの間にチェーン42が捲回されている。このような構成により容器本体2は上下反転や回転が可能となり、一方向あるいは両方向に連続回転させる動作、適宜の角度で揺動させる動作、あるいは、ブレーキ機能を具えたモータ40により適宜の角度で停止させて静止させるなどの動作も可能となる。また詳しくは後述するが、これにより工程毎に必要な混合、含浸、あるいは酸化反応を促進させるために好ましい位置で回転を停止させてその位置を維持(静止)することなども行うことができる。
また前記支持軸4は、内部に往路と復路とが形成されて成るものであり、ロータリージョイント43を用いて熱媒発生装置6に接続されており、前記ジャケット3の内側に熱媒体を循環供給できるように構成されている。
更に前記支持軸5は中空状とされており、固気分離のための分離装置7に接続され、以降順次、冷凍機8aが具えられた凝縮器8、真空ポンプPが接続されている。また前記ろ液排出口24aに接続された管路は二路に分岐するとともに、それぞれに遮断バルブ28、29が接続され、遮断バルブ29は前記支持軸5の中空空間に連通されている。
本発明の製造装置1は一例として上述のように構成されるものであり、以下、この製造装置1を用いて実施される、本発明の固相系酸化反応法を用いた有機化合物の製造方法について説明するが、この説明に先立って、固相系酸化反応法並びに固相系酸化反応法で使用される各種物質の説明を行う。 Thecontainer 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 theheat 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 aseparation 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.
Theproduction 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.
また前記支持軸4は、内部に往路と復路とが形成されて成るものであり、ロータリージョイント43を用いて熱媒発生装置6に接続されており、前記ジャケット3の内側に熱媒体を循環供給できるように構成されている。
更に前記支持軸5は中空状とされており、固気分離のための分離装置7に接続され、以降順次、冷凍機8aが具えられた凝縮器8、真空ポンプPが接続されている。また前記ろ液排出口24aに接続された管路は二路に分岐するとともに、それぞれに遮断バルブ28、29が接続され、遮断バルブ29は前記支持軸5の中空空間に連通されている。
本発明の製造装置1は一例として上述のように構成されるものであり、以下、この製造装置1を用いて実施される、本発明の固相系酸化反応法を用いた有機化合物の製造方法について説明するが、この説明に先立って、固相系酸化反応法並びに固相系酸化反応法で使用される各種物質の説明を行う。 The
The support shaft 4 has a forward path and a return path formed therein, and is connected to the
Further, the support shaft 5 has a hollow shape and is connected to a
The
前記固相系酸化反応法は、固体分散相Sの粉体及び固体触媒Cの粉体の混合物Mを用い、この混合物Mの粉体の中に、原料有機化合物Oと、酸化剤の一例である過酸化水素水Hとを含浸させて両者を接触させ、原料有機化合物Oを酸化して製品としての有機化合物の一例であるエポキシ化合物Eを得るものである。
従来、このような二相不均一系での酸化反応では、溶媒を用いて液相中で酸化反応が行われていたが、固相系酸化反応法では溶媒の代わりに、固体分散相を媒体として用い、例えば、この固体分散相粉体中に、固体触媒Cの粉体を混合し、反応試剤である有機化合物(原料有機化合物O)と、酸化剤(過酸化水素水H)とを含浸させて、見かけ上、粉体状態のまま酸化反応を行うものである。
このため、酸化反応中に反応系を混合・撹拌する必要がなく、静置した状態で酸化反応を行うことができるものである。 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.
従来、このような二相不均一系での酸化反応では、溶媒を用いて液相中で酸化反応が行われていたが、固相系酸化反応法では溶媒の代わりに、固体分散相を媒体として用い、例えば、この固体分散相粉体中に、固体触媒Cの粉体を混合し、反応試剤である有機化合物(原料有機化合物O)と、酸化剤(過酸化水素水H)とを含浸させて、見かけ上、粉体状態のまま酸化反応を行うものである。
このため、酸化反応中に反応系を混合・撹拌する必要がなく、静置した状態で酸化反応を行うことができるものである。 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.
なお、固体分散相S、固体触媒C、原料有機化合物O及び過酸化水素水Hの混合あるいは含浸態様としては、上述した態様の他に、固体分散相Sの粉体中に固体触媒Cの粉体を混合し、原料有機化合物Oを含浸させたものと、過酸化水素水Hを含浸させた別の固体分散相Sの粉体とを混合する態様を採ることもできる。更には、原料有機化合物Oと過酸化水素水Hとをそれぞれ別々に固体分散相Sの粉体中に含浸させた後、この固体分散相Sの粉体同士及び固体触媒Cの粉体を混合する態様等を採ることもでき、見かけ上、粉体状態のまま酸化反応を行うことが可能であれば、特にその態様が限定されるものではない。
また上述の説明においては、液体の原料有機化合物Oを混合物Mに含浸させる態様を記載したが、原料有機化合物Oは液体状態のものもあれば粉体状態のものもあるため、本明細書においては、混合物Mに原料有機化合物Oを加えることを、含浸の態様を含めての意味で混合(混合工程)とした。 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.
また上述の説明においては、液体の原料有機化合物Oを混合物Mに含浸させる態様を記載したが、原料有機化合物Oは液体状態のものもあれば粉体状態のものもあるため、本明細書においては、混合物Mに原料有機化合物Oを加えることを、含浸の態様を含めての意味で混合(混合工程)とした。 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.
ここで前記固体分散相Sとしては、固体触媒C、原料有機化合物O、過酸化水素水Hを分散し、これらにより劣化することなく、かつ酸化反応を阻害しない性質を有するものであって、好ましくは酸化反応を促進する性質を有する物質の粉体が採用される。
具体的には、アパタイトなどリン酸塩類、珪藻土〔主成分:シリカ〕、白陶土〔主成分:シリカアルミナ〕、ハイドロタルサイトなどクレイ類、フッ化カルシウムなどフッ化物類、シリカ、チタニア、アルミナなどの酸化物類を採用することができる。このうち、リン酸塩類、珪藻土、シリカ、アルミナ、白陶土、シリカアルミナ及びフッ化カルシウムから選択される固体分散相を採用することが好ましく、高い収率を達成できる。また特に、アパタイト、珪藻土及びフッ化カルシウムから選択される固体分散相を採用した場合には、更に高い収率を達成することができる。 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.
具体的には、アパタイトなどリン酸塩類、珪藻土〔主成分:シリカ〕、白陶土〔主成分:シリカアルミナ〕、ハイドロタルサイトなどクレイ類、フッ化カルシウムなどフッ化物類、シリカ、チタニア、アルミナなどの酸化物類を採用することができる。このうち、リン酸塩類、珪藻土、シリカ、アルミナ、白陶土、シリカアルミナ及びフッ化カルシウムから選択される固体分散相を採用することが好ましく、高い収率を達成できる。また特に、アパタイト、珪藻土及びフッ化カルシウムから選択される固体分散相を採用した場合には、更に高い収率を達成することができる。 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.
なお前記アパタイトとはリン酸カルシウムの一種であり、フッ素アパタイト、塩素アパタイト、炭酸アパタイト、水酸アパタイト等がリン灰石系鉱物として存在するものであり、固相系酸化反応法においてはフッ素アパタイトが特に好適に用いられる。
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.
