JP2015160182A - Sublimation refining apparatus and sublimation refining method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the discharge of a valuable specimen to the outside of a system.SOLUTION: A sublimation refining apparatus 1 condensing a sublimed substance 14 to be treated includes: a discharge amount measurement means 12 detecting the substance 14 to be treated being discharged to the subsequent stage of a sublimation purification tube 2 from the sublimation purification tube 2; and an inert gas introduction amount adjustment means 6 introducing the inert gas to the sublimation purification tube 2 of the front stage of the sublimation purification tube 2. The inert gas is introduced when detecting the discharge of the substance 14 to be treated and the substance 14 to be treated is not discharged from the sublimation purification tube 2 by lowering the temperatures of heating means 4a, 4b, 4c and 4d.

Description

  The present invention relates to a sublimation purification apparatus and a sublimation purification method for purifying and separating a substance to be treated using a difference in sublimation temperature from a mixture containing a sublimable organic compound as a substance to be treated.

As a conventional sublimation purification apparatus, there is known a sublimation purification apparatus that performs sublimation purification by sublimating an organic compound powder and then condensing it inside a sublimation purification tube (see, for example, Patent Document 1).
Hereinafter, the sublimation purification apparatus will be described with reference to FIG.

  As shown in FIG. 3, the sublimation purification apparatus 101 includes a sublimation purification pipe 102, a sublimation purification pipe (inner pipe) 102a, a decompression means 103, a heating means 104a, a heating means 104b, a heating means 104c, a flange 105a, and a flange 105b.

The sublimation purification tube 102 has a cylindrical shape having openings at one or more locations in the longitudinal direction. The sublimation purification tube (inner tube) 102 a has a cylindrical shape having openings at one or more locations in the longitudinal direction, and one or more sublimation purification tubes 102 are installed in the sublimation purification tube 102. The heating means 104a, the heating means 104b, and the heating means 104c have a donut shape having an opening at the center, and continuously cover the outer periphery of the sublimation purification tube 102 in the circumferential direction, and are in close contact with the sublimation purification tube 102 Are arranged to be.
A flange 105 a and a flange 105 b are fixed to one or more openings in the longitudinal direction of the sublimation purification pipe 102, and the flange 105 b includes an outlet 106. Although piping in the middle is omitted, the outlet 106 of the flange 105 b is connected to the decompression means 103. A to-be-treated substance heating container 107 is installed inside the sublimation purification tube 102, and the to-be-treated substance heating container 107 is filled with the to-be-treated substance 108.

  The heating means 104a, the heating means 104b, and the heating means 104c each include a heating wire 109. When the pressure inside the sublimation purification tube 102 and the sublimation purification tube (inner tube) 102a is reduced by the pressure reduction means 103, the heating wire 104 of the heating means 104a is energized and the temperature of the heating means 104a is heated above the sublimation temperature of the substance 108 to be treated. Since the target substance heating container 107 is heated, the target substance 108 is sublimated.

  At this time, the sublimation temperature depends on the degree of decompression, and the greater the degree of decompression, the lower the sublimation temperature. In addition, based on the idea of the degree of decompression and the mean free path in the sublimated material, the greater the degree of decompression, the less the sublimated material is impeded by movement, so other sublimated materials The distance traveled without collision (mean free path) becomes longer. On the other hand, if the degree of decompression is small, the mean free path is shortened because it easily collides with other sublimated materials.

  In the heating unit 104 c, the heating unit 104 c is heated at a temperature slightly lower than the sublimation temperature of the target material 108. As a result, the inner wall surface temperature of the sublimation purification tube (inner tube) 102a is heated at a temperature lower than the sublimation temperature of the material 108 to be treated.

  The to-be-treated substance 108 sublimated in the to-be-treated substance heating container 107 diffuses in the sublimation purification pipe (inner pipe) 102a, and the temperature of the inner wall surface of the sublimation purification pipe (inner pipe) 102a condenses the to-be-treated substance 108. If it contacts the inner wall surface of the sublimation purification tube (inner tube) 102a at a place where it should be, for example, a temperature lower than the sublimation temperature, that is, the condensation temperature, it condenses, but if it does not contact, it is discharged as it is.

