JP4545467B2 - Supercritical fine particle production equipment - Google Patents

Description

  The present invention relates to an apparatus for producing fine particles using a supercritical fluid, and in particular, by circulating and using solvent gas and co-solvent gas that have been exhausted to the outside, the running cost is reduced and the yield is increased. It relates to a device that can be used.

Recently, attention has been paid to the physical properties of supercritical fluids, and researches are being actively conducted on using them as new solvents to replace liquid solvents. Specifically, in the production of powders of foods, pharmaceuticals, agricultural chemicals, chemicals, etc., research on particle production methods using supercritical technology has been carried out, and the RESS method (Rapid Expansion of Supercritical Solutions) is used as the method. ) As well as the SAS method (Supercritical Antisolvent). The RESS process is one flow type RESS method of FIG. 4 using supercritical particle manufacturing apparatus D 'shown in (a), a solute dissolved than by mixing the solute dissolved already cosolvent SM and the supercritical fluid F A critical fluid S is obtained, and this solute-dissolving supercritical fluid S is ejected into the collector 2 ′ and rapidly expanded by decompression to create a supersaturated dissolution state of the solute M and precipitate the solute M as a powder G It is to let you.
A batch-type RESS method, which is one of the RESS methods, uses a supercritical fine particle production apparatus D ′ shown in FIG. 4B, and charges a solute M and a cosolvent H in a reactor 1 ′. A supercritical fluid F ′ is supplied to the reactor 1 ′ to obtain a solute-dissolving supercritical fluid S, and this solute-dissolving supercritical fluid S is ejected into the collector 2 ′ and rapidly expanded by decompression, and the solute is dissolved. A supersaturated dissolution state of M is created to precipitate the solute M as a granular material G (see, for example, Patent Document 1).
Also, the SAS process, supercritical particle production apparatus D shown in FIG. 4 (c) by spraying the solute dissolved already cosolvent SM in 'using a supercritical fluid F collector 2 was filled with' co Only the solvent H is dissolved in the supercritical fluid F, and the solute M is precipitated as a granular material G.

Even in the supercritical fine particle production apparatus D ′ used in either the RESS method or the SAS method, the solvent gas FG (carbon dioxide) and the cosolvent gas HG (vaporized cosolvent H) used as the solvent are externally provided. In particular, in the flow-type RESS method and the SAS method, a large amount of the co-solvent H is used to dissolve the solute M in the co-solvent H and then dissolve it in the supercritical fluid F. It has become enormous.
Further, although the fine particles G0 flowing out without being collected by the collector 2 'are captured by the filter 8', they are discharged without being captured by the filter 8 '. G1 is discharged to the outside together with the solvent gas FG and the auxiliary solvent gas HG.
Of course, it is possible to capture such ultrafine particles G1 with a finer filter, but it has not been possible to completely recover.
Japanese Patent Application No. 2003-174475 (FIG. 1)

  The present invention has been made in view of such a background. In particular, the solvent gas and the co-solvent gas that have been exhausted to the outside are circulated and used, and the solute deposited in the collector is completely removed. The technical issue is to develop a new supercritical fine particle production apparatus that can reduce the running cost and further increase the yield by collecting.

That is, the supercritical fine particle manufacturing apparatus according to claim 1 is configured to pressurize and raise the temperature of carbon dioxide as a solvent by a pump and a preheater to obtain a supercritical fluid, and with respect to the supercritical fluid and ethanol as a cosolvent. It is mixed and solute dissolved already co-solvent obtained by dissolving a solute to give a solute dissolved supercritical fluid, to rapidly expand further sprayed into the collector of the solute dissolved supercritical fluid from using a nozzle In the apparatus for obtaining a granular material by precipitating a solute , a co-solvent is placed in the housing at the subsequent stage of the collector, and the gas cleaning is configured to send a gas to be cleaned into the co-solvent. A condenser tank for condensing and liquefying the solvent gas separated by the gas scrubber, and a liquid reservoir tank for storing the liquefied solvent, and the liquid reservoir tank and the pump. First part By connecting the conduit with the conduit, it is intended that comprised Featuring being configured to allow recycling of the solvent gas.
According to this invention, since the solvent gas used as the supercritical fluid can be used effectively, the running cost can be reduced.