また前記珪藻土とは、主に珪藻の殻からなる軟質の岩石又は土壌で、シリカを主成分とするものであるが、シリカ以外にもアルミナ、酸化鉄、アルカリ金属の酸化物等が含まれていることが多い。また珪藻土はポーラスで高い空隙率を有し、ケーク嵩密度が0.2~0.45程度のものが好ましい。更に珪藻土の中でも焼成品が好ましく、また淡水産珪藻土が好ましいが、他の珪藻土を採用することも可能である。
このような珪藻土の具体例としては、セライト社製のセライト(登録商標)やイーグルピッチャーミネラルズ社製のセラトム(商品名)を例示することができる。また、これらを炭酸ナトリウム等とともに焼成したものも採用することができる。 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.
このような珪藻土の具体例としては、セライト社製のセライト(登録商標)やイーグルピッチャーミネラルズ社製のセラトム(商品名)を例示することができる。また、これらを炭酸ナトリウム等とともに焼成したものも採用することができる。 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.
また前記ハイドロタルサイト類とは、(M2+)1 -x(M3+)x (OH)2 (An-)x / n ・aH2 O(式中、M2+は2価金属イオンを示し、M3+は3価金属イオンを示し、An-はn価のアニオンを示し、そしてxおよびaはそれぞれ0<x<0.5、0≦a<1の範囲を示す。)よりなる群から選択された少なくとも一種からなり、M2+としてはMg、Ca又はZnが、M3+としてはAl又はFeが、An-としてはOH- 、ClO4 - 、NO3 - 、SO4 2-、CO3 2-、SiO3 2-、HPO4 2-、PO4 3-又はCH3 COO- を挙げることができる。
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.
次に前記固体触媒Cとしては、タングステン、モリブデン及びバナジウムからなる群より選択された金属の酸化物、タングステン、モリブデン及びバナジウムからなる群より選択された金属を含有する酸素酸及びその塩類、並びに鉄、マンガン及びルテニウムからなる群より選択された元素の酸化物、ハロゲン化物及び硫酸塩が採用される。
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.
また前記タングステン、モリブデン及びバナジウムからなる群より選択された金属の酸化物としては、WO3 、MoO3 、V2 O5 を挙げることができる。タングステン、モリブデン及びバナジウムからなる群より選択された金属を含有する酸素酸及びその塩類としては、タングステン酸(H2 WO4 )、Na2 WO4 等のタングステン酸塩、モリブデン酸(H2 MoO4 )、Na2 MoO4 等のモリブデン酸塩、バナジン酸、NH4 VO3 等のバナジン酸塩、タングステン、モリブデン又はバナジウムを含有するイソポリ酸類及びその塩類、タングステン、モリブデン又はバナジウムを含有するヘテロポリ酸類およびその塩類を例示することができる。なお、前記タングステン、モリブデン又はバナジウムを含有するイソポリ酸類、ヘテロポリ酸類とは、(Q3 [PW6 Mo6 O4 0 ]、Q7 [PV4 Mo8 O4 0 ]等として表される混成物や、Q3 {PO4 [W(O)(O2 )]4 }、Q2 [W2 O3 (O2 )4 ]等として表されるパーオキソ型化合物も含む意味である。(式中、Qは、対カチオンを表す。)
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 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.)
また前記ヘテロポリ酸類のヘテロ原子としては、リン、ホウ素、珪素、ゲルマニウム、ランタノイド系元素、マンガン、ニッケル、鉄、コバルト又はルテニウム等を挙げることができる。又、前記イソポリ酸の塩類又はヘテロポリ酸類の塩類の対カチオンとしては、テトラブチルアンモニウム、ブチルアンモニウム、ベンジルトリメチルアンモニウム、セチルピリジニウムの有機カチオン類、及びアンモニウム、カリウム、ナトリウム、カルシウム等の無機カチオン類を挙げることができる。
より具体的には、タングステンを含有するイソポリタングステン酸類としては、(NH4 )6 W7 O2 4 、(NH4 )1 0 [H2 W1 2 O4 2 ]、(CetylPy)1 0 [H2 W1 2 O4 2 ]、(CetylPy)4 [W1 0 O3 2 ]、K4 [W1 0 O3 2 ]等を挙げることができ、タングステンを含有するヘテロポリタングステン酸類としては、(CetylPy)3 [PW1 2 O4 0 ]、(CetylPy)5 H2 [PW1 1 O3 9 ]、Na9 [PW9 O3 4 ]等を挙げることができ、更に前記のヘテロポリタングステン酸類中のリン(P)を、ホウ素(B)、ケイ素(Si)、ゲルマニウム(Ge)等で置き換えたものを例示することができる。なお、式中のCetylPyはセチルピリジニウムを表す。 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 2W 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.
より具体的には、タングステンを含有するイソポリタングステン酸類としては、(NH4 )6 W7 O2 4 、(NH4 )1 0 [H2 W1 2 O4 2 ]、(CetylPy)1 0 [H2 W1 2 O4 2 ]、(CetylPy)4 [W1 0 O3 2 ]、K4 [W1 0 O3 2 ]等を挙げることができ、タングステンを含有するヘテロポリタングステン酸類としては、(CetylPy)3 [PW1 2 O4 0 ]、(CetylPy)5 H2 [PW1 1 O3 9 ]、Na9 [PW9 O3 4 ]等を挙げることができ、更に前記のヘテロポリタングステン酸類中のリン(P)を、ホウ素(B)、ケイ素(Si)、ゲルマニウム(Ge)等で置き換えたものを例示することができる。なお、式中のCetylPyはセチルピリジニウムを表す。 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
また前記モリブデンを含有する酸素酸及びその塩類としては、前記タングステンを含有する酸素酸及びその塩類として例示した化合物中のタングステンを、モリブデンで置換した化合物を例示することができる。バナジウムを含有する酸素酸及びその塩類としては、前記のタングステンを含有する酸素酸及びその塩類として例示した化合物中のタングステンを、バナジウムで置換した化合物を例示することができる。
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.
更に前記固体触媒Cの中でも、タングステン又はモリブデンの酸化物、タングステン又はモリブデンを含有するイソポリ酸類、及びタングステン又はモリブデンを含有するヘテロポリ酸類からなる群より選択される触媒が好ましく、特に、タングステンを含有するイソポリ酸類又はヘテロポリ酸類からなる群より選択される触媒が、高い選択率が得られるため好ましい。
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.
また前記鉄、マンガン及びルテニウムからなる群より選択された元素の酸化物、ハロゲン化物や硫酸塩としては、FeCl3 、MnSO4 、RuCl3 等を挙げることができる。
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 .
また固相系酸化反応法においては、前記固体触媒Cは固体分散相Sに固定化される必要はなく、単に固体触媒Cの粉体と固体分散相Sの粉体を混合するだけでよい。例えば、予め固体分散相Sの粉体に固体触媒Cの粉体を添加し、粉体同士を攪拌混合する方法により、酸化反応システムの固相となる混合物を得ることができる。固体触媒Cの粉体及び固体分散相Sの粉体の粒度は特に限定されないが、入手の容易な粒径5~100μm程度の粉体を用いることができ、生成物の高い収率等を実現することができる。
In the solid-phase oxidation reaction method, the solid catalyst C does not need to be immobilized on 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 a powder having a particle size of about 5 to 100 μm, which is easily available, can be used, and a high yield of the product is realized. can do.