  In this conventional sublimation purification apparatus, as shown above, the inner wall surface of the sublimation purification pipe (inner pipe) 102a inside the heating means 104c is lower than the sublimation temperature of the substance to be treated 108, so that it is condensed. The components can be recovered as sublimation purified material 110.

  In general, since organic compounds are vulnerable to heat, the degree of reduced pressure is increased to lower the sublimation temperature, thereby suppressing the heat applied to the organic compounds. Therefore, the mean free path is long.

JP 2007-246424 A

  In such a conventional sublimation purification apparatus, there has been a problem that the substance to be treated is discharged out of the sublimation purification tube due to incompatibility of temperature setting during sublimation purification of an expensive and small amount of unknown sample or newly developed sample.

  The present invention solves the above-described conventional problems, and an object of the present invention is to provide a sublimation purification apparatus that suppresses the discharge of a substance to be treated.

  In order to achieve this object, the present invention comprises a sublimation purification tube having at least one opening, a heating unit for heating the sublimation purification tube to the sublimation purification tube, and a decompression unit for reducing the pressure inside. A sublimation purification tube is provided with a target substance heating container filled with a target substance, and the sublimation purification pipe and the target substance heating container are heated by the heating means, whereby the submerged purification pipe is heated in the target substance heating container. A sublimation purification apparatus that sublimates a substance to be treated and condenses the sublimated substance to be treated on the sublimation purification pipe, and detects the substance to be treated discharged from the sublimation purification pipe downstream of the sublimation purification pipe. And an inert gas introduction amount adjusting means for introducing an inert gas into the sublimation purification pipe before the sublimation purification pipe, and introducing the inert gas when the discharge of the substance to be treated is detected. , By lowering the temperature of the heating means, by a sublimation purification apparatus from the sublimation purification tube so as not to discharge the substance to be treated, it is to achieve the intended purpose.

According to the present invention, the sublimation purification apparatus includes a sublimation purification tube having at least one opening, a heating unit for heating the sublimation purification tube to the sublimation purification tube, and a pressure reduction unit for reducing the pressure inside.
A sublimation purification tube is provided with a target substance heating container filled with a target substance, and the sublimation purification pipe and the target substance heating container are heated by the heating means, whereby the submerged purification pipe is heated in the target substance heating container. A sublimation purification apparatus that sublimates a substance to be treated and condenses the sublimated substance to be treated on the sublimation purification pipe, and detects the substance to be treated discharged from the sublimation purification pipe downstream of the sublimation purification pipe. And an inert gas introduction amount adjusting means for introducing an inert gas into the sublimation purification pipe before the sublimation purification pipe, and introducing the inert gas when the discharge of the substance to be treated is detected. The sublimation purification apparatus prevents the treated substance from being discharged from the sublimation purification tube by lowering the temperature of the heating means, thereby preventing an expensive and small amount of the treated substance from being discharged. It is possible to obtain.

Schematic sectional view of the sublimation purification apparatus of Embodiment 1 of the present invention The figure which shows the signal processing of the control means of Embodiment 1 of this invention Schematic sectional view of a conventional sublimation purification device

  The sublimation purification apparatus according to claim 1 of the present invention includes a sublimation purification tube having at least one opening, a heating unit for heating the sublimation purification tube, and a decompression unit for reducing the pressure inside the sublimation purification tube. An inside of the purification tube is provided with a to-be-treated substance heating container filled with the to-be-treated substance, and the sublimation purification pipe and the to-be-treated substance heating container are heated by the heating means, whereby the to-be-treated substance in the to-be-treated substance heating container is heated. A sublimation purification apparatus for sublimating a processing substance and condensing the sublimated purification target substance on the sublimation purification pipe, wherein a discharge amount for detecting the treatment substance discharged from the sublimation purification pipe at a subsequent stage of the sublimation purification pipe A measuring means and an inert gas introduction amount adjusting means for introducing an inert gas into the sublimation purification pipe before the sublimation purification pipe, and introducing the inert gas when the discharge of the substance to be treated is detected; Previous By lowering the temperature of the heating means, in which from the sublimation purification tube so as not to discharge the substance to be treated.

  As a result, when an expensive and small amount of material to be treated is discharged out of the sublimation purification tube, the amount of discharge is detected, an inert gas is introduced according to the amount of discharge, and the degree of decompression is reduced. The sublimation is suppressed, the average free path of the sublimated material is shortened and held in the sublimation purification tube, and the temperature of the heating means is lowered to adhere to the inner wall surface. There is an effect that it can be suppressed.