Further, the supercritical fine particle production apparatus according to claim 2 pressurizes and raises the temperature of carbon dioxide as a solvent by a pump and a preheater to make a supercritical fluid, and against this supercritical fluid and ethanol as a cosolvent. a solute dissolved already co-solvent obtained by dissolving a solute are mixed to obtain a solute dissolved supercritical fluid, by rapid expansion and further sprayed into the collector of the solute dissolved supercritical fluid from the nozzle In the apparatus for obtaining a granular material by precipitating a solute, a gas scrubber is configured such that a co-solvent is provided in the housing at the subsequent stage of the collector, and a gas to be cleaned is fed into the co-solvent . is equipped, the tube between with comprising a liquid reservoir tank for storing the solute dissolved already cosolvent to be separated and / or generated by the gas scrubber, and the liquid reservoir tank, and the pre-heater and the collector Connecting the road with a pipeline Accordingly, those comprising as characterized by being configured to allow recycling solutes dissolved already co-solvent.
According to the present invention, the cosolvent and the solute can be effectively used, so that the running cost can be reduced and the yield can be increased.

Furthermore, in the supercritical fine particle production apparatus according to claim 3 , the carbon dioxide as a solvent is pressurized and heated by a pump and a preheater to form a supercritical fluid, and the solute or solute is added to the supercritical fluid in the reactor. The solute-dissolving supercritical fluid is obtained by dissolving methanol as a co-solvent added as appropriate, and this solute-dissolving supercritical fluid is sprayed from the nozzle into the collector to rapidly expand the solute. In the apparatus for obtaining a granular material by precipitation, a gas scrubber is provided at the subsequent stage of the collector, in which a co-solvent is provided in the housing, and a gas to be cleaned is fed into the co-solvent. A condensing tank for condensing and liquefying the solvent gas separated by the gas scrubber, and a liquid reservoir tank for storing the liquefied solvent, and a pipe in the former stage portion of the liquid reservoir and the pump By connecting the door in line, it is intended that comprised Featuring being configured to allow recycling of the solvent gas.
According to this invention, since the solvent gas used as the supercritical fluid can be used effectively, the running cost can be reduced.

Furthermore, in the supercritical fine particle production apparatus according to claim 4 , the carbon dioxide as a solvent is pressurized and heated by a pump and a preheater to form a supercritical fluid, and a solute or solute is added to the supercritical fluid in the reactor. The solute-dissolving supercritical fluid is obtained by dissolving methanol as a co-solvent added as appropriate, and this solute-dissolving supercritical fluid is sprayed from the nozzle into the collector to rapidly expand the solute. In the apparatus for obtaining a granular material by precipitation, a gas scrubber is provided at the subsequent stage of the collector, in which a co-solvent is provided in the housing, and a gas to be cleaned is fed into the co-solvent. , together comprising a liquid reservoir tank for storing the solute dissolved already cosolvent to be separated and / or generated by the gas scrubber, and the liquid reservoir tank, and a pipe line between the preheater and the collector Tie by pipe And by, those comprising as characterized by being configured to allow recycling solutes dissolved already co-solvent.
According to the present invention, the cosolvent and the solute can be effectively used, so that the running cost can be reduced and the yield can be increased.

Furthermore, in the supercritical fine particle production apparatus according to claim 5 , the carbon dioxide as a solvent is pressurized and heated by a pump and a preheater to form a supercritical fluid, and the supercritical fluid is filled in the collector. by spraying the solute dissolved already co-solvent obtained by dissolving a solute from a nozzle against ethanol as co-solvent, the only co-solvent is dissolved in the supercritical fluid, to obtain a granular material to precipitate solute device In the above, a gas scrubber is provided at the rear stage of the collector, in which a co-solvent is provided in the housing, and a gas to be cleaned is fed into the co-solvent, and is separated by the gas scrubber. By providing a condensing tank for condensing and liquefying the solvent gas and a liquid reservoir tank for storing the liquefied solvent, and connecting the liquid reservoir tank and the pipe line of the previous stage of the pump by a pipe line , Solvent gas It is configured to allow recycling those comprising as said.
According to this invention, since the solvent gas used as the supercritical fluid can be used effectively, the running cost can be reduced.

Furthermore, in the supercritical fine particle production apparatus according to claim 6 , the carbon dioxide as a solvent is pressurized and heated by a pump and a preheater to form a supercritical fluid, and the supercritical fluid is filled in the collector. by spraying the solute dissolved already co-solvent obtained by dissolving a solute from a nozzle against ethanol as co-solvent, the only co-solvent is dissolved in the supercritical fluid, to obtain a granular material to precipitate solute device And a gas scrubber configured to send a gas to be cleaned into the cosolvent, and is separated and / or separated by the gas scrubber. or together with the generated comprising a liquid reservoir tank for storing the solute dissolved already cosolvent, and the liquid reservoir tank, by connecting the pipe between the preheater and the collector in line, solute dissolved circulation benefit the already co-solvent That is configured to be those comprising as said.
According to the present invention, the cosolvent and the solute can be effectively used, so that the running cost can be reduced and the yield can be increased.
The above problems can be solved by using the configuration of the invention described in each of the claims as a means.