次に前記原料有機化合物Oとしては、例えば、シクロオクテン、1-デセン、2-オクテン1-オール、アリルベンゼン、ジシクロペンタジエン、1、5-シクロオクタジエン、(R)-(+)-リモネン、ベンジルアルコール、α-フェネチルアルコール、パラトリメチルスルフィド、γ-ピコリンなどがある。
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.
以下、本発明の製造装置1の作動態様と併せて、本発明の固相系酸化反応法を用いた有機化合物の製造方法について説明する。なおこの実施例では一例として、原料有機化合物Oを過酸化水素Hにより酸化することにより、有機化合物としてのエポキシ化合物Eが得られるものとした。
〔混合物調製工程〕(図2S1、図3(a)、(b)参照)
初めに、遮断バルブ22、23、25を閉じるとともに遮断バルブ28、29を開けた状態で、モータ40を起動して、図3(a)に示す様に容器本体2の上下を反転させる。次いで蓋体24を開き、容器本体2内に固体触媒Cの粉体と固体分散相Sの粉体とを投入する。次いで容器本体2と蓋体24との間にフィルタ支持材27及びフィルタ27aを挟持するようにして蓋体24を閉鎖し、この状態でモータ40を起動して容器本体2を回転させることにより、固体触媒Cの粉体と固体分散相Sの粉体とを混合して混合物Mを調製する。
なお上述の手法以外にも、フィルタ支持材27及びフィルタ27を容器本体2に挟持して遮断バルブ22を開き、容器本体2外にて固体触媒Cと固体分散相Sを混合し、この混合物を遮断バルブ22から容器本体2内に投入することなどにより、混合物Mを調製することもできる。 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 themanufacturing 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, thefilter 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.
〔混合物調製工程〕(図2S1、図3(a)、(b)参照)
初めに、遮断バルブ22、23、25を閉じるとともに遮断バルブ28、29を開けた状態で、モータ40を起動して、図3(a)に示す様に容器本体2の上下を反転させる。次いで蓋体24を開き、容器本体2内に固体触媒Cの粉体と固体分散相Sの粉体とを投入する。次いで容器本体2と蓋体24との間にフィルタ支持材27及びフィルタ27aを挟持するようにして蓋体24を閉鎖し、この状態でモータ40を起動して容器本体2を回転させることにより、固体触媒Cの粉体と固体分散相Sの粉体とを混合して混合物Mを調製する。
なお上述の手法以外にも、フィルタ支持材27及びフィルタ27を容器本体2に挟持して遮断バルブ22を開き、容器本体2外にて固体触媒Cと固体分散相Sを混合し、この混合物を遮断バルブ22から容器本体2内に投入することなどにより、混合物Mを調製することもできる。 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
[Mixture preparation step] (see FIG. 2S1, FIG. 3 (a), (b))
First, with the shut-off
In addition to the above-described method, the
〔混合工程〕(図2S2、図3(c)参照)
次いで、遮断バルブ28、29を閉じ、遮断バルブ23を開き、供給管26を通じて容器本体2内に液体の原料有機化合物Oを供給装置(図示省略)から供給して、前記混合物Mに含浸させる。原料有機化合物Oを含浸した混合物Mは、見かけ上、粉体状態を呈している。なお、遮断バルブ28を若干開き、原料有機化合物Oの供給により容器本体2内が加圧状態とならないように排気を行う。排気を終えれば遮断バルブ28を閉じる。
更に、必要であればモータ40を起動して、容器本体2を回転させることにより、混合物Mの全域に万遍なく原料有機化合物Oを行渡らせることもできる。また、より均一に吸収させるために、原料有機化合物Oの供給装置(図示省略)と、遮断バルブ23との間を、可撓性のチューブ(図示省略)により接続することで、容器本体2を連続あるいは間欠的に揺動させながら原料有機化合物Oの供給を行うようにする。
そして容器本体2内での混合物Mの揺動による流動状態に合わせて、前記供給装置(図示省略)により適宜供給を行ったり、あるいは、揺動を間欠的に止めて、容器本体2を適宜の角度に傾斜させた状態で堆積する混合物Mに向けて供給管26を指向させて供給するようにすることもできる。なお、この揺動時においても上述と同様に若干の排気が行われる。 [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 the supply of the raw 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 themotor 40 and rotating the container body 2. Moreover, in order to absorb more uniformly, the container main body 2 is connected by connecting the raw material organic compound O supply device (not shown) and the shut-off 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 thecontainer body 2, supply is appropriately performed by the feeding device (not shown), or the rocking is stopped intermittently, so that the container body 2 is appropriately 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.
次いで、遮断バルブ28、29を閉じ、遮断バルブ23を開き、供給管26を通じて容器本体2内に液体の原料有機化合物Oを供給装置(図示省略)から供給して、前記混合物Mに含浸させる。原料有機化合物Oを含浸した混合物Mは、見かけ上、粉体状態を呈している。なお、遮断バルブ28を若干開き、原料有機化合物Oの供給により容器本体2内が加圧状態とならないように排気を行う。排気を終えれば遮断バルブ28を閉じる。
更に、必要であればモータ40を起動して、容器本体2を回転させることにより、混合物Mの全域に万遍なく原料有機化合物Oを行渡らせることもできる。また、より均一に吸収させるために、原料有機化合物Oの供給装置(図示省略)と、遮断バルブ23との間を、可撓性のチューブ(図示省略)により接続することで、容器本体2を連続あるいは間欠的に揺動させながら原料有機化合物Oの供給を行うようにする。
そして容器本体2内での混合物Mの揺動による流動状態に合わせて、前記供給装置(図示省略)により適宜供給を行ったり、あるいは、揺動を間欠的に止めて、容器本体2を適宜の角度に傾斜させた状態で堆積する混合物Mに向けて供給管26を指向させて供給するようにすることもできる。なお、この揺動時においても上述と同様に若干の排気が行われる。 [Mixing step] (see FIG. 2S2, FIG. 3C)
Next, the
Furthermore, if necessary, the raw material organic compound O can be spread over the entire area of the mixture M by starting the
Then, according to the flow state due to the rocking of the mixture M in the
〔含浸工程〕(図2S3、図3(c)参照)
次いで遮断バルブ23を開き、供給管26を通じて容器本体2内に過酸化水素水Hを供給装置(図示省略)から供給して、前記原料有機化合物Oが含浸された混合物Mに更に含浸させる。原料有機化合物Oと過酸化水素水Hとを含浸した混合物Mは、見かけ上、粉体状態を呈している。
なお上記混合工程と同様に、遮断バルブ28を若干開き、過酸化水素水Hの供給により容器本体2内が加圧状態とならないように排気を行う。排気を終えれば遮断バルブ28を閉じる。また上記混合工程と同様に、必要であればモータ40を起動して、容器本体2を回転させることにより、混合物Mの全域に万遍なく過酸化水素水Hを行渡らせることもできる。更にまた上記混合工程と同様に、より均一に吸収させるために、過酸化水素水Hの供給装置(図示省略)と、遮断バルブ23との間を、可撓性のチューブ(図示省略)により接続することで、容器本体2を連続あるいは間欠的に揺動させながら過酸化水素水Hの供給を行うようにする。 [Impregnation step] (see FIG. 2S3, FIG. 3C)
Next, the shut-offvalve 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, theshutoff 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.