  Further, the sublimation purification method according to claim 2 is a sublimation purification method in which a material to be treated is sublimated by heating inside the sublimation purification tube, and the sublimated purification material is condensed. Discharge amount measuring means for detecting discharged substance to be processed and inert gas introduction amount adjusting means for introducing inert gas into the sublimation purification pipe are provided, and when the discharge of the to-be-treated substance is detected, the inert gas Is introduced, and the temperature of the heating means is lowered.

  As a result, when an expensive and small amount of material to be treated is discharged out of the sublimation purification tube, the amount of discharge is detected, an inert gas is introduced according to the amount of discharge, and the degree of decompression is reduced. The sublimation is suppressed, the average free path of the sublimated material is shortened and held in the tube, and the temperature of the heating means is lowered, and it adheres to the inner wall surface and is discharged out of the sublimation purification tube. There is an effect that can be suppressed.

  Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1)
FIG. 1 shows a schematic cross-sectional view of the sublimation purification apparatus of the first embodiment.

  The components of the sublimation purification apparatus 1 are shown below.

  A cylindrical sublimation purification tube 2 having openings at the ends is also provided inside a cylindrical sublimation purification tube outer tube 3 having openings at both ends.

  Heating means 4 a, 4 b, 4 c, 4 d are provided outside the sublimation purification outer tube 3.

  The heating means 4a, 4b, 4c and 4d are heaters using heating wires such as nichrome wires as heating elements.

  The piping member 18 is joined to the rear stage of the sublimation purification outer pipe 3 in an airtight state by the flange portion 9, the O-ring 10 and the clamp 11, and communicates therewith.

  The piping member 18 is joined to the decompression means 5 in an airtight manner through a piping that is omitted midway.

  The discharge amount measuring means 12 is provided in the piping member 18 through a flange portion so as not to disturb the airtightness.

  A substance heating container 8 is provided inside the sublimation purification tube 2.

  The inert gas introduction pipe 7 in the previous stage of the sublimation purification pipe outer pipe 3 is connected to the inert gas introduction amount adjusting means 6, and the inert gas is supplied from the gas cylinder 13. An inert gas can be supplied while maintaining an internal airtight state.

  A control unit 16 is electrically connected to the discharge amount measuring means 12, the inert gas introduction amount adjusting means 6, and the heating means 4a, 4b, 4c, 4d. The control unit 16 is a threshold value input means as a numeric keypad. And a threshold value storage means which is an internal memory and a determination means which is a signal processing device.

  The substance to be treated heating container 8 is filled with a substance to be treated 14. The to-be-processed substance 14 is an organic pigment | dye used for organic EL, such as tris (8- quinolinolato) aluminum, and organic semiconductors, such as a pentacene.

  The sublimation purification tube 2 and the sublimation purification tube outer tube 3 can withstand the heating of the heating means 4a, 4b, 4c, and 4d, and are inert to the sublimation purification material 15, such as noble metals, fluorine, and polyimide. A resin such as alumina, a ceramic such as alumina, or a glass such as quartz is used.

  Nitrogen or argon is used as the inert gas in the gas cylinder 13.

  As the discharge amount measuring means 12, a film thickness meter using a crystal resonator, a means using a spectroscopic method using a light emitting means such as a laser, a means using mass spectrometry, or the like is used.

  In the above configuration, the pressure reducing means 5 depressurizes the sublimation purification pipe 2, the sublimation purification pipe outer pipe 3, and the piping member 18, and energizes the heating wire of the heating means 4a to sublimate the temperature of the heating means 4a. When heated to a temperature higher than the temperature, the material heating container 8 is heated, so that the material to be processed 14 is sublimated.

  The substance to be treated 14 sublimated in the substance to be treated heating container 8 diffuses inside the sublimation purification pipe 2 and the sublimation purification pipe outer pipe 3. Since the region of the sublimation purification tube 2 heated by the heating means 4a is higher than the sublimation temperature of the substance 14 to be treated, it continues to contact, reflect and diffuse without condensing.

  The scattered material to be treated 14 condenses when it comes into contact with a place where the material to be treated 14 is to condense, for example, a region heated to a sublimation temperature or a condensing temperature by the heating means 4d.

