JP2009066519A - Separator employing distillation and membrane separation in combination - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a separator for a liquid mixture which saves consumption energy, has improved separation efficiency and separation capability, and makes facilities compact. <P>SOLUTION: The separator comprises a distillation means 100 for separating a liquid mixture and membrane separation means for separating a mixed vapor discharged out of the tower summit part of the distillation means by a membrane separation method. The distillation means is provided with a distillation tower 1 filled with a filler 10 and a partial condenser 2 and the membrane separation means is provided with separation membrane modules 3a... 3d each having a vapor separation treatment chamber 31 and a separation membrane 32 installed in the treatment chamber, and a heating means 4 for heating the treatment chamber. The mixed vapor discharged through the partial condenser is supplied to the membrane modules and heated in the treatment chamber and separated by membrane separation. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a separation device for a multi-component liquid mixture. More specifically, the present invention relates to a separation apparatus that combines a distillation means for separation by a distillation method and a membrane separation means for separation by a membrane separation method.

  One typical separation method for separating the components of a liquid mixture is a distillation method. The distillation method is carried out using a distillation column. When components are separated by a normal evaporation method (distillation operation) or an azeotropic mixture or a liquid mixture having a low relative volatility with close boiling points, the following is performed. Have a problem.

In distilling azeotropes, the separation concentration is limited. For example, ethanol and an aqueous mixed solution have an azeotropic boiling point at an ethanol concentration of 89 mol% (95.6 wt%), so that ethanol cannot be concentrated by more than 95.6 wt% by a normal distillation method. Therefore, when distilling an azeotropic mixture, for example, an azeotropic distillation method is employed in which another component is added to the mixture as an entrainer to form another azeotropic mixture, and distillation is performed together with the entrainer. However, this method requires the addition of an azeotropic distillation tower, an entrainer regeneration tower, etc., which increases the size of the equipment and increases the energy consumption.
In addition, when separating a liquid mixture having a close boiling point and a low relative volatility by the distillation method, it is necessary to increase the number of theoretical columns of the distillation column, so that the height of the distillation column is increased and the equipment is installed. Increased size and energy consumption.

  There is a membrane separation method as another component separation method of the liquid mixture. The membrane separation method uses a separation membrane to separate components of a liquid mixture, and examples thereof include a pervaporation method (PV method) and a vapor permeation method (VP method). In the PV method, a specific liquid (permeate) is vaporized by bringing the liquid mixture into contact with one side of the separation membrane (supply side = primary side) and depressurizing the opposite side (permeation side = secondary side). This is a membrane separation method (pervaporation method). On the other hand, in the VP method, a liquid mixture is vaporized (vaporized), supplied in a vapor state and brought into contact with a separation membrane, and the permeation side (secondary side) is depressurized to permeate (separate) specific vapor. This is a separation method (vapor transmission method). Such a membrane separation method has attracted attention as a new method for separating or concentrating a liquid mixture that could not be separated by a simple method, that is, an azeotropic mixture described above or a liquid mixture having a low boiling point and a low relative volatility. Has been. In the PV method, generally, a method of heating a liquid mixture and bringing the heated liquid into contact with a separation membrane is generally employed.

  When the liquid mixture is separated into components by the membrane separation method, the separation efficiency can be improved by concentrating as much as possible the separation object (liquid or gas) and supplying it to the membrane separation apparatus. Then, the method of separating using the distillation method and the membrane separation method together is tried. As an example of this combined method, the liquid mixture is distilled in a distillation tower, and the mixed vapor to be distilled is liquefied and recovered by a condenser, and then the recovered mixed liquid is heated and vaporized (vaporized). Is used to supply the membrane to a membrane separator for separation. According to this method, it is possible to concentrate or separate an azeotropic mixture or a liquid mixture having a boiling point close to a high concentration.

  However, the above combined method liquefies and recovers the mixed vapor distilled from the distillation column, and then heats the liquid again to supply it to the membrane separation apparatus. Have.

As another separation method using both the distillation method and the membrane separation method, the azeotropic distillation method and the membrane separation method are combined, the entrainer is collected from the top of the azeotropic distillation column, and the ethyl tert-butyl ether is collected from the bottom of the azeotropic distillation column, A method has been proposed in which a mixed liquid rich in ethanol is extracted from the middle side surface of an azeotropic distillation column and sent to a membrane separation apparatus, and ethanol is separated by a membrane separation method (see Patent Document 1). However, since Patent Document 1 employs an azeotropic distillation method, it has the above-described problems such as an increase in equipment size.
JP 7-278035 A

  In view of the above circumstances, an object of the present invention is to provide a liquid mixture separation device that can reduce energy consumption, improve separation efficiency and separation performance, and can make equipment compact.

In order to achieve the above object, the present invention is a separation apparatus comprising a distillation means for separating a liquid mixture, and a membrane separation means for separating a mixed vapor distilled from the top of the distillation means by a membrane separation method, The distillation means includes a distillation column filled with a packing, and a partial condenser provided at the top of the distillation tower. The membrane separation means includes a vapor separation treatment chamber and a separation membrane provided in the treatment chamber. A separation membrane module having heating means for heating the inside of the processing chamber, and supplying the mixed vapor distilled through the partial condenser to the membrane module to heat the inside of the processing chamber for membrane separation. (1st invention). In the present invention, the “demultiplexer” is a kind of partial capacitor (Partial capacitor).
It is used as a term that means a heat exchanger for cooling that has an action (function) such as Condenser.