次いで遮断バルブ23を開き、供給管26を通じて容器本体2内に過酸化水素水Hを供給装置(図示省略)から供給して、前記原料有機化合物Oが含浸された混合物Mに更に含浸させる。原料有機化合物Oと過酸化水素水Hとを含浸した混合物Mは、見かけ上、粉体状態を呈している。
なお上記混合工程と同様に、遮断バルブ28を若干開き、過酸化水素水Hの供給により容器本体2内が加圧状態とならないように排気を行う。排気を終えれば遮断バルブ28を閉じる。また上記混合工程と同様に、必要であればモータ40を起動して、容器本体2を回転させることにより、混合物Mの全域に万遍なく過酸化水素水Hを行渡らせることもできる。更にまた上記混合工程と同様に、より均一に吸収させるために、過酸化水素水Hの供給装置(図示省略)と、遮断バルブ23との間を、可撓性のチューブ(図示省略)により接続することで、容器本体2を連続あるいは間欠的に揺動させながら過酸化水素水Hの供給を行うようにする。 [Impregnation step] (see FIG. 2S3, FIG. 3C)
Next, the shut-off
As in the above mixing step, the
〔酸化反応工程(図2S4、図3(d)参照)
次いで熱媒発生装置6からジャケット3内に熱媒としての湯水を供給するものであり、この実施例では一例として容器本体2内を25℃に保つようにした。そして容器本体2を温度調整(加熱または冷却)した熱媒はジャケット3から排出される。
そして有機化合物O及び過酸化水素水Hを含浸した混合物Mは、図3(d)に示されるように、フィルタ27aの上面に、ほぼ均一な層厚となるように堆積するものであり、所定の時間(ここでは一例として六時間)静置される。このとき、混合物Mの粉体表面が特殊な反応場となって、見かけ上、粉体状態のままエポキシ化が穏やかに進み、高純度のエポキシ化合物E(酸化物)が得られるものである。この際、固体触媒Cの劣化は極めて少なく、またこの反応によって生成される副生産物は水だけとなる。
なお特には図示しないが、混合物Mに埋もれる位置であり、且つ平面視においてフィルタ27aの中央付近となる位置、すなわちジャケット3から最も遠い位置に温度センサ(図示省略)のセンシング位置を配して酸化反応工程中の温度を測定し、温度上昇に応じて熱媒発生装置6からジャケット3に供給される湯水の温度あるいは供給量を調整するようにしてもよい。 [Oxidation reaction step (see FIG. 2S4, FIG. 3 (d))
Next, hot water as a heating medium is supplied from theheating 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 thefilter 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 thefilter 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.
次いで熱媒発生装置6からジャケット3内に熱媒としての湯水を供給するものであり、この実施例では一例として容器本体2内を25℃に保つようにした。そして容器本体2を温度調整(加熱または冷却)した熱媒はジャケット3から排出される。
そして有機化合物O及び過酸化水素水Hを含浸した混合物Mは、図3(d)に示されるように、フィルタ27aの上面に、ほぼ均一な層厚となるように堆積するものであり、所定の時間(ここでは一例として六時間)静置される。このとき、混合物Mの粉体表面が特殊な反応場となって、見かけ上、粉体状態のままエポキシ化が穏やかに進み、高純度のエポキシ化合物E(酸化物)が得られるものである。この際、固体触媒Cの劣化は極めて少なく、またこの反応によって生成される副生産物は水だけとなる。
なお特には図示しないが、混合物Mに埋もれる位置であり、且つ平面視においてフィルタ27aの中央付近となる位置、すなわちジャケット3から最も遠い位置に温度センサ(図示省略)のセンシング位置を配して酸化反応工程中の温度を測定し、温度上昇に応じて熱媒発生装置6からジャケット3に供給される湯水の温度あるいは供給量を調整するようにしてもよい。 [Oxidation reaction step (see FIG. 2S4, FIG. 3 (d))
Next, hot water as a heating medium is supplied from the
The mixture M impregnated with the organic compound O and the hydrogen peroxide solution H is deposited on the upper surface of the
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
なおこのような温度測定に基づいた湯水の温度あるいは供給量の調整を行うことを考慮した場合、混合物Mを、容器本体2の内面に広範囲に接触した状態で堆積させ、この状態で酸化反応工程を実施することも好ましい実施例の一つである。
このため酸化反応工程時の製造装置1の姿勢を、図3(d)に示した状態ではなく、遮断バルブ22が下方になるように容器本体2を180°回転させ、遮断バルブ22の上に混合物Mを堆積させた状態としたり、あるいは、この状態から容器本体2を90°回転させて遮断バルブ22が水平の位置になるようにして、主に容器本体2の内面上に混合物Mを堆積させた状態とするような形態を採ることも可能である。なおこれらの形態が採られる場合にも、温度センサ(図示省略)のセンシング位置が混合物Mに埋もれるようにする。 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 thecontainer 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 themanufacturing 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.
このため酸化反応工程時の製造装置1の姿勢を、図3(d)に示した状態ではなく、遮断バルブ22が下方になるように容器本体2を180°回転させ、遮断バルブ22の上に混合物Mを堆積させた状態としたり、あるいは、この状態から容器本体2を90°回転させて遮断バルブ22が水平の位置になるようにして、主に容器本体2の内面上に混合物Mを堆積させた状態とするような形態を採ることも可能である。なおこれらの形態が採られる場合にも、温度センサ(図示省略)のセンシング位置が混合物Mに埋もれるようにする。 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
For this reason, the attitude of the
またジャケット3内に供給される湯水の調整に関しては、例えば、容器本体2からの放熱が大きく、混合物Mが所定の温度より低温である場合などは、混合物Mが所定の温度となるように湯水の温度を調整して供給する。また、ジャケット3から排出される湯水の温度を、温度センサ(図示省略)により測定し、温度上昇あるいは温度降下に応じて熱媒発生装置6からジャケット3に供給される湯水の温度の調整を行うようにしてもよい。
そして上述した酸化反応工程が終了した時点で、ジャケット3への湯水の供給が停止される。 Regarding the adjustment of hot water supplied into thejacket 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 thejacket 3 is stopped.
そして上述した酸化反応工程が終了した時点で、ジャケット3への湯水の供給が停止される。 Regarding the adjustment of hot water supplied into the
Then, when the above-described oxidation reaction step is completed, the supply of hot water to the
なお以上の説明では、容器本体2を回転させることなく静置した状態で酸化反応工程を行う場合を示したが、容器本体2を回転させながら酸化反応工程を行うこともできる。すなわち、酸化反応工程においては、時間経過と共に最適な反応を生じせしめる温度管理を行うことで、酸化反応工程を効率的に進行させることができるものであり、酸化反応による発熱が多い段階で放熱を積極的に行う場合、あるいは酸化反応を促進させるために加温を積極的に行う場合などは、ジャケット3内の湯水とできるだけ広範囲に接触させて熱交換させるように、本体容器2の緩やかな回転と停止、すなわち回転と静置状態を適宜組み合わせて行うことも好ましい。
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.
