JPS6231961B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a technique that allows high-yield recovery of a high-purity specific component from a mixture containing the specific component by pressure crystallization. be.

[Conventional technology]

The pressure crystallization method involves introducing a raw material consisting of a liquid phase consisting of multiple components or a solid/liquid mixture into a high-pressure container,
This is a method of applying high pressure to the raw material with the liquid phase discharge pipe closed to promote crystallization of specific components,
By this operation, a state in which crystals of a specific component (hereinafter also referred to as a captured component) and residual liquid (hereinafter also referred to as a removed component) are mixed is obtained. Therefore, by unblocking the drain pipe, applying pressure to the solid-liquid coexistence state, and discharging the liquid removed component out of the system via a filter, and separating the solid and liquid while squeezing the remaining solid phase, high purity can be obtained. Specific ingredients can be obtained.
FIG. 10 is a vertical cross-sectional view of the main parts illustrating an apparatus used for this type of pressure crystallization, in which 1 is a high-pressure vessel, 2 is a filter, 3 is a heat insulating support material, 4 is a piston, and 5 is a supply pipe. Discharge side block, 6 is raw material supply pipe,
7 shows a removed component discharge pipe, and the basics of the pressure crystallization procedure using this device will be briefly explained as follows.

The drain valve V ₇ is closed and the liquid supply valve V ₆ is opened to supply the raw material from the raw material supply pipe line 6 into the high pressure container 1 .

When the liquid supply is finished, the liquid supply valve V ₆ is closed, and the piston 4 is lowered to apply high pressure to the raw material in the container 1, thereby promoting crystallization of a specific component.

When the crystallization is finished, drain valve V ₇ is opened and the process moves on to the filtering and squeezing process. In this step, the liquid present in the container 1 is squeezed and discharged through the filter 2, and the liquid is passed through the gap provided on the back side of the filter 2, through the drain passage 8 of the supply/discharge side block 5, and into the discharge pipe. It reaches channel 7 and is discharged from drain valve _V7 .

After the filtration and squeezing are completed, the high-pressure container 1 is opened and the collected component solidified into a cake is taken out under atmospheric pressure, or alternatively, it is melted into a liquid and taken out from the high-pressure container.

[Problem that the invention seeks to solve]

By the way, in the above-mentioned over-squeezing process, a high pressure of several hundred to several thousand atmospheres is applied, and the liquid material is sequentially discharged through the filter 2, but at this time, the collected components near the filter 2 are under strong pressure. This results in a compacted state, making it extremely difficult to remove the liquid material from the center of the container at the end of the compression stage. Particularly when using a large-diameter high-pressure container, liquid removed components remaining in the center of the container 1 are a major cause of lowering the purity of specific components or prolonging the time required for liquid phase removal. It is becoming.

In view of these problems, the present inventors have conducted various studies in an attempt to establish a technique that can efficiently compress and remove the liquid material in the center of the container and increase the purity of specific components. As a result, the cylindrical filter is formed into a gently tapered shape that expands downward, and the cake-like collected components are buckled and broken in response to the forward movement of the piston, allowing the liquid inside the cake to flow out. He developed a method to promote this and filed a patent application. That is, in this invention, the first
As schematically shown in FIG. 1, the cylindrical filter 2 has a truncated cone shape, and the cake-shaped collected component is subjected to a squeezing force in the direction of the arrow by the piston 4. For example, the state shown by the solid line in FIG. When the state shown in the figure is reached, the cross-sectional area inside the filter 2 is gradually increasing, so that the cake-like material inside is squeezed out while repeatedly buckling and breaking. Since a liquid outflow passage is formed, the solid-liquid separation efficiency is significantly increased. However, even with this invention, if the high-pressure container has a large diameter, some liquid may still remain inside the cake.

Under these circumstances, the present invention aims to provide a technology that can efficiently remove the liquid substance inside the cake (collection component) especially during squeezing and significantly increase the purity of a specific component. be.