  If comprised like this invention, in the distillation means, the mixed vapor | steam of a liquid mixture will raise the inside of a distillation column, contacting with a packing. In this ascending process, heat is exchanged by contact with the packing, and the component having a high boiling point is liquefied and adheres to the packing, and the component having a low boiling point is not liquefied but rises as it is and is introduced into the partial condenser. In this way, the mixed steam is heated in contact with the packing while rising in the distillation column, and the high boiling point component is liquefied and flows down in the middle of the column and circulates to the bottom of the column, thereby mixing. Steam is subjected to component separation treatment (primary treatment) in the distillation column.

  On the other hand, the steam (primary treated mixed steam) introduced into the condenser without being liquefied in the distillation tower is heat-exchanged with cold heat while passing through the condenser, and the high-boiling components in the steam are liquefied. Then, it is refluxed into the distillation column, and the low boiling point component is not liquefied but maintained in a gas (vapor) state, passes through a partial condenser, is distilled out of the vessel, and is supplied to the membrane separation means. Thus, since the mixed vapor separated in the distillation tower (primary treatment) is finely separated again in the partial condenser (secondary treatment), the liquid mixture is a distillate vapor concentrated to a high concentration. It becomes.

  The distillate vapor supplied from the distillation means is introduced into the vapor separation treatment chamber of the separation membrane module, and this vapor is heated in the treatment chamber by the heating means and subjected to component separation treatment by the membrane separation method.

  In the present invention, the membrane separation means may employ a configuration including a plurality of the membrane modules (second invention). Moreover, the separation membrane of the said membrane module can employ | adopt the separation membrane comprised with the zeolite membrane (3rd invention).

The present invention has the following effects.
(1) The distillation means comprises a distillation column filled with a packing and a partial condenser provided at the top of the tower, so that the liquid mixture can be concentrated to a high concentration by the distillation means. At the same time, the equipment can be made compact.
(2) Since the distillate distilled through the fractionator of the distillation means is supplied to the separation membrane module of the membrane separation means and heated in the vapor separation treatment chamber, the membrane is separated. The energy consumption required can be reduced and the separation efficiency and separation performance can be improved.
(3) The azeotropic mixture can be concentrated to a concentration equal to or higher than the azeotropic point, and a liquid mixture having a boiling point close to that can be concentrated with high accuracy.
(4) According to the second invention, in addition to the above effects, the separation performance can be further improved.
(5) According to the third invention, in addition to the above-mentioned effects, the effects excellent in heat resistance, solvent resistance, and acid resistance are exhibited.

  Hereinafter, an example of an embodiment of the present invention will be described with reference to the drawings.

  1 to 4 show an embodiment (Embodiment 1) of the present invention. FIG. 1 is an explanatory diagram schematically showing the overall configuration of the separation device, FIG. 2 is an enlarged cross-sectional view schematically showing the configuration of the divider, and FIG. 3 is an enlarged cross-sectional view taken along line AA in FIG. FIG. 4 and FIG. 4 are explanatory views schematically showing the structure of the separation membrane in an enlarged manner.

  1 to 4, the separation apparatus of the present invention includes a distillation means 100 for separating a liquid mixture, and a membrane separation means 200 for separating a mixed vapor distilled from the top of the distillation means 100 by a membrane separation method. It is configured.

The distillation means 100 includes a distillation column 1 and a partial condenser 2 provided at the top of the distillation column 1. The diameter and length of the distillation column 1 are set appropriately. Although the distillation column 1 of Embodiment 1 is formed in a cylindrical shape, it may be formed in a rectangular tube shape or the like.
The distillation column 1 is filled with a packing 10 to ensure a large gas-liquid contact area. The filling 10 is not particularly limited as long as the vapor of the liquid mixture can be circulated, and any generally used one can be selected and employed. For example, a ceramic tube, a glass bulb, a stainless steel coil pack, a single turn, a McMahon, a helipack, a sulzer packing, and the like can be given. However, the present invention is not limited to the above, and it is of course possible to use a separately developed one.

The partial condenser 2 separates again the mixed steam introduced after being separated in the distillation column 1 from the boiling point difference. As shown in detail in FIG. 2, the partial reducer 2 according to Embodiment 1 is formed in a cylindrical shape, and includes a heat exchange chamber 20 provided with a steam inlet 21 and a distillation outlet 22 facing each other on the side, And a coil tube 23 (pipe coil) for heat exchange provided in the chamber 20.
The size of the heat exchange chamber 20 of the partial condenser 2 is appropriately determined according to the size of the distillation column 1 and the like. The heat exchange chamber 20 of Embodiment 1 is formed in a cylindrical shape with both ends (left and right ends in FIGS. 1 and 2) closed. Both ends of the coil tube 23 are kept airtight and project outside the heat exchange chamber 20, and an inlet 23a for a heat exchange medium (working fluid) is formed at one end and an outlet 23b is formed at the other end. The heat exchange medium is supplied from the inlet 23a, circulates through the coil tube 23, and flows out from the outlet 23b. The partial condenser 2 is provided in such a manner that the inlet 21 communicates with the top opening 10a (see FIG. 2) of the distillation column 1 and is connected to the top of the column 1 while maintaining airtightness.