〔回収工程〕(図2S5、図3(e)、(f)参照)
次いで抽出または直接減圧蒸留によってエポキシ化合物Eと水を容器本体2の外部に取り出す。
ここでは一例として抽出による手法を説明するものであり、遮断バルブ23を開き、図3(e)にて示されるように、フィルタ27aの上面に酸化反応工程を終えた混合物Mが堆積している状態で、供給管26から容器本体2内に溶剤R(ヘキサン、ペンタン、酢酸エチル等)を注入し、必要であれば遮断バルブ23を閉じ、熱媒発生装置6からの湯水をジャケット3に供給して加熱を行いながら、モータ40を起動して容器本体2を回転させた後、蓋体24を下にした位置で一定時間静置する。その後、遮断バルブ28を開き、次いで遮断バルブ25を開いて容器本体2内にエアを導入し(図3(f))、容器本体2内の液体を加圧(~0.01MPaG)することによりろ過を行う。なお必要に応じて、フィルタ27a下方の空間を減圧するようにしてもよいし、加圧も減圧も行わずにろ過を行うようにしてもよい。
そしてエポキシ化合物Eが溶解された溶剤R(ろ液)は、ろ液排出口24aから外部に取り出されるものであり、ろ液の濃縮や、ろ液からの析出操作が行われることによりエポキシ化合物Eが回収されることとなる。遮断バルブ28からのろ液の排出がなくなった時点で、遮断バルブ25、28を閉じる。なお溶媒Rについては適宜回収して再使用することもできる。
なお、必要に応じて、上述した溶剤Rの注入から、エポキシ化合物Eが溶解された溶剤Rの外部への取り出しを繰り返すことで、混合物M中のエポキシ化合物Eを回収することも行われる。 [Recovery Step] (See FIG. 2S5, FIG. 3 (e), (f))
Next, the epoxy compound E and water are taken out of thecontainer body 2 by extraction or direct distillation under reduced pressure.
Here, an extraction method will be described as an example, and theshutoff 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 thefiltrate 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.
次いで抽出または直接減圧蒸留によってエポキシ化合物Eと水を容器本体2の外部に取り出す。
ここでは一例として抽出による手法を説明するものであり、遮断バルブ23を開き、図3(e)にて示されるように、フィルタ27aの上面に酸化反応工程を終えた混合物Mが堆積している状態で、供給管26から容器本体2内に溶剤R(ヘキサン、ペンタン、酢酸エチル等)を注入し、必要であれば遮断バルブ23を閉じ、熱媒発生装置6からの湯水をジャケット3に供給して加熱を行いながら、モータ40を起動して容器本体2を回転させた後、蓋体24を下にした位置で一定時間静置する。その後、遮断バルブ28を開き、次いで遮断バルブ25を開いて容器本体2内にエアを導入し(図3(f))、容器本体2内の液体を加圧(~0.01MPaG)することによりろ過を行う。なお必要に応じて、フィルタ27a下方の空間を減圧するようにしてもよいし、加圧も減圧も行わずにろ過を行うようにしてもよい。
そしてエポキシ化合物Eが溶解された溶剤R(ろ液)は、ろ液排出口24aから外部に取り出されるものであり、ろ液の濃縮や、ろ液からの析出操作が行われることによりエポキシ化合物Eが回収されることとなる。遮断バルブ28からのろ液の排出がなくなった時点で、遮断バルブ25、28を閉じる。なお溶媒Rについては適宜回収して再使用することもできる。
なお、必要に応じて、上述した溶剤Rの注入から、エポキシ化合物Eが溶解された溶剤Rの外部への取り出しを繰り返すことで、混合物M中のエポキシ化合物Eを回収することも行われる。 [Recovery Step] (See FIG. 2S5, FIG. 3 (e), (f))
Next, the epoxy compound E and water are taken out of the
Here, an extraction method will be described as an example, and the
The solvent R (filtrate) in which the epoxy compound E is dissolved is taken out from the
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.
〔再生工程〕(図2S6、図3(g)、(h)参照)
上述のようにろ液(エポキシ化合物Eが溶解された溶剤R)が排出された後には、フィルタ27a上に混合物Mのろ過ケーキが残存するものであり、このろ過ケーキには固体触媒Cの粉体と固体分散相Sの粉体が含まれているが、この他にエポキシ化合物Eが溶解された溶剤R及び水が含まれている。そこで、このろ過ケーキを乾燥させることにより、固体触媒Cと固体分散相Sを再利用可能な乾燥した粉体の状態に戻すものである。まず熱媒発生装置6からジャケット3内に熱媒としての湯水を供給するとともに、冷凍機8aを起動し、冷媒を冷凍機8aから凝縮器8に供給する。次に、真空ポンプPを起動し、遮断バルブ29を開き、モータ40を起動して容器本体2を回転させる。この回転によりろ過ケーキはフィルタ27aから剥離するなどして、本体容器2内面に接触すると共にジャケット3から供給される湯水の熱により加熱されて溶剤R及び水が蒸発し、その蒸気は真空ポンプPにより吸引され、分離装置7内のフィルタ(図示省略)により微粉が除去された後、凝縮器8において凝縮して回収される。この凝縮液は適宜再利用される。なお、分離装置7内においても凝縮が生じることがあり、ここで生じたドレンも適宜回収されて再利用される。
また、前記本体容器2を回転させるのではなく、含浸工程で述べた様に揺動させて本再生工程を行うこともできる。この場合、上述の回収工程でのエアの代わりに、温風発生装置(図示省略)と、遮断バルブ25との間を、可撓性のチューブ(図示省略)により接続し、遮断バルブ25を開き、容器本体2を連続あるいは間欠的に揺動させつつ、供給管26から温風を供給することにより、溶剤R及び水の迅速な蒸発を行うことができる。 [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 thefilter 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 themain 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.