  However, when the material properties of the substance 14 to be treated are not known, such as a new sample, and the heating means 4b, 4c, and 4d are not appropriately set to the sublimation temperature at which the heating means 4b, 4c, and 4d condense, that is, the condensation temperature is not set. Without condensing, it is discharged out of the sublimation purification pipe 2 and detected as the discharged substance 17 by the discharge amount measuring means 12.

  The known value is determined by the control unit 16, and when the threshold value is exceeded, the inert gas is introduced through the inert gas introduction amount adjusting means 6, and the heating means 4a, 4b, 4c, 4d Reduce temperature.

  By introducing the active gas, by increasing the pressure inside the sublimation purification pipe 2 and the sublimation purification pipe outer pipe 3, the sublimation of the substance to be treated 14 is suppressed, and the average free path of the sublimated substance 14 to be treated is reduced. By shortening, the probability that the to-be-processed substance 14 will contact, reflect, and refract an inert gas molecule etc. will raise the probability of contacting the sublimation purification pipe | tube 2, and will suppress discharge | emission amount. In addition, the to-be-processed substance 14 condenses to the sublimation purification pipe | tube 2 by reducing the temperature of heating means 4a, 4b, 4c, 4d.

  The operation of the control unit 16 will be described with reference to FIG. The control unit 16 is provided with threshold value setting means, threshold value storage means, discharge amount change calculation means, and determination means. The control unit 16 calculates the discharge amount change based on the signal from the discharge amount measuring means 12. Since the threshold value set before operating the sublimation purification apparatus 1 is stored in the threshold value storage means, the determination means compares the threshold value with the discharge amount change. Based on the determination result, the inert gas introduction amount adjusting means 6 and the heating means 4a, 4b, 4c and 4d are operated.

  If the heating means 4b, 4c, and 4d are appropriately set for the material 14 to be treated, the components condensed in the sublimation purification tube 2 can be recovered as the sublimation purification material 15.

  After the production, when the sublimation purification material 15 is collected, the sublimation purification material 15 condensed in the sublimation purification tube 2 is scraped off and collected.

  The heating means 4b, 4c, and 4d are not appropriately set for the substance 14 to be treated, and the sublimation purification tube suppresses the discharge amount by introducing an inert gas and lowering the temperature of the heating means 4a, 4b, 4c, and 4d. When condensed to 2, the material 14 to be treated that has condensed in the sublimation purification pipe 2 is scraped off and collected. And the temperature of heating means 4a, 4b, 4c, 4d is changed, and sublimation purification is performed again.

  The target substance 14 to be sublimated and purified in the first embodiment of the present invention is an organic dye used for organic EL such as tris (8-quinolinolato) aluminum or an organic semiconductor such as pentacene, and has a characteristic of sublimating under reduced pressure. If so, the same effect can be obtained with respect to other organic compounds, and the purified sublimation substance 15 is obtained by purifying the substance 14 to be purified without losing a small amount of material that is expensive. It is done.

  As described above, in the present embodiment, the sublimation purification tube 2 having at least one opening, the heating means 4a, 4b, 4c, and 4d for heating the sublimation purification tube 2 to the sublimation purification tube 2 and the inside The sublimation purification pipe 2 is provided with a decompression means 5 for decompressing, and the sublimation purification pipe 2 is provided with a target substance heating container 8 filled with the target substance 14. A sublimation purification apparatus 1 that sublimates the target substance 14 in the target substance heating container 8 by heating the target substance heating container 8 and condenses the sublimated target substance 14 in the sublimation purification tube 2. And a discharge amount measuring means 12 for detecting a substance 14 to be treated discharged from the sublimation purification pipe 2 at the subsequent stage of the sublimation purification pipe 2, and an inert gas to the sublimation purification pipe 2 at the front stage of the sublimation purification pipe 2. Introducing inert gas The sublimation purification pipe 2 is provided by providing an amount adjusting means 6 and introducing an inert gas when the discharge of the substance 14 to be treated is detected and lowering the temperature of the heating means 4a, 4b, 4c, 4d. The material 14 to be treated is not discharged from the air.