  According to the present invention, the solvent gas and the co-solvent gas that have been exhausted to the outside in the past are circulated and used, thereby reducing the consumption and reducing the running cost, and the solute deposited in the collector. Can be fully recovered to increase the yield.

One of the best modes of the supercritical fine particle production apparatus of the present invention is as described in the following examples, and is a supercritical fine particle production apparatus for realizing a flow-type RESS method, a batch-type RESS method, and a SAS method. Each of the configurations and the operation modes thereof 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.

First, the supercritical fine particle production apparatus D for carrying out the flow-type RESS method will be described. As shown in FIG. 1, the supercritical fine particle production apparatus D increases the temperature of the solvent by a pump 5 and a preheater 6 and raises the temperature. with a, and the supercritical fluid F, a mixture of a solute dissolved already cosolvent SM Newsletter solute dissolved supercritical fluid S, further the solute dissolved supercritical fluid S in the collector 2 from the nozzle 20 It is an apparatus for obtaining a granular material G by depositing a solute M by spraying and rapidly expanding.
The supercritical fine particle production apparatus D is provided with a system for obtaining the supercritical fluid F. For example, the carbon dioxide filled in the cylinder 3 is cooled in the chiller unit 4 and then pumped. A configuration is adopted in which the critical point is exceeded by increasing the pressure and increasing the temperature by 5 and the preheater 6. Carbon dioxide can be obtained at a relatively low price, has a critical temperature of 31.1 ° C., a critical pressure of 7.38 MPa, and is a solvent that can be easily separated because it becomes a gas at normal temperature and normal pressure. .

And the main conduit 7 between the collector 2 and the preheater 6, solute dissolved already cosolvent feed line 72 for supplying a solute dissolved already cosolvent SM are connected, in the main conduit 7 Ultra it is mixed with supercritical fluid F solute dissolved already cosolvent SM, in which solute dissolved supercritical fluid S is generated.

Hereinafter, various members constituting the supercritical fine particle production apparatus D will be described in detail.
First, the collector 2 will be described. The collector 2 is provided with a nozzle 20 for ejecting the solute-dissolving supercritical fluid S into a casing formed so as to maintain an airtight state. The nozzle 20 is connected to the main pipeline 7, and a filter 23 is provided between the preheater 6 and the nozzle 20 for the purpose of preventing clogging of the nozzle 20. Moreover, the pressure sensor P2 for measuring the pressure in the collector 2 is provided.
Further, a filter 8 for capturing the fine particles G0 flowing out from the exhaust port 24 is provided at the next stage of the exhaust port 24 in the collector 2.

  Next, the cylinder 3 will be described. This is a member for holding a liquefied solvent gas FG (in this embodiment, liquefied carbon dioxide), and a valve V1 is provided at the mouth.

  Next, the chiller unit 4 will be described. The chiller unit 4 includes an appropriate cooling means and a cooling surface. By cooling the liquid touching the cooling surface, bubbles are generated at the inlet of the pump 5. It is a device to prevent.

  Next, the pump 5 will be described. This is a member for increasing the pressure of the fluid supplied from the cylinder 3, and is provided with an inverter for controlling the flow rate at an appropriate rotational speed.

  Next, the preheater 6 will be described. This is a member for raising the temperature of the solvent gas FG boosted by the pump 5, and comprises an appropriate heating means.

The above members are connected by a main pipe 7 made of SUS304, SUS316, SUS316L, or the like in the order of the cylinder 3, the chiller unit 4, the pump 5, the preheater 6, and the collector 2, and the main pipe Valves V2, V3 and V4 are provided between the devices in FIG.
Further, a return pipe 71 having a relief valve 71 a is provided between the rear stage part of the pump 5 in the main pipe line 7 and the front stage part of the chiller unit 4, and the pressure is increased through the return pipe 71. By feeding back the solvent gas FG, the pressure of the fluid can be adjusted.

Also in the front portion of the main conduit 7, specifically the valve V3 between the collector 2 and the preheater 6 is connected to a solute dissolved already cosolvent supply conduit 72 connected to a tank (not shown) is intended, the pump 72a and a check valve 72b is equipped for this solute dissolved already cosolvent supply line 72.
Incidentally, the collector 2 and the main pipe line 7 before and after this are arranged in the thermostat, or an appropriate heater is wound around the collector 2 and the main pipe line 7 before and after the thermostat tank. The temperature may be maintained at a desired temperature.
The configuration up to this point is the same as that of the existing supercritical fine particle production apparatus D ′ used in the flow-type RESS method shown in FIG. 4A, and the configuration unique to the present invention will be described below. I do.