上述のようにろ液(エポキシ化合物Eが溶解された溶剤R)が排出された後には、フィルタ27a上に混合物Mのろ過ケーキが残存するものであり、このろ過ケーキには固体触媒Cの粉体と固体分散相Sの粉体が含まれているが、この他にエポキシ化合物Eが溶解された溶剤R及び水が含まれている。そこで、このろ過ケーキを乾燥させることにより、固体触媒Cと固体分散相Sを再利用可能な乾燥した粉体の状態に戻すものである。まず熱媒発生装置6からジャケット3内に熱媒としての湯水を供給するとともに、冷凍機8aを起動し、冷媒を冷凍機8aから凝縮器8に供給する。次に、真空ポンプPを起動し、遮断バルブ29を開き、モータ40を起動して容器本体2を回転させる。この回転によりろ過ケーキはフィルタ27aから剥離するなどして、本体容器2内面に接触すると共にジャケット3から供給される湯水の熱により加熱されて溶剤R及び水が蒸発し、その蒸気は真空ポンプPにより吸引され、分離装置7内のフィルタ(図示省略)により微粉が除去された後、凝縮器8において凝縮して回収される。この凝縮液は適宜再利用される。なお、分離装置7内においても凝縮が生じることがあり、ここで生じたドレンも適宜回収されて再利用される。
また、前記本体容器2を回転させるのではなく、含浸工程で述べた様に揺動させて本再生工程を行うこともできる。この場合、上述の回収工程でのエアの代わりに、温風発生装置(図示省略)と、遮断バルブ25との間を、可撓性のチューブ(図示省略)により接続し、遮断バルブ25を開き、容器本体2を連続あるいは間欠的に揺動させつつ、供給管26から温風を供給することにより、溶剤R及び水の迅速な蒸発を行うことができる。 [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
Further, instead of rotating the
なお、ろ過ケーキからの溶剤Rの除去の完了は、容器本体2内の温度変化から、あるいは凝縮器8での凝縮液の発生が止まることなどにより確認され、その後、フィルタ27aを下方にしてフィルタ27a面が水平になる位置で回転を止め、遮断バルブ29を閉じ、真空ポンプPと冷凍機8aを停止させる。その後バルブ28を開けて本体容器2内を大気圧に戻す。
このように再生工程においては、上述の回転あるいは揺動と乾燥とにより、ろ過ケーキは解砕されて粉体化し、固体触媒Cの粉体と固体分散相Sの粉体を含む粉体の混合物Mとしての再利用が可能な状態となる。
そして図2に示すように、製造を継続する判断が成され (S7)、再生利用が可能と判断されれば(S8)、混合物調製工程を経由せずに、混合工程、含浸工程、酸化反応工程、回収工程、再生工程が順次実施される。
なお再生利用が可能か否かの判断は、遮断バルブ22などから混合物Mを一部採取して、その物性を確認すること等により行われる。再利用に不適であると判断されるときは(S8)、本体容器2をモータ40により180°反転させて遮断バルブ22を下方にして停止させ、遮断バルブ22を開き、混合物Mを排出(S9)し、上述したように、新たに混合物調製工程(S1)から製造を開始すればよい。
因みに前記混合物Mの再利用は、少なくとも二十五回可能であることが本出願人によって確認されている。 The completion of the removal of the solvent R from the filter cake is confirmed by the temperature change in thecontainer 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 theshutoff 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.
このように再生工程においては、上述の回転あるいは揺動と乾燥とにより、ろ過ケーキは解砕されて粉体化し、固体触媒Cの粉体と固体分散相Sの粉体を含む粉体の混合物Mとしての再利用が可能な状態となる。
そして図2に示すように、製造を継続する判断が成され (S7)、再生利用が可能と判断されれば(S8)、混合物調製工程を経由せずに、混合工程、含浸工程、酸化反応工程、回収工程、再生工程が順次実施される。
なお再生利用が可能か否かの判断は、遮断バルブ22などから混合物Mを一部採取して、その物性を確認すること等により行われる。再利用に不適であると判断されるときは(S8)、本体容器2をモータ40により180°反転させて遮断バルブ22を下方にして停止させ、遮断バルブ22を開き、混合物Mを排出(S9)し、上述したように、新たに混合物調製工程(S1)から製造を開始すればよい。
因みに前記混合物Mの再利用は、少なくとも二十五回可能であることが本出願人によって確認されている。 The completion of the removal of the solvent R from the filter cake is confirmed by the temperature change in the
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
Incidentally, it has been confirmed by the present applicant that the mixture M can be reused at least 25 times.
以上述べたように本発明によれば、単一の容器本体2内において、固相系酸化反応法を実施するための混合物調製工程、混合工程、含浸工程、酸化反応工程、回収工程を実施することができるものであり、更に混合物Mを容器本体2から取り出すことなく再生工程を実施することができるため、二回目以降の混合物調製工程を省略することができ、固相系酸化反応法による有機化合物の製造を、極めて効率的且つ低コストで行うことができるものである。
更に容器本体2の容量は1000リットル以上とすることができるため、工業化レベルでの有機化合物の製造が実現可能となる。
また上述した実施例では、全工程でハロゲン化物を用いることなく実施することができるため、ハロゲンを除去するための精製工程を要することがなく、完全なハロゲンフリーの有機化合物(エポキシ化合物E)を得ることができる。 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 thesingle 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 containermain 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. Obtainable.
更に容器本体2の容量は1000リットル以上とすることができるため、工業化レベルでの有機化合物の製造が実現可能となる。
また上述した実施例では、全工程でハロゲン化物を用いることなく実施することができるため、ハロゲンを除去するための精製工程を要することがなく、完全なハロゲンフリーの有機化合物(エポキシ化合物E)を得ることができる。 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
Furthermore, since the capacity | capacitance of the container
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. Obtainable.
〔他の実施例〕
本発明は上述した実施例を基本となる実施例とするものであるが、本発明の技術的思想に基づいて、以下に示すような実施例を採ることもできる。
まず上述した製造装置1は、容器本体2を上下反転や揺動させることにより、粉体の混合、含浸あるいは乾燥などを効果的行い、本発明の固相系酸化反応法を用いた有機化合物の製造方法を実施するものであったが、例えば図4に示すように、攪拌装置91を具えた製造装置9を利用して、混合、含浸、あるいは乾燥などを効果的に行い、本発明の固相系酸化反応法を用いた有機化合物の製造方法を実施することも可能である。
なお製造装置9を用いた製造方法は、製造装置1を用いた製造方法とほぼ同様であるため、以下、製造装置9の主要な構成及び製造装置9を用いる場合の製造方法の要部、並びに製造装置1を用いる場合の製造方法と異なる部分について説明する。 [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, themanufacturing 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 themanufacturing 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.
本発明は上述した実施例を基本となる実施例とするものであるが、本発明の技術的思想に基づいて、以下に示すような実施例を採ることもできる。
まず上述した製造装置1は、容器本体2を上下反転や揺動させることにより、粉体の混合、含浸あるいは乾燥などを効果的行い、本発明の固相系酸化反応法を用いた有機化合物の製造方法を実施するものであったが、例えば図4に示すように、攪拌装置91を具えた製造装置9を利用して、混合、含浸、あるいは乾燥などを効果的に行い、本発明の固相系酸化反応法を用いた有機化合物の製造方法を実施することも可能である。
なお製造装置9を用いた製造方法は、製造装置1を用いた製造方法とほぼ同様であるため、以下、製造装置9の主要な構成及び製造装置9を用いる場合の製造方法の要部、並びに製造装置1を用いる場合の製造方法と異なる部分について説明する。 [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
Since the manufacturing method using the
まず攪拌装置91は、例えば1条のリボン羽根911を具えて構成されたものであり、モータ90により製造装置9におる逆円錐状の容器本体93内で回転されるものである。前記リボン羽根911は、らせん状の羽根板であり、本体容器93の底部に具えられたフィルタ27aの直上から本体容器93の上部まで連続しており、本体容器93の内壁面の近傍を羽根板が回転するものである。このためリボン羽根911が回転すると、本体容器93の底部に位置する混合物Mは、本体容器93の内壁面に沿って本体容器93の上部に持ち上げられた後、本体容器93の中心部側に落下させられるため、混合物Mは本体容器93内で激しく攪拌されることになる。
なお容器本体93は、基本となる実施例で示した本体容器2と同様に、密閉可能とされるものであり、攪拌装置91の回転軸が貫通する部分には図示しない適宜のシール機構が具えられている。 First, the stirringdevice 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 containermain 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.