The distillation means 100 of Embodiment 1 includes a storage tank 11 that stores a liquid mixture 81, and the storage tank 11 is connected to an intermediate portion of the distillation tower 1 through a pipe line 11a. A pump 12 and a preheater 13 are disposed in the pipe line 11a, and the liquid mixture in the storage tank 11 is continuously or intermittently sent to the appropriate amount by the pump 12, and is heated by the heater 13 to be distilled. 1 is supplied.
A circulation pipe 14 is provided on the bottom side of the distillation column 1, and a heating unit 15 (boiler, heater, etc.) is provided in the pipe 14. The liquid mixture 81 supplied into the distillation column 1 passes through the pipe line 14 and is vaporized by being heated by the heating unit 15, and the vaporized mixed vapor passes through the pipe line 14 from an appropriate portion at the bottom of the column to enter the column 1. Introduced continuously.

  Further, the distillation means 100 of the first embodiment includes a discharge pipe 16 at the bottom of the distillation column 1, and the discharge pipe 16 is provided with an open / close valve 17. The discharge pipe 16 is provided to open the valve 17 and discharge the liquid in the distillation column 1 when necessary. In this case, the valve 17 may be opened / closed and the pump 12 may be turned on / off in association with each other. Further, the valve 17 can be opened and closed by detecting the liquid level of the liquid mixture at the bottom of the column and turning it on and off.

As the heat exchange medium, water (water temperature, for example, about 5 ° C. to about 35 ° C.) such as tap water or well water, hot water at a desired temperature (for example, about 35 ° C. to about 50 ° C.), or the like can be used. When water is used as the medium, tap water may be used as it is, but a cooling tower, a cooler or the like (not shown) may be provided to circulate and use the water. When hot water is used as the medium, for example, a heater (not shown) is installed in the medium line, and hot water heated to a desired temperature (for example, 35 ° C. to 50 ° C.) is supplied to the coil tube and circulated. It can be constituted as follows. Further, the temperature of the coil tube 23 and the atmospheric temperature in the chamber 20 are adjusted or changed by the flow rate per unit time of the medium flowing in the coil tube 23, the number of turns of the coil tube, the coil diameter, the tube diameter, or the supply pressure. can do.
In the first embodiment, as described above, an example in which a coil type is used as the divider 2 is disclosed, but a shell and tube type divider or the like can also be employed.

  The membrane separation means 200 includes an arbitrary number (one or more) of separation membrane modules, a heating means 4, a vacuum pump 5, a concentrated vapor condenser 6, and the like. Embodiment 1 discloses an example in which first to fourth four separation membrane modules 3a to 3d are arranged side by side. In this case, the number of the membrane modules can be arbitrarily increased or decreased.

  Each of the first to fourth membrane modules 3 a to 3 d includes a vapor separation processing chamber 31 and a separation membrane 32 provided in the processing chamber 31. The processing chamber 31 of the first embodiment is a cylinder having an appropriate diameter and length that has one end (lower end in FIG. 1) closed and a permeate vapor chamber 33 (steam outlet) at the other end (upper end in FIG. 1). Tube). The diameter and length of the processing chamber 31 are determined according to the size and the like (diameter and length) of the separation membrane. Each processing chamber 31 includes a steam inlet 34 on one end side (lower end side in FIG. 1) and a steam outlet 35 on the other end side (upper end side in FIG. 1).

  The steam inlet 34 of the processing chamber 31 of the first membrane module 3a is connected to the outlet 22 of the partial condenser 2 by a pipe line 36a. The processing chambers 31 of the first and second membrane modules 3a and 3b, the second and third membrane modules 3b and 3c, and the third and fourth membrane modules 3c and 3d are located on the front side. The steam outlet 35 of the processing chamber 31 and the steam inlet 34 of the processing chamber 31 located on the rear side are connected by pipes 36b, 36c, and 36d, respectively. The steam outlet 35 of the processing chamber 31 of the fourth membrane module 36 d is connected to a concentrate recovery tank 62 by a pipe 61. The concentrated vapor condenser 6 is provided in the pipe 61.

  In the first embodiment, the opening / closing valve 26 is provided at an appropriate portion of the pipe line 36a. Further, a branch pipe 27 is provided between the valve 26 and the outlet 22 of the pipe 36a and connected to the pipe 36a. The branch pipe 27 is provided with an opening / closing valve 28.

  In the first to fourth membrane modules 3a to 3d of the first embodiment, a drain 38 having an opening / closing valve 37 is provided at the bottom (lower end in FIG. 1) of each processing chamber 31. In the first embodiment, an outer peripheral surface of the pipe line 36a is covered with a pipe line 36a that connects the distillation outlet 22 of the partial condenser 2 and the steam inlet 34 of the processing chamber 31 of the first membrane module 3a. The ribbon heater 39 provided is provided. Further, a temperature sensor 24 is provided which is positioned in the vicinity of the distillation outlet 22 in the pipe 36a and measures the tower top temperature (temperature of the distillation outlet 22 portion). The sensor 24 is electrically connected to a control unit 25 having a temperature indicator or the like. The pipes 36a to 36d are preferably provided with heat insulation properties by covering the outer peripheral surface with a heat insulating material or the like. In the above case, instead of the ribbon heater 39, the pipe line 36a is formed of a double pipe, and a heat medium is circulated through the gap between the inner pipe and the outer pipe to heat the inner pipe. It can also be adopted.