Specifically, a gas scrubber 9 is connected to the subsequent stage of the collector 2, and this gas scrubber 9 has an exhaust port 91 formed in the upper part of a hollow casing 90 and exhausted in the lower part. An outlet 92 is formed.
The exhaust port 91 is connected to a portion on the cylinder 3 side among the connection portions of the main pipe line 7 and the return pipe line 71 by a solvent return pipe line 73, and the solvent return pipe line 73. Is provided with a condensing tank 73a and a liquid reservoir 73b. The solvent return line 73 between the exhaust port 91 and the condensing tank 73a is provided with a pump 73c and a filter 73d.
Further to the discharge port 92, between the inlet side of the pump 72a in the solute dissolved already cosolvent feed line 72 is intended to be connected by a solute cosolvent return line 74, the solute cosolvent return line 74 is provided with a liquid storage tank 74a and a valve V6.

  The supercritical fine particle production apparatus D of the present invention shown in this embodiment is configured as described above as an example, and the operation mode of this apparatus will be described below. In this embodiment, acetylsalicylic acid is used as the solute M, carbon dioxide supercritical fluid F is used as the solvent, ethanol is further used as the co-solvent H, and finally a granular material G having a particle size of about 0.01 mmφ is obtained. The process of obtaining will be described. Incidentally, a supercritical fluid F such as methanol or water can also be used as a solvent.

(1) the solute M was dissolved in the cosolvent H in a suitable vessel at the beginning first generation of solutes dissolved already cosolvent is intended to obtain a solute dissolved already cosolvent SM, to ethanol 50ml in this embodiment 2.5 g of acetylsalicylic acid was dissolved.
At this time, a cosolvent H (ethanol) is placed in the housing 90 of the gas washer 9.

(2) Generation of Supercritical Fluid and Solute Dissolving Supercritical Fluid Next, valves V1 to V4 are opened from a state in which all valves V1 to V6 are closed, and carbon dioxide that is liquid in the cylinder 3 is the main pipe. It is introduced into the passage 7 and first cooled in the chiller unit 4. The solvent gas FG is increased in pressure and heated by the action of the pump 5 and the preheater 6 to exceed the critical point, and is located in the main pipeline 7 in a state of becoming a supercritical fluid F. The flow rate pressure of the fluid is monitored by the pressure sensor P1, and by appropriately adjusting the opening degree of the relief valve 71a, a part of the pressurized gas is fed back to the front part of the chiller unit 4, and the pump 5 by the inverter is used. The desired value is obtained by the rotational speed control. In this embodiment, the pressure of the supercritical fluid F was increased to 15 MPaG, and the temperature was increased to 45-60 ° C.
Then, after the main conduit 7 becomes stable supercritical state, by activating the pump 72a, will be solute dissolved already cosolvent SM is positioned in the main conduit 7 with the supercritical fluid F, where intermingles with each other Accordingly, a solute dissolving supercritical fluid S is generated.

(3) Generation of granular material Since the inside of the collector 2 is at atmospheric pressure, the solute-dissolving supercritical fluid S is sprayed from the nozzle 20 and rapidly expands in the collector 2 to form the solute M. is deposited acetylsalicylic acid, eventually granular material G of the desired properties is obtained, Ru recovered adsorbed on the collection sheet 25.
At this time, the solvent gas FG which is carbon dioxide which has become gas with the precipitation of the solute M flows out from the exhaust port 24 together with the co-solvent gas HG and the fine particles G0, and the filter 8 makes most of the fine particles G0. Is captured.

(4) Recovery of solvent The solvent gas FG, the co-solvent gas HG, and the ultrafine particles G1 not captured by the filter 8 are fed into the co-solvent H in the gas scrubber 9, where The solvent gas FG rises in the co-solvent H in the form of a gas, and eventually, the pump 73c is pressurized from the exhaust port 91 via the solvent return pipe 73, if necessary, and reaches the condensing tank 73a where it is liquefied. After being stored in the liquid storage tank 73b, it is sent to the front stage portion of the chiller unit 4 in the main pipe line 7 and is increased in pressure and temperature by the pump 5 and the preheater 6 to be used again as the supercritical fluid F as a solvent. It is.