なお容器本体93は、基本となる実施例で示した本体容器2と同様に、密閉可能とされるものであり、攪拌装置91の回転軸が貫通する部分には図示しない適宜のシール機構が具えられている。 First, the stirring
The container
次に製造装置9を利用した、本発明の固相系酸化反応法を用いた有機化合物の製造方法について説明すると、この実施例においても図2に示すフローチャートに沿って行われるものであり、混合物調整工程では、投入口92より固体触媒C及び固体分散相Sを容器本体93に投入し、攪拌装置91のリボン羽根911の回転により固体触媒Cと固体分散相Sを攪拌・混合して、均一な混合物Mとする。
次いで混合工程では、リボン羽根911の回転により混合物Mを攪拌しつつ供給管26から原料有機化合物Oを供給することで、原料有機化合物Oは混合物Mと均一に混合されることとなる。
次いで含浸工程では、リボン羽根911の回転により混合物Mを攪拌しつつ供給管26から過酸化水素水Hを供給することで、過酸化水素水Hは混合物Mと均一に混合されることとなる。
次いで酸化反応工程では、リボン羽根911の回転を停止し、これにより混合物Mが静置され、熱媒発生装置6から本体容器93の外面に具えられたジャケット3に供給される熱媒による温度調整が成された状態で酸化反応が行われる。なお、必要に応じてリボン羽根911を回転して混合物Mを攪拌し、ジャケット3内の熱媒との熱交換を促進することができる。
次いで回収工程では、リボン羽根911の回転を停止した状態で供給管26から溶剤Rを注入すると、酸化反応工程において混合物M中に生成されたエポキシ化合物Eは溶剤Rに溶解され、この溶剤がフィルタ27aを通過してろ液排出口24aから製造装置9外に取り出される。なお、必要に応じてリボン羽根911を回転しながら溶剤Rの注入を行うことにより、エポキシ化合物Eの溶剤Rへの溶解を促進することができる。
次いで再生工程では、リボン羽根911を回転し、ジャケット3には熱媒を供給し、真空ポンプPにより容器本体93内において蒸発する溶剤Rと水とが排気され、これによりろ過ケーキは乾燥した固体触媒Cの粉体及び固体分散相Sの粉体の混合物Mとして再生され、以降、再生利用が可能と判断されれば、混合物調製工程を経由せずに、混合工程、含浸工程、酸化反応工程、回収工程、再生工程が順次実施される。
なお、容器本体93から混合物Mを取り出す必要を生じる場合は、容器本体93の底部付近に具えられた排出装置94のダンパ部941を開いたり、あるいは、容器本体93から蓋体24を取り外したり、更には図示しない蝶番機構を用いて容器本体93から蓋体24を開くことにより、混合物Mの排出を行うことができる。 Next, a method for producing an organic compound using the solid-phase oxidation reaction method of the present invention using theproduction 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 thesupply 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 thesupply pipe 26 while stirring the mixture M by the rotation of the ribbon blade 911.
Next, in the oxidation reaction step, the rotation of theribbon 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 thesupply 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, theribbon 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 containermain 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.
次いで混合工程では、リボン羽根911の回転により混合物Mを攪拌しつつ供給管26から原料有機化合物Oを供給することで、原料有機化合物Oは混合物Mと均一に混合されることとなる。
次いで含浸工程では、リボン羽根911の回転により混合物Mを攪拌しつつ供給管26から過酸化水素水Hを供給することで、過酸化水素水Hは混合物Mと均一に混合されることとなる。
次いで酸化反応工程では、リボン羽根911の回転を停止し、これにより混合物Mが静置され、熱媒発生装置6から本体容器93の外面に具えられたジャケット3に供給される熱媒による温度調整が成された状態で酸化反応が行われる。なお、必要に応じてリボン羽根911を回転して混合物Mを攪拌し、ジャケット3内の熱媒との熱交換を促進することができる。
次いで回収工程では、リボン羽根911の回転を停止した状態で供給管26から溶剤Rを注入すると、酸化反応工程において混合物M中に生成されたエポキシ化合物Eは溶剤Rに溶解され、この溶剤がフィルタ27aを通過してろ液排出口24aから製造装置9外に取り出される。なお、必要に応じてリボン羽根911を回転しながら溶剤Rの注入を行うことにより、エポキシ化合物Eの溶剤Rへの溶解を促進することができる。
次いで再生工程では、リボン羽根911を回転し、ジャケット3には熱媒を供給し、真空ポンプPにより容器本体93内において蒸発する溶剤Rと水とが排気され、これによりろ過ケーキは乾燥した固体触媒Cの粉体及び固体分散相Sの粉体の混合物Mとして再生され、以降、再生利用が可能と判断されれば、混合物調製工程を経由せずに、混合工程、含浸工程、酸化反応工程、回収工程、再生工程が順次実施される。
なお、容器本体93から混合物Mを取り出す必要を生じる場合は、容器本体93の底部付近に具えられた排出装置94のダンパ部941を開いたり、あるいは、容器本体93から蓋体24を取り外したり、更には図示しない蝶番機構を用いて容器本体93から蓋体24を開くことにより、混合物Mの排出を行うことができる。 Next, a method for producing an organic compound using the solid-phase oxidation reaction method of the present invention using the
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
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
Next, in the oxidation reaction step, the rotation of the
Next, in the recovery process, when the solvent R is injected from the
Next, in the regeneration step, the
When it is necessary to take out the mixture M from the container
また上述した二つの実施例では、混合物調製工程、混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を全て同一の容器本体2、93内で行うようにしたが、これらの工程の一部または複数を、容器本体2、93の外部において行うようにしてもよい。
まず前記再生工程を、容器本体2、93の外部において行う実施例について説明する。具体的には、製造装置1の場合、回収工程を終了した後、フィルタ27a上に位置する混合物Mのろ過ケーキを、容器本体2の回転によりフィルタ27aから剥離させ、遮断バルブ22から排出できる程度に解砕した後、遮断バルブ22から外部に排出する。また製造装置9の場合には、前述したようにして容器本体93から、混合物Mのろ過ケーキを外部に排出する。
そして製造装置1、9の構成機器として別途用意された乾燥機(図示省略)を用いてろ過ケーキの乾燥を行い、乾燥したものは必要に応じて解砕し、粉体の混合物Mとして再生するものである。
このように容器本体2、93外で再生された混合物Mは、本体容器2、93内に供給され、上述した基本となる実施例と同様に原料有機化合物Oをこの混合物Mに含浸あるいは混合させる混合工程が実施され、続いて含浸工程、酸化反応工程、回収工程が順次実施されるものである。 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.