[Means for solving problems]

The structure of the pressure crystallization method according to the present invention is to pressurize the mixture to obtain a solid-liquid coexistence state in which a specific component is solidified,
In separating the solid-liquid to recover specific components, there is a step of: creating a state in which most of the mixture charged in a high-pressure container becomes a solid phase under pressure; A step of separating the liquid phase while maintaining the temperature at a temperature of The gist of this method is to carry out the step of discharging the collected liquid to the outside of the high-pressure chamber. Further, the apparatus according to the present invention is an apparatus used for implementing the above-mentioned high-pressure crystallization method, which comprises: A: a high-pressure container that maintains a mixture in a solid-liquid coexistence state under pressure; and B: a liquid-phase separation system. A squeezing mechanism that squeezes the solid phase in the high-pressure container at least in a subsequent stage; C: A filter that separates the liquid phase and the solid phase; D: A flow rate regulator or pressure that adjusts the flow rate of the liquid discharged through the filter. The gist of the present invention is that it comprises: a regulator; and E: a volume expansion mechanism capable of partially expanding the volume of the high-pressure container at any time.

[Effect]

In the present invention: A mixture containing a liquid or partially solidified specific part is charged into a high-pressure container and pressurized to promote solidification of the specific component, and then: The mixture in a solid-liquid mixed state is maintained at high pressure. The basic process of separating the liquid phase while performing the process is no different from the conventional pressure crystallization method, and the equipment configuration also has the minimum functionality to carry out this basic method. This is common to known pressure crystallizers.

However, in the present invention, in order to prevent the above-mentioned problems that occur during the pressing process of solid materials (particularly insufficient removal of liquid by pressing out the liquid inside the cake-like material), the pressure of the liquid phase separated in the pressing process is increased by increasing the pressure in the high-pressure chamber. The point at which the pressure becomes lower than the pressure (that is, the point at which most of the liquid phase in the high-pressure vessel is discharged outside the vessel and the crystal grains begin to be squeezed...
...However, the present invention differs from conventional pressure crystallization methods in that it forms a low-pressure part in a part of the high-pressure container, with some liquid phase remaining inside the cake. Features exist. In other words, when a low-pressure area is formed at an appropriate location in the high-pressure container during or at the end of the compression process, the liquid phase within the cake moves toward this low-pressure area through the grain boundaries, and is compressed into a cake. The solid material causes buckling failure as it moves toward the low-pressure area, and this buckling failure forms a flow path for the liquid remaining inside the solid material, and the liquid quickly leaches toward the low-pressure area. It's coming. Therefore, by discharging this liquid material to the outside of the high-pressure container, the liquid material left inside can be removed as quickly and as much as possible, and the solid matter (collected material) remaining in the high-pressure container can be removed. (minutes) can be dramatically improved.

The device according to the present invention is equipped with a configuration for forming the above-mentioned low-pressure part in a high-pressure container, and the details will be clarified in the examples below, but the point is that a volume expansion mechanism is attached to the high-pressure container. By activating the volume expansion mechanism during or at the end of the compression process, the volume of the high-pressure container is expanded to form a low-pressure part in this part, and liquid leaches out and cake-like solids are produced in this part. It is designed to cause buckling failure as described above.

〔Example〕

DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure and effects of the present invention will be described in detail below with reference to the drawings showing embodiments. FIG. 1 is a schematic vertical cross-sectional view of the main parts illustrating a high-pressure crystallization apparatus according to the present invention, and the basic configuration of the apparatus is substantially the same as the example shown in FIG. 8. However, in this example, a volume expansion member 9 that constitutes a volume expansion mechanism is provided so as to penetrate through the supply/discharge side block 5 and protrude into the high pressure vessel 1 at its tip. is provided with a filter and has a liquid passage 10 formed therein, and is configured to be movable into and out of the high-pressure container 1 (11 is a hydraulic chamber, and _V11 is an oil supply/drain valve).

The pressure crystallization procedure using this apparatus is carried out as follows.

By opening the valve _V11 and filling the hydraulic chamber 11 with high pressure oil, the volume expanding member 9 is made to protrude into the container 1, and the valve _V11 is closed.

The drain valves V ₇ and V ₁₀ are closed, and the liquid supply valve V ₆ is opened to supply the raw material from the raw material supply pipe line 6 into the high-pressure vessel 1 .

When the liquid supply is finished, the liquid supply valve V ₆ is closed, and the piston 4 is lowered to apply high pressure to the raw material in the container 1, thereby promoting crystallization of a specific component.