(5) Solute and co-solvent recovery On the other hand, in the gas scrubber 9, the co-solvent gas HG sent from the collector 2 is liquefied, and the very fine particles G1 are dissolved in the co-solvent H, and the solute. so that the dissolving already cosolvent SM is generated. And as such a series of particle production takes place, the solute dissolved already cosolvent SM in the gas scrubber 9 are those coming growing concentration at the time became a desired concentration or gas scrubber 9, the liquid level valve V6 is opened when it becomes the desired value, after being stored in the liquid vessel 74a, is sent to the front portion of the pump 72a in the solute dissolved already cosolvent supply line 72, a solute dissolved again It is used as a finished auxiliary solvent SM.
When the solvent gas FG in the system becomes excessive, the solvent gas FG is exhausted to the outside by opening the valve V5 as appropriate.

Next, the supercritical fine particle production apparatus D for carrying out the batch-type RESS method will be described. As shown in FIG. 2, the apparatus is pressurized and heated by a pump 5 and a preheater 6 to increase the temperature of the supercritical fluid F. In addition, the solute M or the solute M and the cosolvent H added as appropriate are dissolved in the supercritical fluid F in the reactor 1 to obtain a solute-dissolving supercritical fluid S, and this solute-dissolving supercritical fluid. It is an apparatus for depositing the solute M by spraying S into the collector 2 from the nozzle 20 and rapidly expanding it, thereby obtaining a granular material G.
The supercritical fine particle production apparatus D is provided with a system for obtaining the supercritical fluid F. Similar to the apparatus shown in the first embodiment, the cylinder 3, the chiller unit 4, the pump 5, and the preheater. 6.
Further, between the preheater 6 and the collector 2, there is provided a reactor 1 for dissolving the solute M in the supercritical fluid F and generating the solute-dissolving supercritical fluid S. Since the apparatus has the same configuration as that of Example 1, only the reactor 1 will be described below.

  The reactor 1 is a container used to dissolve the solute M in the supercritical fluid F as a solvent, and is configured to be hermetically sealed using SUS304, SUS316, SUS316L, or the like as a material. In this example, carbon dioxide supercritical fluid F was used as a solvent, and therefore, it was designed to withstand a maximum pressure of 20.0 MPaG and a maximum temperature of 150 ° C. as an example. In addition, the reactor 1 is provided with a stirrer 10 for stirring and mixing the solute M and the supercritical fluid F as necessary.

  The supercritical fine particle production apparatus D of the present invention shown in this embodiment is configured as described above as an example, and the operation mode of this apparatus will be described below. In this example, naphthalene is used as the solute M, a supercritical fluid F of carbon dioxide is used as the solvent, and methanol is used as the cosolvent H. Finally, a granular material G having a particle size of about 0.01 mmφ is obtained. The process will be described. Incidentally, a supercritical fluid F such as methanol or water can also be used as a solvent.

(1) Feeding of raw materials First, the solute M is fed into the reactor 1 with the valves V1, V2, V3, and V4 closed, and a co-solvent H is further fed as necessary. The co-solvent H increases the solubility of the solute M when mixed with the supercritical fluid F, and an appropriate one is selected according to the solute M.

(2) Generation of Supercritical Fluid Next, valves V 1, V 2, V 3 are opened, and carbon dioxide, which is liquid in the cylinder 3, is introduced into the main pipeline 7 and is first cooled in the chiller unit 4. The solvent gas FG is boosted and heated by the action of the pump 5 and the preheater 6 to exceed the critical point, and is supplied to the reactor 1 in a state of becoming a supercritical fluid F.
In this example, the pressure of the supercritical fluid F in the reactor 1 was increased and increased so that the pressure was 15 MPaG and the temperature was 45 to 60 ° C.
The flow rate pressure of the gas is monitored by the pressure sensor P1, and by appropriately adjusting the opening degree of the relief valve 71a, a part of the boosted gas is fed back to the front part of the chiller unit 4, and the pump 5 by the inverter is used. The desired value is obtained by the rotational speed control.

(3) Generation of solute-dissolving supercritical fluid The reactor 1 is sequentially supplied with the supercritical fluid F, and the pressure sensor P2 detects that the pressure in the reactor 1 has reached a predetermined value. At this point, the valve V3 is closed. At this time, the solute M is dissolved in the supercritical fluid F in the reactor 1 and a solute-dissolving supercritical fluid S is generated. The stirrer 10 is appropriately activated to promote the dissolution. .

(4) Generation and collection of powder and granule When the valve V4 is opened, the inside of the collector 2 is at atmospheric pressure, so the solute-dissolving supercritical fluid S is sprayed from the nozzle 20 and rapidly in the collector 2. The swell expands and naphthalene, which is the solute M, is deposited, and eventually the desired granular material G is obtained. And this granular material G will adhere to the collection | recovery sheet | seat 25 distribute | arranged in the collector 2, and will be collect | recovered.
At this time, if there is an undissolved solute M in the reactor 1, this is captured by the filter 23, so that clogging of the nozzle 20 can be avoided.
At this time, the solvent gas FG, which is carbon dioxide that has become gas with the precipitation of the solute M, flows out from the exhaust port 24 together with the cosolvent gas HG, the cosolvent gas HG, and the fine particles G0. Most of the particles G0 are captured.

