JP2005035938A - Method for isolating and refining organic material in magnetic field - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for isolating and refining various organic materials from their mixture by a simple means. <P>SOLUTION: The method for isolating and refining each of organic materials comprises applying magnetic force onto a melted organic mixture and isolating each of the resultant refined organic materials on a smooth curved surface. Alternatively, the method comprises solidifying each of the above resultant refined organic materials. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for separating and purifying organic substances in a magnetic field.

In general, both organic and inorganic materials are obtained as a mixture. Various separation methods are used for effective use as a pure single substance. For example, various chromatography, recrystallization, distillation, steam distillation and the like. Although these methods have their respective characteristics, they have a problem that they require a large amount of equipment and energy, and a lot of cost and time are required for maintenance and maintenance.
On the other hand, in recent years, powerful and large superconducting magnets (superconducting magnets) have become available at a relatively low cost, and development of technologies for applying superconducting magnets to various industrial processes has been promoted.

  Accordingly, an object of the present invention is to provide a method for separating and purifying various organic mixtures by a simple technique in view of such a current situation.

In the process of examining the behavior of a non-magnetic substance, that is, a diamagnetic or paramagnetic substance in a strong magnetic field, the present inventors have a particularly large magnetic field gradient in the strong magnetic field even in the liquid state. In place, there is the possibility of moving due to the strength of the magnetic field, the magnetic field gradient and the magnetic force determined by the substance's intrinsic diamagnetism or paramagnetism, and therefore the effect of the magnetic force is slight, We found that it differs depending on the substance.
Ferromagnetic materials can move in a strong magnetic field even in the form of fine powder, but non-magnetic materials are practically impossible to move even in a strong magnetic field in the fine powder or crystalline state. Therefore, when heated, melted and made into a liquid state, when a strong magnetic field is applied to form a magnetic field gradient (a magnetic field in which the magnetic force changes with a gradient in a certain range), the magnetic force acting on organic substances also differs. It shows a different movement, so that the mixture can be separated from each other and then returned to the solid state again by cooling. In this way, separation can be performed using temperature control.

In this way, even though it is a non-magnetic substance on a horizontal plane, it is moved by a strong magnetic force, but as it is, it continues to move in a certain direction, so that the mixture cannot be separated. Therefore, it has been found that it is effective to move on a slope that is smooth and has a continuously changing gradient. The liquid on the smooth slope that receives the magnetic force in the horizontal direction moves up the smooth slope and reaches the point where it was just suspended, depending on the magnitude of the magnetic force received in the horizontal direction and the resultant force of gravity in the vertical direction. And stop. A substance that receives a large magnetic force reaches a point where the slope of the slope is large and stops, and a substance that is less sensitive to the magnetic force stops in a balanced manner with a slight movement.
Furthermore, it has been clarified that the material of the material constituting the smooth slope has a great influence on the magnetic separation. Since the interfacial tension always works between the material constituting the smooth slope and the separated material on it, the force moved by the magnetic force depending on the magnitude of the interfacial tension, The degree of going up the slope is different.
As described above, there are four main requirements that affect magnetic separation: the magnitude of magnetic force, keeping the substance to be separated in a liquid state, the slope of the smooth slope, and the surface physical properties of the substance constituting the slope. Conceivable.
The present invention has been made based on these findings.

That is, the present invention
(1) Applying magnetic force to the melted organic substance mixture to separate the purified organic substance on a smooth curved surface;
(2) Provided is a method for separating and purifying an organic substance as described in (1), wherein the purified organic substance is then solidified.

  By the separation and purification method of the present invention, various organic substances that are solid at room temperature can be easily separated and purified. Only under extremely limited and mild conditions, overheating and cooling are not performed, and, besides using strong magnetic force, only using universally existing gravity and stable interfacial tension with the container surface, An unstable substance can be easily separated without deteriorating the original properties of the substance.