  The separation membrane 32 is formed by synthesizing (depositing) a separation membrane on the surface of a porous support. Examples of the porous support include porous materials made of ceramics such as alumina, zirconia, silicon nitride and silicon carbide, metals such as stainless steel, nickel and aluminum, and organic polymers such as polyethylene, polysulfone and polyimide. , Those having an average pore diameter of about 0.05 to 10 μm and a porosity of about 10 to 60% can be used. Separation membranes are classified into hydrophilic membranes and hydrophobic membranes. Examples of the hydrophilic membrane include PVA (polyvinyl alcohol), chitosan, zeolite, and the like. Examples of the zeolite used as the separation membrane include A type, T type, X type, and Y type. Moreover, as a hydrophobic film | membrane, a silicon system etc. are mentioned, for example. In this invention, it can select arbitrarily from what was illustrated above and can employ | adopt. In addition, the said material was mentioned as an example and does not limit the use material of this invention.

  As shown in detail in FIG. 4, the separation membrane 32 of Embodiment 1 synthesizes (deposits) a zeolite membrane 32b (separation membrane) on the outer surface of a tubular porous support 32a and seals one end. It is formed of a tubular zeolite membrane that is stopped (not shown) and has the other end 32c. The separation membrane 32 is connected to the permeate vapor chamber 33 (steam outlet) while maintaining airtightness at the open end, and is disposed in each processing chamber 31. As a result, the inside of the processing chamber 31 and the vapor outlet 33 are separated by the separation membrane.

  Although the dimension of the porous support body 32a is not specifically limited, For example, the range of about 5-100 mm in outer diameter, about 0.2-2 mm in thickness, and about 100-2000 mm in length can be mentioned. Moreover, as a film thickness of a zeolite membrane, the range of about 10-50 micrometers can be mentioned, for example (however, it does not limit to the said range).

  The permeate vapor chambers 33 of the membrane modules 3 a to 3 d are connected to the vacuum pump 5 by pipe lines 51. A permeate vapor condenser 52 and a permeate recovery container 53 are interposed in the pipe line 51. The vapor discharged from the permeated vapor chamber 33 is condensed and liquefied by the condenser 52 and collected in the container 53. In this case, the condenser 52 and the container 53 can be configured by a trap in which both are combined.

  The pump 5 depressurizes the inside of each separation membrane 32 and the permeate vapor chamber 33 at an appropriate vacuum degree. The degree of vacuum to be reduced is not particularly limited, and examples thereof include a degree of vacuum of 13.0 to 5000 Pa, preferably about 130 to 2600 Pa (1 to 20 mmHg).

  The heating means 4 heats the inside of each of the vapor separation processing chambers 31 of the first to fourth membrane modules to a desired temperature. The heating means 4 of the first embodiment forms and surrounds each processing chamber 31 with an appropriate space 41 (see FIG. 3) between the outer peripheral surface of the processing chamber 31 and maintains airtightness. A heating chamber 40 for heat exchange is provided. Each heating chamber 40 includes a heating medium (heating medium) inlet 42 on one end side (lower end side in FIG. 1) and a heating medium outlet 43 on the other end side (upper end side in FIG. 1). As the heat medium, for example, oil or the like can be employed.

  The heating medium inlet 42 of the heating chamber 40 of the first membrane module 3a is connected to the heating medium outlet 43 of the heating chamber 40 of the fourth membrane module 3d by a pipe 44. The heating chambers 40 of the first and second membrane modules 3a and 3b and the second and third membrane modules 3b and 3c are arranged on the rear side with the heat medium outlet 43 of the heating chamber 40 located on the front side. The heating medium inlet 42 of the heating chamber 40 located is connected by pipe lines 45a, 45b, and 45c, respectively. A heating unit 46 (heating kettle, heater, etc.) and a feed pump 47 are provided in the pipe 44. Thereby, a heat medium is comprised so that it may circulate through each heating chamber 40 (space part 41).

  In Embodiment 1, oil is adopted as the heat medium. However, it is not limited to oil. The temperature of the heating medium is appropriately determined according to the type of the liquid mixture to be separated, and can be, for example, about 80 ° C to 160 ° C, preferably about 100 ° C to 140 ° C.

  The separation apparatus according to Embodiment 1 has the above-described configuration. Next, an example of a method of using the liquid mixture 81 to be separated as an aqueous ethanol solution and its effects will be described. The open / close valve 17 of the distillation column 1, the open / close valve 28 of the branch pipe 27, and the open / close valve 37 of each membrane module are closed. The preheater 13, the ribbon heater 39, the heating units 15 and 46, the vacuum pump 5 and the feed pump 47 are turned on. Further, a refrigerant (tap water or the like) having a desired temperature is continuously supplied to the coil tube 23 of the divider 2 at a desired flow rate so as to be circulated. In this state, the pump 12 is operated to supply an appropriate amount of the aqueous ethanol solution 81 in the storage tank 11 into the distillation column 1. After supplying a predetermined amount of the aqueous ethanol solution, the pump 12 is stopped. The aqueous ethanol solution sent from the storage tank is heated by the pre-heater 13 and supplied into the distillation tower. A part of the aqueous solution is vaporized by the heating, and this vapor rises in the tower 1, but most of the aqueous solution 81 a is at the bottom of the tower. To flow down. The opening / closing valve 26 of the pipe line 36a is opened.

The aqueous solution flowing down to the bottom of the column passes through the pipe line 14 and is heated and vaporized by the heating unit 15, and this vapor (mixed vapor) is sequentially supplied into the distillation column 1 through the pipe line 14 while contacting the packing 10. Ascend in tower 1. In this ascending process, the mixed steam is heat-exchanged by contact with the packing, and in the mixed steam, the component having a high boiling point (aqueous component) is liquefied and adheres to the packing, circulates to the bottom of the column, and the component having a low boiling point ( The ethanol component is not liquefied but rises as it is and is sequentially introduced into the partial condenser 2. The liquid recirculated to the bottom of the column is heated by the heating unit 15 to be vaporized again, supplied into the column, and separated into a gas phase and a liquid phase in the same way as described above in the column.
As described above, while the mixed steam is rising in the distillation tower 1, the high boiling point component is liquefied and flows down in the middle of the tower and circulates to the bottom of the tower, whereby the mixed steam is a component in the distillation tower 1. Separation processing (primary processing) is performed.