When the crystallization is finished, drain valves V ₇ and V ₁₀ are opened to squeeze out the liquid in the container 1, and it is discharged from the drain pipe 10 and drain passage 8 to the outside of the container via the drain pipes 7 and 10. Ru. Discharge pipe 7 (and/or 10)
A pressure regulator 12 is provided, and controls the inside of the high-pressure container 1 to be maintained at a predetermined pressure or higher by adjusting the discharge amount of the liquid material. The reason for this is that if the pressure inside the high-pressure container 1 drops too much, part of the collected components that have been painstakingly crystallized under high pressure will melt again, reducing the recovery rate. When the outflow of the liquid is finished, the internal pressure of the discharge pipe 7 (and 10) begins to drop, so the pressure regulating valve 12 is operated to adjust the outflow amount so that the pressure does not drop too much. It is also possible to use a flow rate regulator instead of the pressure regulator 12 to detect the end of the outflow of the liquid and to adjust the amount of outflow of the liquid.

When the discharge of the liquid in the high-pressure container 1 is almost completed and the pressure in the discharge pipe 7 (and 10) becomes lower than the pressure in the high-pressure container 1, this signal is transmitted to the oil supply/drain valve V ₁₁ . is opened, the oil in the hydraulic chamber 11 is discharged, and the volume expanding member 9 is lowered. As a result, the tip of the volume expanding member 9
The inside of the container 1 is evacuated and a low-pressure part B is formed in this part as shown in FIG. It moves toward the low-pressure part B as if being crushed and cracking. The cracks that occur during this movement process become passageways for the liquid left behind inside the cake-like solid.
The liquid flows out in the direction of the evacuated volume expansion member 9 and in the direction of the cylindrical filter 2 on the outer circumferential side, and flows out into the discharge pipe 1.
0 and is discharged to the outside of the vessel through the drain passage 8 and the discharge pipe 7.

In this way, the liquid matter remaining in the container can be efficiently removed, and the purity of the collected components can be dramatically increased. In particular, in this example, the volume expanding member 9 is arranged so that the low pressure part B is formed in the center of the high pressure container 1, where the liquid is most likely to remain, so that the liquid inside can be removed more efficiently. I can do it.
In addition, when the cross-sectional area of the high-pressure vessel 1 is narrow, the first,
As shown in Figure 2, there is one volume expanding member 9 in the center.
However, when the cross-sectional area of the high-pressure vessel 1 is wide, it is sufficient to provide a plurality of volume expansion members 9a, 9b as shown in FIG. It is also possible to promote the outflow of liquids by installing a In this case, the molten volume expanding members 9a and 9b may be operated by a common hydraulic cylinder as shown, or may be operated by separate hydraulic cylinders. Of course, the operating mechanism of the volume expanding member 9 is not limited to a hydraulic cylinder, and it is of course possible to employ other fluid pressure operating systems such as an air cylinder, or a solenoid mechanism.

In addition, in the above example, since a filter is also placed at the tip of the volume expansion member 9, not only is the discharge of the remaining liquid material after the formation of the low pressure section B promoted, but also the filter is disposed at the tip of the volume expansion member 9, so that the remaining liquid material is not only discharged from the center part in the previous over-squeezing process. Since the liquid material is also discharged, the squeezing time itself can be considerably shortened. However, it is not necessary to provide a filter at the tip of the volume expanding member 9, and it may be a simple solid reciprocating member as shown in FIG. 4, for example. In this case, low pressure part B
The lower surface of the high-pressure container 1 (i.e., the upper surface of the supply/discharge side block 5) and the distal end surface of the volume expansion member 9 are aligned in the circumferential direction so that the liquid material flowing down during formation immediately flows toward the cylindrical filter 2 on the outer periphery. It is best to form it so that it slopes downward.

FIG. 5 is a schematic longitudinal sectional view showing another embodiment of the present invention, and the most protruding position of the volume expanding member 9 coincides with the upper surface of the supply/discharge side block 5, but it is necessary to retract it. Therefore, this is an example in which the low pressure part B is formed below the lower surface of the high pressure vessel 1, and in this case as well, the outflow of residual liquid due to cracks is promoted, as in the previous example. . However, in this case, since the liquid flowing down toward the low pressure part B will accumulate on the upper surface side of the volume expanding member 9, a filter should be formed on the upper surface of the volume expanding member 9, and a discharge pipe 10 should also be formed. Of course.

FIG. 6 shows still another example of the volume expansion member 9, in which a tube-shaped volume expansion member 9 is disposed on the upper surface of the supply/discharge side block 5. During pressurized crystallization, the inside of the volume expanding member 9 is filled with pressurized fluid to inflate it as shown by the broken line, and at the end of the compression, the internal fluid is released and it contracts as shown by the solid line. This forms a low pressure section B.