In the present invention, organic substances are separated and purified by magnetic force. The source of the magnetic field for that purpose is not limited to this, but a superconducting magnet is preferred, and in particular, it is particularly preferred to use a helium-free superconducting magnet because of its operability and cost. . A commercially available helium-free superconducting magnet can be used as it is. In the present invention, the strength of the magnetic field is preferably about 1 to 10 Tesla, more preferably 5 to 10 Tesla.
For example, in the case of a typical commercially available 10 Tesla superconducting magnet, the magnetic force is maximized at a point 100 mm away from the center of the magnetic field, so the mixture to be separated is placed there. For example, when separating a mixture of organic compounds having a melting point of not less than room temperature and not more than 100 ° C., the mixture is placed in a container placed on a copper sample table whose temperature is controlled by circulating water, and the mixture is completely at a temperature above the melting point. After confirming that the mixture has melted, the mixture can be placed in a place where the magnetic force of the superconducting magnet is maximized and magnetically separated.

  In the present invention, the method for melting the organic mixture by temperature control is not particularly limited, and a conventionally used heating method can be used.

In the present invention, the organic mixture is melted, magnetically separated, and solidified on a smooth curved surface. An example of a container having a smooth curved surface is a container having a smooth concave surface, which is horizontal in the center, but whose gradient increases as it moves away from the center. The simplest is a constant radius of curvature. For example, a spherical sample dish with
The material constituting the smooth curved surface is not limited thereto, but examples of relatively easily available materials include glass (GL), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), Examples include polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), nylon (hydrophilic polymer, Ny), cellophane (hydrophilic polymer, Cell), polycarbonate, and the like. A smooth curved surface composed of these substances can be appropriately selected in accordance with the organic substance to be separated and purified.

After installing a smooth curved container containing the mixture, by generating a magnetic field and acting as a magnetic force, the molten liquid mixture moves in the smooth curved container by the magnetic force, The interfacial tension acting between the container and the substance to be separated, the magnitude of the magnetic force based on the inherent paramagnetic or diamagnetic magnitude of the substance, and the force pulled back to the container center by gravity determined according to the gradient of the curved surface of the container. At the position of the balance of the three, stop with the liquid. At this time, since the balance position of each substance is different depending on each substance, it is separated into each component while remaining in a liquid state.
Then, by cooling the container to below the melting point of the lower substance in the mixture, each separated component solidifies and solidifies at each position, and is easily taken out from the magnetic field at room temperature. It can be purified. At this time, in fact, on a smooth curved surface, each substance is kept in a liquid without being solidified to a temperature much lower than the melting point (supercooling), so it is cooled to a temperature much lower than the melting point. It is necessary. In the present invention, the cooling method for solidifying the organic substance is not particularly limited, and a conventionally used cooling method can be used.