On the other hand, the steam (primarily treated mixed steam) introduced into the heat exchange chamber 20 of the partial condenser 2 without being liquefied in the distillation column is heat-exchanged by contact with the coil tube 23, and the high steam in the steam is Boiling components (water-based components) are condensed (liquefied) and circulated into the distillation column 1, and low-boiling components (ethanol-based components) are not liquefied and rise while maintaining a gas (vapor) state. After passing through the inside 20, it is distilled out of the outlet from the outlet, and is supplied into the steam separation processing chamber 31 from the steam inlet 34 of the first membrane module 3 a through the pipe 36 a.
As described above, the mixed vapor separated in the distillation column 1 (primary treatment) is finely separated again in the partial condenser 2 (secondary treatment), so that the liquid mixture (ethanol aqueous solution) has a high concentration. Distilled steam concentrated in

Distilled steam that flows out of the outlet from the outlet 22 of the partial condenser 2 is heated by the ribbon heater 39 and passes through the conduit 36a from the steam inlet 34 of the processing chamber 31 of the first membrane module 3a. Introduced continuously. The introduced steam is heated by the heat medium in the heating chamber 40 and the inside of the separation membrane 32 (tubular zeolite membrane) is depressurized with an appropriate degree of vacuum. The hydrophilic component (mainly water component) selectively permeates from the outside to the inside of the separation membrane 32 (zeolite membrane).
The permeate vapor flows inside the separation membrane 32, is discharged from the permeate vapor chamber 33 (steam outlet), is sucked by the vacuum pump through the pipe 51, is condensed by the permeate vapor condenser 52, and is transferred to the permeate recovery container 53. To be recovered.

  As described above, the mixed vapor introduced into the processing chamber 31 of the first membrane module 3a is dehydrated by the separation membrane 32, and ethanol, which is a hydrophobic component, does not pass through the separation membrane, so that the mixed vapor is concentrated. The mixed steam (primary concentrated steam) concentrated as described above is discharged from the steam outlet 35 of the processing chamber 31 to the outside of the chamber, and passes through the pipe 36b from the steam inlet 34 of the processing chamber 31 of the second membrane module 3b. 31 is introduced. Then, the hydrophilic component in the vapor selectively permeates through the separation membrane 32 in the chamber 31 in the same manner as described above, and this permeated vapor flows through the separation membrane 32 and is collected into the container 53 through the pipe 51. Is done.

  The mixed steam introduced into the processing chamber 31 of the second membrane module 3b as described above is dehydrated by the separation membrane and concentrated again, and this concentrated mixed steam (secondary concentrated steam) is stored in the processing chamber 31. The steam is discharged from the steam outlet 35 to the outside of the room, and is introduced into the chamber 31 from the steam inlet 34 of the processing chamber 31 of the third membrane module 3c through the conduit 36c. In the same manner as described above, the water is dehydrated by the separation membrane 32 and further concentrated, and the permeated vapor flows through the separation membrane 32 and is collected into the container 53 through the pipe 51, and the concentrated mixing. The steam (tertiary concentrated steam) is discharged from the steam outlet 35 of the processing chamber 31 to the outside, and is introduced into the chamber 31 from the steam inlet 34 of the processing chamber 31 of the fourth membrane module 3d through the conduit 36d.

  The tertiary concentrated vapor introduced into the processing chamber 31 of the fourth membrane module 3d is dehydrated by the separation membrane 32 in the chamber 31 and further concentrated and purified in the same manner as described above, and the permeated vapor passes through the pipe 51. It passes through and is collected in the container 53. The concentrated and refined steam (quaternary concentrated steam) is discharged outside from the steam outlet 35 of the processing chamber 31, passes through the pipeline 61, is condensed in the concentrated steam condenser 6, and is recovered in the recovery tank 62. Is done. The liquid recovered in the tank 62 becomes a solution (ethanol) concentrated and purified to a concentration equal to or higher than the azeotropic concentration (95.6% by weight) of the aqueous ethanol solution. For example, a product that can be used as it is as a bioethanol product Is obtained.

On the other hand, during the separation operation, the temperature measured by the temperature sensor 24 provided on the top of the partial condenser 2 (the temperature of the distillate distilled from the outlet 22 of the partial condenser 2) is a predetermined temperature or higher, for example, When the temperature reaches about 90 ° C., the heating unit 15 is turned off, the valve 26 of the pipe 36a is closed, and the valve 28 of the branch pipe 27 is opened to release to the atmosphere. Then, the valve 17 at the bottom of the tower is opened, and the aqueous solution (mostly water) in the tower 1 is discharged outside and recovered. When the water component in the mixed steam increases, the temperature of the steam increases in proportion to the mixing ratio of the water component in the steam. That is, when the mixing ratio of the ethanol component in the aqueous solution decreases, the mixing ratio of the water component in the steam increases accordingly.
Therefore, when the temperature reaches a predetermined temperature (for example, about 90 ° C.), as described above, the valve 17 is opened, the aqueous solution in the tower 1 is discharged, the valve 17 is closed after being discharged. Then, the pump 12 is operated to supply an appropriate amount of the aqueous ethanol solution in the storage tank 11 into the distillation column 1, and the separation operation is resumed in the same manner as described above. The aqueous solution discharged and recovered from the bottom of the tower may be reused, for example, by returning it to the storage tank 11.