  As a result, when an expensive and small amount of the material to be treated 14 is discharged, the amount of discharge is detected, and an inert gas is introduced according to the amount of discharge to reduce the degree of decompression, thereby sublimating the material to be processed 14. By suppressing the average free path of the treated substance 14 that has been sublimated, the treated substance 14 existing in the sublimation purification pipe 2 is held in the pipe, and the temperature of the heating means 4a, 4b, 4c, 4d is lowered. By making it adhere, it has the effect that it can suppress discharging outside the sublimation purification pipe | tube 2 by making it adhere to an inner wall surface.

  Further, in the present embodiment, the sublimation purification material 15 is one type, but the same effect can be obtained even when a plurality of types exist.

  In the present embodiment, the recovery method of the sublimation purification material 15 is not particularly limited. However, when all of the target substance 14 filled in the target substance heating container 8 has been sublimated, The operation may be stopped, and the sublimation purification tube 2 may be taken out when the inside of the sublimation purification tube 2 reaches room temperature and normal pressure, and scraped with a spatula or the like.

  In the present embodiment, the heating means 4a, 4b, 4c, and 4d are provided with heating wires. However, the heating means 4a, 4b, 4c, and 4d are not limited to this configuration, and are not limited to the sublimation purification tube outer tube 3. 3 can be heated with a ribbon heater or the like if the structure can be heated in close contact with 3.

In the present embodiment, the structure of the decompression means 5 is not particularly limited, but the interior of the sublimation purification pipe 2 such as a rotary pump, a diaphragm pump, a diffusion pump, and a turbo molecular pump can be decompressed to about 10 ⁻⁵ Pa. Any vacuum pump may be used as long as it has a sufficient capability, and the same effect can be obtained even when a plurality of vacuum pumps are used in combination.

  The sublimation purification apparatus according to the present invention is expensive and can be obtained as a sublimation purification substance without losing a small amount of material. Therefore, the sublimation purification apparatus used for organic EL, organic solar cells, organic semiconductors, etc. It is useful as a purification and separation means.

DESCRIPTION OF SYMBOLS 1 Sublimation purification apparatus 2 Sublimation purification pipe 3 Sublimation purification pipe outer tube 4a Heating means 4b Heating means 4c Heating means 4d Heating means 5 Decompression means 6 Inert gas introduction amount adjustment means 7 Inert gas introduction pipe 8 Processed substance heating container 9 Flange 10 O-ring 11 Clamp 12 Discharge amount measuring means 13 Gas cylinder 14 Substance to be treated 15 Sublimation purification substance 16 Control unit 17 Discharge substance 18 Piping member 101 Sublimation purification apparatus 102 Sublimation purification pipe 102a Sublimation purification pipe (inner pipe)
103 Depressurizing means 104a Heating means 104b Heating means 104c Heating means 105a Flange 105b Flange 106 Outlet 107 Substance to be treated heating substance 108 Substance to be treated 109 Heating wire 110 Sublimation purification substance

Claims (2)

A sublimation purification tube having at least one opening;
The sublimation purification tube is equipped with a heating means for heating the sublimation purification tube and a decompression means for reducing the pressure inside.
The sublimation purification tube is equipped with a substance heating container to be treated to fill the substance to be treated,
By heating the sublimation purification tube and the material heating container by the heating means,
Sublimate the target substance in the target substance heating container,
A sublimation purification device for condensing the sublimated material to be treated in the sublimation purification tube,
A discharge amount measuring means for detecting a substance to be treated discharged from the sublimation purification tube downstream of the sublimation purification tube;
Provided with an inert gas introduction amount adjusting means for introducing an inert gas into the sublimation purification tube in the previous stage of the sublimation purification tube,
Introducing an inert gas when detecting the discharge of the substance to be treated,
By reducing the temperature of the heating means,
A sublimation purification apparatus for preventing the substance to be treated from being discharged from the sublimation purification tube. A sublimation purification method for sublimating by heating a substance to be treated inside a sublimation purification tube and condensing the sublimated substance to be treated,
A discharge amount measuring means for detecting a substance to be processed discharged from the sublimation purification tube;
An inert gas introduction amount adjusting means for introducing an inert gas into the sublimation purification pipe is provided,
Introducing an inert gas when detecting the discharge of the substance to be treated,
By reducing the temperature of the heating means,
A sublimation purification method for preventing the substance to be treated from being discharged from the sublimation purification tube.

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