まず前記再生工程を、容器本体2、93の外部において行う実施例について説明する。具体的には、製造装置1の場合、回収工程を終了した後、フィルタ27a上に位置する混合物Mのろ過ケーキを、容器本体2の回転によりフィルタ27aから剥離させ、遮断バルブ22から排出できる程度に解砕した後、遮断バルブ22から外部に排出する。また製造装置9の場合には、前述したようにして容器本体93から、混合物Mのろ過ケーキを外部に排出する。
そして製造装置1、9の構成機器として別途用意された乾燥機(図示省略)を用いてろ過ケーキの乾燥を行い、乾燥したものは必要に応じて解砕し、粉体の混合物Mとして再生するものである。
このように容器本体2、93外で再生された混合物Mは、本体容器2、93内に供給され、上述した基本となる実施例と同様に原料有機化合物Oをこの混合物Mに含浸あるいは混合させる混合工程が実施され、続いて含浸工程、酸化反応工程、回収工程が順次実施されるものである。 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
First, an embodiment in which the regeneration step is performed outside the
Then, the filter cake is dried using a dryer (not shown) separately prepared as a component device of the
The mixture M regenerated outside the container
また、上述のように容器本体2、93の外部で再生された混合物Mを、製造装置1、9の構成機器として別途用意された混合機(図示省略)を用いて、原料有機化合物Oの含浸あるいは混合を行った後、このものを容器本体2、93内に移し、過酸化水素水Hを供給管26から供給して含浸工程を行い、続いて酸化反応工程、回収工程を行うようにする形態を採ることもできる。
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.
更にまた、固体触媒と固体分散相とを混合する混合物調製工程も、製造装置1、9の構成機器として別途用意された混合機を用いて、容器本体2、93の外部で行うことも可能である。
このように、混合物調製工程、混合工程、あるいは再生工程のいずれか一つまたは複数を、容器本体2、93を用いることなく行った場合には、例えば、効率的な混合機、乾燥機を用いることにより、製造時間の短縮を図ることができるといった利点がある。 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.
このように、混合物調製工程、混合工程、あるいは再生工程のいずれか一つまたは複数を、容器本体2、93を用いることなく行った場合には、例えば、効率的な混合機、乾燥機を用いることにより、製造時間の短縮を図ることができるといった利点がある。 Furthermore, the mixture preparation step for mixing the solid catalyst and the solid dispersed phase can also be performed outside the
Thus, when any one or more of the mixture preparation step, the mixing step, and the regeneration step are performed without using the
1 製造装置
2 容器本体
20 開口部
21 原料供給口
22 遮断バルブ
23 遮断バルブ
24 蓋体
24a ろ液排出口
25 遮断バルブ
26 供給管
27 フィルタ支持材
27a フィルタ
28 遮断バルブ
29 遮断バルブ
3 ジャケット
4 支持軸
40 モータ
41 軸受
42 チェーン
43 ロータリージョイント
5 支持軸
51 軸受
6 熱媒発生装置
7 分離装置
8 凝縮器
8a 冷凍機
9 製造装置
90 モータ
91 攪拌装置
911 リボン羽根
92 投入口
93 容器本体
94 排出機構
C 固体触媒
E エポキシ化合物
H 過酸化水素水
M 混合物
O 原料有機化合物
P 真空ポンプ
R 溶剤
S 固体分散相 DESCRIPTION OFSYMBOLS 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
2 容器本体
20 開口部
21 原料供給口
22 遮断バルブ
23 遮断バルブ
24 蓋体
24a ろ液排出口
25 遮断バルブ
26 供給管
27 フィルタ支持材
27a フィルタ
28 遮断バルブ
29 遮断バルブ
3 ジャケット
4 支持軸
40 モータ
41 軸受
42 チェーン
43 ロータリージョイント
5 支持軸
51 軸受
6 熱媒発生装置
7 分離装置
8 凝縮器
8a 冷凍機
9 製造装置
90 モータ
91 攪拌装置
911 リボン羽根
92 投入口
93 容器本体
94 排出機構
C 固体触媒
E エポキシ化合物
H 過酸化水素水
M 混合物
O 原料有機化合物
P 真空ポンプ
R 溶剤
S 固体分散相 DESCRIPTION OF
Claims (6)
- 固体触媒の粉体と固体分散相の粉体とを混合して粉体の混合物を調製する混合物調製工程と、
前記混合物に原料有機化合物を加える混合工程と、
前記混合工程における処理が行われた混合物に酸化剤を含浸させる含浸工程と、
前記含浸工程における処理が行われた混合物中の原料有機化合物と酸化剤とを反応させる酸化反応工程と、
前記酸化反応工程で生成された有機化合物を溶剤に溶解させた状態で回収する回収工程と、
を順次実施することにより有機化合物を得る有機化合物の製造方法において、
少なくとも前記含浸工程、酸化反応工程及び回収工程を同一の容器本体内において行うことを特徴とする固相系酸化反応法を用いた有機化合物の製造方法。 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. - 前記回収工程が実施された後の、固体触媒の粉体と固体分散相の粉体とを含む混合物を再利用するための再生工程が実施されるものであり、
前記再生工程により再生された混合物を用いて、
前記混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を繰り返して行うことを特徴とする請求項1記載の固相系酸化反応法を用いた有機化合物の製造方法。 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. - 前記含浸工程、酸化反応工程及び回収工程に加え、
前記混合物調製工程、混合工程あるいは再生工程の内、
いずれか一つの工程あるいは複数の工程を、
前記同一の容器本体内において行うことを特徴とする請求項2記載の固相系酸化反応法を用いた有機化合物の製造方法。 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. - 密閉可能な容器本体と、
この容器本体内に設けられたフィルタと、
容器本体内に気体を供給する装置と、
容器本体内を所望の温度とするための温度調整機構とを具えて構成された装置において、
固体触媒の粉体と固体分散相の粉体とを混合して粉体の混合物を調製する混合物調製工程と、
前記混合物に原料有機化合物を加える混合工程と、
前記混合工程における処理が行われた混合物に酸化剤を含浸させる含浸工程と、
前記含浸工程における処理が行われた混合物中の原料有機化合物と酸化剤とを反応させる酸化反応工程と、
前記酸化反応工程で生成された有機化合物を溶剤に溶解させた状態で回収する回収工程と、
を順次実施することにより有機化合物を得ることができる有機化合物の製造装置において、
少なくとも前記含浸工程、酸化反応工程及び回収工程を同一の容器本体内において行うことができるように構成されていることを特徴とする固相系酸化反応法を用いた有機化合物の製造装置。 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. - 前記回収工程が実施された後の、固体触媒の粉体と固体分散相の粉体とを含む混合物を再利用するための再生工程を実施することができるように構成されるものであり、
前記再生工程により再生された混合物を用いて、
前記混合工程、含浸工程、酸化反応工程、回収工程及び再生工程を繰り返して行うことができるように構成されていることを特徴とする請求項4記載の固相系酸化反応法を用いた有機化合物の製造装置。 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. - 前記含浸工程、酸化反応工程及び回収工程に加え、
前記混合物調製工程、混合工程あるいは再生工程の内、
いずれか一つの工程あるいは複数の工程を、
前記同一の容器本体内において行うことができるように構成されていることを特徴とする請求項5記載の固相系酸化反応法を用いた有機化合物の製造装置。 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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