  The drains 38 of the first to fourth membrane modules 3a... 3d open the valve 37 when necessary, such as when the operation of the separator is stopped, and discharge the residual liquid remaining in the processing chambers 31. For the rest, keep the rest closed. The discharged liquid may be reused.

  In addition, it can also comprise so that the ethanol aqueous solution in the storage tank 11 may be continuously supplied to the distillation tower 1 for an appropriate amount, and may be separated. In the case of adopting this configuration, for example, the ON / OFF operation mechanism of the pump 12 and the valve 17 are configured by electromagnetic valves, the opening / closing operation of the valve 17 based on the measured temperature of the temperature sensor 24 described above, and the ON / OFF of the pump 12. An OFF (drive, stop) operation may be configured to be automatically controlled by the control unit 25.

  Moreover, in the above-mentioned Embodiment 1, although the usage example which isolate | separates ethanol aqueous solution as a liquid mixture was demonstrated, a liquid mixture is not limited to this. The liquid mixture to be separated in the present invention includes a liquid mixture of water and alcohols such as methanol and propanol, a liquid mixture of water and ketones such as acetone and methyl ethyl ketone, and water and halogens such as carbon tetrachloride and trichloroethylene. Examples thereof include liquid mixtures with organic liquids such as chemical hydrocarbons. However, the liquid mixture to be separated is not limited to the above.

  Furthermore, in the first embodiment, the example in which the separation membrane module is disposed in the vertical orientation is disclosed. However, in the present invention, it is needless to say that the configuration in which the separation membrane module is disposed in the lateral orientation or the like can be employed.

  FIG. 5 is an explanatory view schematically showing a configuration of a main part of a separation apparatus according to another embodiment (Embodiment 2) of the present invention. In the separation device according to the second embodiment and each embodiment disclosed below, the same reference numerals are assigned to the same components as those already described in the first embodiment, and the description thereof is omitted. The separation apparatus according to the second embodiment is characterized by the structure on the bottom side of the distillation column 1.

  The distillation means 100 of the separation apparatus of the second embodiment includes a circulation pipe 70 instead of the discharge pipe 16 of the first embodiment on the bottom side of the distillation tower 1, and a pump 71 is interposed in the pipe 70. It is provided. A switching line 73 is connected to the upper side of the pump 71 of the line 70 via a switching valve 72 such as a three-way cock. The valve 72 is switched to the circulation side, and the liquid mixture (aqueous solution) in the tower bottom is circulated in the tower bottom by the pump 71 and mixed. Then, when necessary, that is, when the temperature measured by the temperature sensor 24 reaches a predetermined temperature, the valve 72 is switched to the switching pipe 73 side so that the aqueous solution in the bottom of the tower is discharged outside and recovered. It is configured. The recovered aqueous solution may be reused as described above. The switching operation of the valve 72 is performed manually or automatically. Other configurations are the same as those in the first embodiment.

  The separation device according to the second embodiment is configured as described above, and is used in the same manner as the separation device according to the first embodiment, and has the same effects as those of the first embodiment.

  FIG. 6 is an explanatory view schematically showing a configuration of a main part of a separation apparatus according to still another embodiment (Embodiment 3) of the present invention. The separation apparatus according to the third embodiment is characterized by the configuration of the mounting arrangement posture of the partial condenser 2 with respect to the distillation column 1.

  The partial condenser 2 of the distillation means 100 according to the third embodiment is formed in a cylindrical shape, provided with a steam inlet 21a at one end and a distillation outlet 22a at the other end, and a heat exchange chamber 20a in the chamber 20a. It is configured to include a coil tube 23 for heat exchange disposed and provided. The partial condenser 2 is provided in such a manner that the inlet 21a communicates with the top opening 10a of the distillation column 1 and is connected in series with the top of the column 1 while maintaining airtightness. Other configurations are the same as those in the first embodiment. Note that the configuration of the second embodiment may be adopted as the configuration on the bottom side of the distillation column 1.

  The separation device according to the third embodiment is configured as described above, and is used in the same manner as the separation device according to the first embodiment. Thus, the same effects as those of the first embodiment can be achieved.

  FIG. 7 shows a main part of a separation apparatus according to still another embodiment (Embodiment 4) of the present invention, and FIG. 7 (a) is an explanatory view schematically showing the configuration of the separation membrane module. FIG. 2B is an enlarged sectional view taken along line BB in FIG. The separation device of the fourth embodiment is characterized by the configuration of the separation membrane module.

  The separation membrane module 3A of the membrane separation means 200 of Embodiment 4 includes a vapor separation processing chamber 31A and a plurality (four in the figure) of separation membranes 32 provided in the processing chamber 31A. . The processing chamber 31A is a cylinder with an appropriate diameter and length that closes one end (lower end in FIG. 7A) and has a permeate vapor chamber 33 (steam outlet) at the other end (upper end in FIG. 7A). It is formed in a shape.

  The diameter and length of the processing chamber 31A are determined according to the number of separation membranes 32 provided in the chamber 31A. The number of separation membranes 32 provided in the processing chamber 31A is arbitrarily determined. Each separation membrane 32 has an opening connected to the permeate vapor chamber 33 (steam outlet) while maintaining airtightness, and is disposed in the processing chamber 31A. Thus, the processing chamber 31A and the permeate vapor chamber 33 are separated from each other by the separation membrane.