(5) Recovery of solvent The solvent gas FG, the co-solvent gas HG, and the ultrafine particles G1 not captured by the filter 8 are fed into the co-solvent H in the gas scrubber 9, where The solvent gas FG rises in the co-solvent H in the form of a gas, and eventually, the pump 73c is pressurized from the exhaust port 91 via the solvent return pipe 73, if necessary, and reaches the condensing tank 73a where it is liquefied. After being stored in the liquid storage tank 73b, it is sent to the front stage portion of the chiller unit 4 in the main pipe line 7 and is increased in pressure and temperature by the pump 5 and the preheater 6 to be used again as the supercritical fluid F as a solvent. It is.

(6) Recovery of solute and co-solvent On the other hand, in the gas scrubber 9, the co-solvent gas HG sent from the collector 2 is liquefied, and the fine particles G1 are dissolved in the co-solvent H, and the solute so that the dissolving already cosolvent SM is generated. And as such a series of particle production takes place, the solute dissolved already cosolvent SM in the gas scrubber 9 are those coming growing concentration at the time became a desired concentration or gas scrubber 9, the liquid level valve V6 is opened when it becomes the desired value, after being stored in the liquid vessel 74a, is sent to the front portion of the pump 72a in the solute dissolved already cosolvent supply line 72, a solute dissolved again It is used as a finished auxiliary solvent SM.
When the solvent gas FG in the system becomes excessive, the solvent gas FG is exhausted to the outside by opening the valve V5 as appropriate.

Next, a supercritical fine particle production apparatus D for carrying out the SAS method will be described. In this apparatus, as shown in FIG. 3, the pressure of the solvent is increased and the temperature is raised by a pump 5 and a preheater 6 to obtain a supercritical fluid F. together, by spraying the solute dissolved already cosolvent SM from the nozzle 20 into the collecting vessel 2 which is filled with the supercritical fluid F, the only co-solvent H is dissolved in the supercritical fluid F, to precipitate solute M This is an apparatus for obtaining the granular material G.
The supercritical fine particle production apparatus D is provided with a system for obtaining the supercritical fluid F. As in the apparatus described in the first embodiment and shown in FIG. 1, the cylinder 3, the chiller unit 4, the pump 5 and the preheater 6.
Further, the supercritical fine particle production apparatus D shown in this embodiment is different from the apparatus shown in FIG. 1 and shown in FIG. 1 only in that a pipe connecting method to the collector 2 and a back pressure valve 75 are provided. Since the configuration is adopted, only this portion will be described below.

Specifically, the to collector 2 is connected the main conduit 7 without the intervention of the nozzle directly to the further collector 2 nozzle 20 provided in the solute dissolved already cosolvent feed line 72 To be connected. Note that the solute dissolved already cosolvent supply line 72 between the check valve 72b and the nozzle 20, the valve 72c is equipped. A main pressure line 7 between the collector 2 and the gas scrubber 9 is provided with a back pressure valve 75 so that the inside of the collector 2 can be maintained at a desired pressure.

  The supercritical fine particle production apparatus D of the present invention shown in this embodiment is configured as described above as an example, and the operation mode of this apparatus will be described below. In this example, acetylsalicylic acid is used as the solute M, a supercritical fluid F of carbon dioxide is used as the solvent, ethanol is further used as the cosolvent H, and finally a granular material G having a particle size of about 0.01 mmφ is obtained. The process of obtaining will be described. Incidentally, a supercritical fluid F such as methanol or water can also be used as a solvent.

(1) the solute M was dissolved in the cosolvent H in a suitable vessel at the beginning first generation of solutes dissolved already cosolvent is intended to obtain a solute dissolved already cosolvent SM, to ethanol 50ml in this embodiment 2.5 g of acetylsalicylic acid was dissolved.
At this time, a cosolvent H (ethanol) is placed in the housing 90 of the gas washer 9.