FIG. 7 shows another example for forming a low-pressure part within a high-pressure chamber. In this example, the cylindrical filter 2 is formed into a truncated conical shape, and the entire high-pressure vessel 1 is connected to a piston by a hydraulic cylinder 15 or the like. It is constructed so that it can be raised and lowered independently of the number 4. At the end of the compression, the hydraulic cylinder 15 is operated to slightly raise the high pressure container 1. Then filter 2
As a result, as shown schematically in FIG. 8, a gap is created on the outer circumferential side of the cake-like pressed product, and a low-pressure portion is formed.

FIG. 9 is a schematic vertical sectional view showing still another pressure crystallizer according to the present invention, and shows an example in which the pressure crystallization itself is performed using pressurized fluid. That is, a flexible tube 14 is attached to a suitable position on the peripheral wall of the high-pressure vessel 1, and the tube 14 is expanded by blowing high-pressure fluid into it, thereby pressurizing the inside of the high-pressure vessel 1 and performing high-pressure crystallization. In this case as well, the same solid-liquid separation promoting effect can be obtained by retracting the volume expanding members 9a and 9b at the final stage of compression to form a low pressure section B and causing cracks in the cake-like solid material.
As described above, the pressure source for pressure crystallization according to the present invention is not limited to piston compression, and various other pressure mechanisms can be adopted, and the specific configuration of the apparatus is based on these pressure mechanisms, etc. The design can be changed as appropriate.

〔Effect of the invention〕

The present invention is constructed as described above, but the key point is to form a low-pressure part in the high-pressure chamber at the final stage of solid-liquid compression, thereby causing cracks in the cake-like solid to form a passage for the residual liquid. As a result, the liquid material can be squeezed out more reliably, and the purity of the specific substance can be significantly increased. In addition, the time required for complete compression can be significantly shortened, and even if a large high-pressure container is used, there will be no loss of purity, making it easy to improve productivity by increasing the size of the container. We can enjoy huge benefits in industrializing the law.

[Brief explanation of the drawing]

1 to 9 show embodiments of the present invention; FIG. 1 is a schematic vertical sectional view of the main part; FIGS. 2 to 9 are conceptual diagrams of the main part showing various modifications of the present invention; and FIG. 11 is a schematic vertical sectional view showing a known pressure crystallizer, and FIG. 11 is an explanatory view showing the solid-liquid separation promoting effect obtained by the invention of the prior application. DESCRIPTION OF SYMBOLS 1... High pressure container, 2... Filter, 3... Heat insulation support material, 4... Piston, 5... Supply/discharge side block, 9... Volume expansion member.

Claims (1)

[Scope of Claims] 1. A pressure crystallization method in which a mixture is pressurized or cooled under pressure to obtain a solidified solid-liquid coexistence state of a specific component, and this is solid-liquid separated to recover the specific component: A step of creating a state in which the mixture charged in a container becomes mostly solid under pressure. A step of separating the liquid phase while maintaining the solid-liquid mixed state at high pressure. A step of separating the liquid. When the pressure of the phase becomes lower than the pressure inside the high-pressure chamber, a step of forming a low-pressure section in a part of the high-pressure chamber is performed: A step of discharging the liquid that collects in the low-pressure section to the outside of the high-pressure chamber. pressure crystallization method. 2. In a pressure crystallizer that pressurizes a mixture to obtain a solidified solid-liquid coexistence state of a specific component, and then separates this into solid-liquid to recover the specific component, A: The mixture is maintained in a solid-liquid coexistence state under pressure. B: A squeezing mechanism that squeezes the solid phase in the high-pressure vessel at least after the liquid phase separation; C: A filter that separates the liquid phase and the solid phase; D: A filtrate discharged through the filter. A pressure crystallizer comprising: a flow rate regulator or a pressure regulator that adjusts the outflow rate of the high-pressure container; and E: a volume expansion mechanism that can partially expand the volume of the high-pressure container at any time. Device. 3. The device according to claim 2, wherein the volume expansion mechanism is a member that protrudes so that it can move forward and backward into the high pressure chamber. 4. The device according to claim 2 or 3, wherein the volume expansion mechanism is provided with a filter and a filtrate outflow passage. 5. The device according to claim 2, wherein the volume expansion mechanism is an axial movement device for a high-pressure container.