  One or a plurality of membrane modules 3A are provided. In the case of adopting a configuration in which one membrane module is provided, the steam inlet 34 of the processing chamber 31A is connected to the outlet 22 of the partial condenser 2 by a conduit 36a and the steam outlet 35 of the processing chamber 31A is connected to the conduit. 61 is connected to the concentrate recovery tank 62. In addition, the heat medium inlet 42 and the heat medium outlet 43 of the heating chamber 40 for heat exchange are connected by a pipe 44 and set.

  In the case of adopting a configuration in which a plurality of membrane modules 3A are provided, the steam inlet 34 of the processing chamber 31A of any one membrane module 3A is connected to the outlet 22 of the condenser 2 by a pipe 36a. In the other membrane module 3A, as in the first embodiment, the steam outlet 35 of the processing chamber 31A located on the front side and the steam inlet 34 of the processing chamber 31A located on the rear side are connected to the pipelines 36b, 36c, and 36d. And the steam outlet 43 of the processing chamber 31A located at the rearmost position is connected to the concentrated liquid recovery tank 62 through a pipe 61.

Further, a heat medium outlet 42 of the heating chamber 40 of the membrane module 3A in which the steam inlet 34 is connected to the distillation outlet 22 and a heat medium outlet 43 of the heating chamber 40 of the membrane module 3A located at the last position are connected by a pipe 44. To do. As in the first embodiment, the other membrane module 3A is provided with a heat medium outlet 43 of the heating chamber 40 of the processing chamber 31A located on the front side and a heat medium inlet 42 of the heating chamber 40 located on the rear side. They are connected and set by paths 45a, 45b and 45c, respectively. Other configurations are the same as those in the first embodiment.
Note that the configuration of the second embodiment may be adopted as the configuration on the bottom side of the distillation column 1. Further, as the partial condenser 2 of the distillation unit 100, the partial condenser 2 having the configuration of the third embodiment can be adopted.

  The separation device according to the fourth embodiment is configured as described above, and is used in the same manner as the separation device according to the first embodiment. Thus, the same effects as those of the first embodiment can be achieved. In addition, according to the separation apparatus of Embodiment 4, the efficiency of the membrane separation action by the membrane separation means 200 is further improved.

  FIG. 8 is an explanatory diagram schematically showing the overall configuration of a separation apparatus according to still another embodiment (Embodiment 5) of the present invention. Embodiment 5 shows an example in which the separation apparatus of the present invention is applied to an experimental apparatus.

  The distillation means 100 of the separation apparatus according to the fifth embodiment includes a kettle 80 having a desired capacity for containing a desired amount of the liquid mixture 81 and heating and evaporating it. The pot 80 is provided with a circulation line 82 on the bottom side, and a pump 83 and a pipe heater 84 are provided in the line 82 so that the liquid mixture 81 in the pot 80 is heated to a desired temperature and circulated. It is configured. The heating temperature of the liquid mixture 81 is adjusted by the voltage applied to the heater 84.

The pot 80 includes a thermometer 85 provided by being inserted into the pot 80, and is configured to be able to measure the temperature of the liquid mixture in the pot 80. The distillation column 1 of the fifth embodiment is configured such that the bottom of the column is opened, and the column bottom is detachably connected to the upper end port 80a of the kettle 80 while being detachably connected. Thus, the liquid mixture in the pot 80 is heated and evaporated, and the mixed vapor is supplied into the tower 1 and raised.
The distillation column 1, the fractionator 2, the kettle 80, the vapor separation processing chamber 31 of the membrane module 3a ... 3d, the heating chamber 40 for heat exchange of the heating means 4 and the respective pipes of the fifth embodiment are made of heat-resistant glass or the like. Manufactured from glass. Other configurations are the same as those in the first embodiment. In the fifth embodiment, some symbols are omitted.

  The separation apparatus according to the fifth embodiment is configured as described above, and circulates the liquid mixture 81 in the kettle 80 while heating and evaporates the kettle 80 to separate components. As a result, the same effects as those of the first embodiment are exhibited. In the fifth embodiment, it is needless to say that a configuration such as employing a flask or the like and heating with a mantle heater or other heater instead of the kettle 80 can be used.

  Note that the separation device of each of the above embodiments is disclosed as an example, and the present invention is not limited to the above embodiment, and does not depart from the technical idea described in the claims. It can be changed arbitrarily.

  Next, an example of an experiment performed using the separation apparatus according to Embodiment 5 of the present invention will be described. In the experimental example, an ethanol 5 wt% (wt%) aqueous solution was used as a raw material (liquid mixture), and the present invention and the comparative example were compared and two types of experiments (experimental example 1 and experimental example 2) were performed. Experimental Example 1 was conducted using only distillation means, and Experimental Example 2 was conducted using a combination of distillation means and membrane separation means. In Experimental Example 1, the distillation means and the membrane separation means are separated, one end of the pipe line is connected to the distillation outlet 22, and a recovery container (none of which is shown) is connected to the other end of the pipe, and the distillate is distilled from the distillation outlet. The distillate vapor to be condensed was condensed by a condenser (not shown) interposed in the pipe line and collected in the container, and the recovered liquid was measured. The pipe is provided with an open / close cock (not shown) located near the outlet. In Experimental Example 2, the recovered liquid collected in the concentrated liquid recovery tank 62 was measured using the separation apparatus according to the fifth embodiment of the present invention in which the distillation means and the membrane separation means were combined.