(2) Generation of Supercritical Fluid Next, valves V 1, V 2, V 3 are opened, and carbon dioxide, which is liquid in the cylinder 3, is introduced into the main pipeline 7 and is first cooled in the chiller unit 4. The solvent gas FG is boosted and heated by the action of the pump 5 and the preheater 6 to exceed the critical point, and is supplied to the collector 2 in a state of becoming a supercritical fluid F.
In this example, the pressure of the supercritical fluid F in the collector 2 was 15 MPaG, and the temperature was 45-60 ° C.
The flow rate pressure of the gas is monitored by the pressure sensor P1, and by appropriately adjusting the opening degree of the relief valve 71a, a part of the boosted gas is fed back to the front part of the chiller unit 4, and the pump 5 by the inverter is used. The desired value is obtained by the rotational speed control.

(3) the pressure of the supercritical fluid F solute dissolved already co-on and the collector 2 solvents opens the valve 72c at the time it was confirmed by the pressure sensor P2 that has become a desired value, already a solute dissolved The cosolvent SM is supplied into the collector 2.

(4) Production and recovery of granular material Since only the co-solvent M is dissolved in the supercritical fluid F in the collector 2, acetylsalicylic acid as the solute H is precipitated, and eventually the desired granular material G is formed. can get. And this granular material G will adhere to the collection | recovery sheet | seat 25 distribute | arranged in the collector 2, and will be collect | recovered.
At this time, the carbon dioxide serving as the solvent gas FG became gas with precipitation of solute M is to flow out through the exhaust port 24 together with the co-solvent gas H G及 beauty fine granules G0, the fine grain body G0 by the filter 8 Most are captured.

(5) Recovery of solvent The solvent gas FG, the co-solvent gas HG, and the ultrafine particles G1 not captured by the filter 8 are fed into the co-solvent H in the gas scrubber 9, where The solvent gas FG rises in the co-solvent H in the form of gas, and eventually reaches the condensing tank 73a from the exhaust port 91 via the solvent return pipe 73, where it is liquefied and stored in the liquid tank 73b. It is sent to the front stage portion of the chiller unit 4 in the main pipe line 7 and is increased in pressure and temperature by the pump 5 and the preheater 6 to be used again as the supercritical fluid F as a solvent.

(6) Recovery of solute and co-solvent On the other hand, in the gas scrubber 9, the co-solvent gas HG sent from the collector 2 is liquefied, and the fine particles G1 are dissolved in the co-solvent H, and the solute so that the dissolving already cosolvent SM is generated. And as such a series of particle production takes place, the solute dissolved already cosolvent SM in the gas scrubber 9 are those coming growing concentration, valve V6 is opened as it becomes a desired concentration, the liquid after being stored in the reservoir tank 74a, it is sent to the front portion of the pump 72a in the solute dissolved already cosolvent supply line 72, is intended to be provided as a solute dissolved already cosolvent SM again.
When the solvent gas FG in the system becomes excessive, the solvent gas FG is exhausted to the outside by opening the valve V5 as appropriate.

It is a block diagram which shows the supercritical microparticle manufacturing apparatus of this invention for enforcing a flow-through RESS method. It is a block diagram which shows the supercritical microparticle manufacturing apparatus of this invention for enforcing a batch type RESS method. It is a block diagram which shows the supercritical microparticle manufacturing apparatus of this invention for implementing SAS method. It is a block diagram which shows the conventional 3 types of supercritical microparticle manufacturing apparatus for enforcing a flow-type RESS method, a batch-type RESS method, and a SAS method.

D supercritical particle production apparatus 1 reactor 10 agitator 2 collector 20 nozzle 23 filter 24 outlet 25 collection sheet 3 cylinder 4 chiller unit 5 pump 6 preheater 7 main line 71 return line 71a relief valve 72 solute dissolved already Auxiliary solvent supply line 72a Pump 72b Check valve 72c Valve 73 Solvent return line 73a Condensing tank 73b Liquid reservoir 73c Pump 73d Filter 74 Solute auxiliary solvent return line 74a Liquid reservoir 75 Back pressure valve 8 Filter 9 Gas washer 90 Housing 91 Exhaust port 92 Discharge port F Supercritical fluid FG Solvent gas G Powder G0 Fine powder G1 Ultrafine powder H Cosolvent HG Cosolvent gas M Solute P1 Pressure sensor P2 Pressure sensor S Solute dissolution supercritical fluid SM Solute dissolution already co-solvent V1 valve V2 valve V3 valve V4 valve V5 valve V Valve

Claims (6)

Boosting the carbon dioxide as a solvent by a pump and preheater, and heated with a supercritical fluid, and the supercritical fluid, solute dissolved already co-solvent obtained by dissolving a solute against ethanol as co-solvent To obtain a solute-dissolving supercritical fluid, and then spraying this solute-dissolving supercritical fluid from the nozzle into the collector to rapidly expand, thereby precipitating the solute and obtaining a granular material In the above, a gas scrubber is provided at the rear stage of the collector, in which a co-solvent is provided in the housing, and a gas to be cleaned is fed into the co-solvent, and is separated by the gas scrubber. By providing a condensing tank for condensing and liquefying the solvent gas and a liquid reservoir tank for storing the liquefied solvent, and connecting the liquid reservoir tank and the pipe line of the previous stage of the pump by a pipe line , Circulating solvent gas Supercritical particle manufacturing apparatus characterized by being configured to use. Boosting the carbon dioxide as a solvent by a pump and preheater, and heated with a supercritical fluid, and the supercritical fluid, solute dissolved already co-solvent obtained by dissolving a solute against ethanol as co-solvent To obtain a solute-dissolving supercritical fluid, and then spraying this solute-dissolving supercritical fluid from the nozzle into the collector to rapidly expand, thereby precipitating the solute and obtaining a granular material And a gas scrubber configured to send a gas to be cleaned into the cosolvent, and is separated and / or separated by the gas scrubber. or together with the generated comprising a liquid reservoir tank for storing the solute dissolved already cosolvent, and the liquid reservoir tank, by connecting the pipe between the preheater and the collector in line, solute dissolved It can recycling the already co-solvent Supercritical particle manufacturing apparatus characterized by being configured to. The pressure of carbon dioxide as a solvent is raised and raised by a pump and a preheater to make a supercritical fluid, and solute or solute and methanol as a co-solvent appropriately added are dissolved in the supercritical fluid in the reactor. The solute-dissolving supercritical fluid is obtained, and further, the solute-dissolving supercritical fluid is sprayed into the collector from the nozzle and rapidly expanded, thereby precipitating the solute and obtaining the granular material. In the latter part of the collector, a co-solvent is provided in the housing, and a gas scrubber configured to send a gas to be cleaned into the co-solvent is provided. The solvent gas separated by the gas scrubber is condensed. And a condensing tank for liquefying and a liquid reservoir tank for storing the liquefied solvent, and by connecting the liquid reservoir tank and a pipe line of the front stage of the pump by a pipe line, Circulation interest Supercritical particle manufacturing apparatus characterized by being configured to allow. The pressure of carbon dioxide as a solvent is raised and raised by a pump and a preheater to make a supercritical fluid, and solute or solute and methanol as a co-solvent appropriately added are dissolved in the supercritical fluid in the reactor. The solute-dissolving supercritical fluid is obtained, and further, the solute-dissolving supercritical fluid is sprayed into the collector from the nozzle and rapidly expanded, thereby precipitating the solute and obtaining the granular material. In the subsequent stage of the collector, a co-solvent is provided in the housing, and a gas scrubber configured to feed a gas to be cleaned into the co-solvent is provided, and is separated and / or generated by the gas scrubber. together comprising a liquid reservoir tank for storing the solute dissolved already cosolvent, and the liquid reservoir tank, by connecting the pipe between the preheater and the collector in line, a solute dissolved already co-solvent Recyclable Supercritical particle manufacturing apparatus characterized by being configured urchin. The pressure of carbon dioxide as a solvent is increased and raised to a supercritical fluid by a pump and a preheater, and a solute is dissolved in ethanol as a cosolvent in a collector filled with the supercritical fluid. by spraying the resulting solute dissolved already cosolvent from the nozzles, the only co-solvent is dissolved in the supercritical fluid, in to precipitate solute apparatus for obtaining powdery grains, downstream of the collector, the enclosure And a condensing tank for condensing and liquefying the solvent gas separated by the gas scrubber, comprising a gas scrubber configured to send a gas to be cleaned into the cosolvent. In addition, a liquid storage tank for storing the liquefied solvent is provided, and the liquid storage tank is connected to the upstream line of the pump by a pipe so that the solvent gas can be circulated and used. Special And supercritical particle manufacturing apparatus. The pressure of carbon dioxide as a solvent is increased and raised to a supercritical fluid by a pump and a preheater, and a solute is dissolved in ethanol as a cosolvent in a collector filled with the supercritical fluid. by spraying the resulting solute dissolved already cosolvent from the nozzles, the only co-solvent is dissolved in the supercritical fluid, in to precipitate solute apparatus for obtaining powdery grains, downstream of the collector, the enclosure the cosolvent is stretched, configured gas scrubber to pump to be cleaned gas is provided in the co-solvent, for storing the solute dissolved already cosolvent to be separated and / or generated by the gas scrubber together comprising a liquid reservoir tank, and the liquid reservoir tank, by connecting the pipe between the preheater and the collector in line, and is configured to allow recycling of the solute dissolved already co-solvent It is characterized by Critical particle production equipment.

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