(Experimental example 1)
First, Experimental Example 1 will be described.
(Experimental equipment: distillation equipment)
Distillation tower: outer diameter 70 mmφ × height 700 mm. Filled inside.
Reducer: outer diameter 50 mmφ × length 150 mm.
Kettle capacity: 10L.
(Measuring method)
The raw material (ethanol 5 wt% aqueous solution) is stored in a kettle with 8000 g (pure content 400 g), the pipe heater voltage is set to 170 V, the raw material is heated while circulating with a pump and evaporated in the kettle. To do. Tap water (20 ° C) is used as a refrigerant for heat exchange of the condenser, the inlet of the coil pipe is connected to a tap, the flow rate of tap water is appropriately adjusted, and the coil pipe is supplied continuously. Circulate.
After the elapse of a predetermined time (1 hour) from the heating of the raw material, the cock is opened, the distilled vapor is discharged from the distillation outlet and recovered, and the concentration (ethanol purity) and recovery rate of the recovered liquid are measured. Table 1 shows. The difference between the comparative example and the present invention is only the presence or absence of supply of a heat exchange medium (tap water) (in the comparative example, no water is supplied). In addition, the said collection | recovery container was replaced | exchanged for another container for every measurement, and the said measurement was performed using the collection | recovery liquid in the replaced container.

  From the results in Table 1, it was confirmed that according to the present invention, the ethanol purity was much higher than that of the comparative example. Regarding the ethanol recovery rate, the comparative example is higher at the beginning of the measurement, but the present invention is dominant from the latter half. Although not shown in Table 1, it was confirmed that the measured values of all the collected liquids according to the present invention at a processing time of 60 minutes were an ethanol purity of 86.0 wt% and a recovery rate of 95%.

(Experimental example 2)
Next, Experimental Example 2 will be described.
(Experimental device ... Membrane separation device)
The separation membrane module uses a tubular zeolite membrane (Zeolite 4A manufactured by Mitsui Engineering & Shipbuilding) with an outer diameter of 12 mmφ and a length of 400 mm. Oil is used as the heating medium. The distillation apparatus is the same as Experimental Example 1.
(Measuring method)
The degree of vacuum by the vacuum pump was adjusted to 3 mmHg (400 Pa), and the temperature of the heating medium was adjusted to 105 ° C. Distillation of the raw material is carried out under the same conditions as in Experimental Example 1. Distilled vapor distilled from the distillation outlet is supplied to the first membrane module and heated in the processing chamber for membrane separation. The permeate vapor is collected in the permeate collection container, and the vapor that does not pass through the separation membrane (concentrated vapor) is discharged from the vapor outlet of the fourth membrane module and collected in the concentrate collection tank. The concentration (ethanol purity) and recovery rate of this recovered liquid were measured, and the measurement results are shown in Table 2. The difference between the comparative example and the present invention is only the presence or absence of supply of a heat exchange medium (tap water) as in Experimental Example 1. The tower top temperature (temperature of the distilled steam near the distillation outlet) was also measured (only the present invention).

  As is apparent from the results in Table 2, according to the present invention, ethanol purified to a concentration (99.5 wt%) higher than the azeotropic concentration (95.6 wt%) was obtained. On the other hand, in the comparative example, the azeotropic concentration was not reached. The ethanol recovery rate was inferior to that of the comparative example at the beginning of the experiment as in Experimental Example 1, but it was also confirmed that it became dominant from the latter half.

  As described above, according to the present invention, the separation performance and the separation efficiency can be greatly improved as compared with the comparative example. This fact was unexpected.

1 is a system diagram showing an overall configuration of a separation apparatus according to an embodiment of the present invention. It is sectional drawing which expands the part of a voltage divider and shows the structure roughly. It is an AA line expanded sectional view of FIG. It is explanatory drawing which expands a separation membrane and shows the structure roughly. It is explanatory drawing which shows roughly the structure of the principal part of the separation apparatus of other embodiment of this invention. It is explanatory drawing which shows schematically the structure of the principal part of the separation apparatus of further another embodiment of this invention. The principal part of the separation apparatus of further another embodiment of this invention is shown, Comprising: The figure (a) is explanatory drawing which shows the structure of a separation membrane module roughly, The figure (b) is the figure (a). It is a BB line expanded sectional view of). It is explanatory drawing which shows roughly the structure of an example which applied the separation apparatus of this invention to the apparatus for experiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Distillation tower 2 Condenser 3a ... 3d Handle 10 for rotation operation Packing material 31 Steam separation processing chamber 32 Separation membrane

Claims (3)

A separation apparatus comprising a distillation means for separating a liquid mixture, and a membrane separation means for separating a mixed vapor distilled from the top of the distillation means by a membrane separation method,
The distillation means includes a distillation column filled with a packing, and a partial condenser provided at the top of the distillation column,
The membrane separation means comprises a vapor separation treatment chamber and a separation membrane module having a separation membrane provided in the treatment chamber, and a heating means for heating the treatment chamber,
A separation apparatus combining distillation and membrane separation, configured to supply mixed steam distilled through the partial condenser to the membrane module and heat in the processing chamber to perform membrane separation.   The separation apparatus according to claim 1, wherein the membrane separation means includes a plurality of the membrane modules.   The separation apparatus combining distillation and membrane separation according to claim 1 or 2, wherein the separation membrane of the membrane module is composed of a zeolite membrane.

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