Next, the present invention will be described in more detail based on examples. In the examples,% indicating composition indicates mass%.
Example 1
A temperature control vessel connected with a water-circulating temperature controller and a heat-resistant hose was prototyped. The temperature control vessel is a cylindrical vessel made of polyvinyl chloride with an outer wall of 98 mm in diameter and 200 mm in length. Inside, a copper water circulation pipe protected by foamed polystyrene insulation and a sample stage are incorporated. It is. The part (plan view (A) side view (B) and sectional view (C)) of the copper sample stage 1 is shown in FIG. In addition, the unit of the numerical value described in FIG. 1 is mm.
A sample pan 2 shown in FIG. 2 was placed on the concave portion 1 a of the copper sample stage 1. 2A is a plan view, and FIG. 2B is a cross-sectional view. The sample pan 2 is made of polyethylene terephthalate having an outer radius of curvature of 76.3 mm, a curved surface diameter of 65 mm, and a thickness of 0.125 mm, and has a smooth concave surface with a constant curvature. This sample pan 2 is prepared by heating, melting and cooling a polyethylene terephthalate film in an electric furnace using a separately prepared stainless steel mold. The sample pan was fixed with four plastic screws so as to be in close contact with the sample stage 1 and kept horizontal.
Next, 100 mg of benzophenone crystals and 100 mg of n-docosane crystals were placed in the center of the sample dish, and the temperature controller was operated to keep the sample stage constant at 70 ° C. Benzophenone and n-docosane melted completely and mixed together to form a homogeneous solution. The sample portion was covered with a copper lid, a heat insulating material, and a polyvinyl chloride lid, and the entire cylindrical container was inserted horizontally into a bore of a helium-free superconducting magnet fixed horizontally. At this time, the superconducting magnet is not operating yet and no magnetic field is generated.
The bore of the helium-free superconducting magnet has an inner diameter of 100 mm, and the cylindrical container is designed to fit just inside it. The position of the sample container was fixed so that the center of the sample pan was positioned 100 mm before the center of the magnetic field, and the sample came there. At this position, the magnetic force determined by the product of the strength of the magnetic field and the magnitude of the magnetic field gradient is maximized.
The rise of the magnetic field was started while maintaining at 70 ° C. in the bore, and after 45 minutes, the magnetic field center shown in FIG. Thereafter, the temperature was lowered to 0 ° C. at a rate of 0.5 ° C. per minute, kept constant for 3 hours, and then raised to 25 ° C. After that, when the cylindrical container is taken out from the bore, and the sample is taken out, the side closer to the center of the sample pan as viewed with the naked eye (the extension line of the line connecting the center of the magnetic field and the center of the pan, 15 mm away from the center of the pan) And two parts on the side near the outer periphery of the sample pan (extension of the line connecting the center of the magnetic field and the center of the pan and 26 mm away from the center of the pan), and clearly different types of crystals are attached. It was. When each portion of the crystal was analyzed using a differential scanning calorimeter, 74% of benzophenone and 26% of n-docosane were found on the crystal near the center of the sample pan. Contained 5% benzophenone and 95% n-docosane, respectively. This result shows the following.

  That is, both benzophenone and n-docosane are completely mixed in the molten state but nevertheless receive a magnetic force having a different size. The action of the magnetic force goes back to each smooth slope against the gravity, but the action of the magnetic force (the force pushed by the magnetic force) is greater for n-docosane than for benzophenone, so n-docosane is more A steep slope is reached. As a result, although both are liquids, they remain separated on their slopes. Thereafter, n-docosane crystallizes first due to a temperature drop, and then benzophenone, and adheres to the surface of the polyethylene terephthalate film. Since both of the surface adhesion forces are strong, the separated state was kept as it was even after taking it out at room temperature outside the magnetic field.

The values of magnetic field strength, magnetic field gradient, and magnetic force index (= magnetic field strength x magnetic field gradient) in this test are shown in FIG. Shown in A), (B), (C).
FIG. 3A shows the relationship between the magnetic field strength Hx (T) and the distance from the magnetic field center. It can be seen from the figure that the magnetic field strength decreases with increasing distance from the center of 10.0 Tesla at the magnetic field center (distance 0).
FIG. 3B is a graph showing the relationship between the strength of the magnetic field and the tangential gradient in FIG. 3A and the distance from the magnetic field center. It can be seen that the minimum value is shown when it exceeds 100 mm from the center of the magnetic field.
FIG. 3C shows an index of magnetic force. As shown in the figure, the value of (magnetic field strength) × (magnetic field gradient), which is an index of magnetic force, takes a maximum value at a distance of 100 mm from the magnetic field center (a point where the magnetic field strength is maximum). Therefore, in this case (when this magnet is used and a magnetic field of 10.0 Tesla is used), the magnetic force becomes maximum at a point of 100 mm, and the curved surface can be climbed with the largest force.

Examples 2-5
100 mg each of benzophenone and n-docosane were used in the same manner as in Example 1, and the sample dish was changed from 0.125 mm thick polyethylene terephthalate to 0.200 mm thick polyterelafluoroethylene (Example 2), 0.300 mm thick. Nylon 66 (Example 3), glass with a thickness of 2 mm (Example 4), and polyvinyl chloride with a thickness of 0.5 mm (Example 5) were tested in the same manner. Got. However, when polyvinyl chloride was used, the separation efficiency was as good as other cases, but the dish was slightly deformed. This was probably because the plasticizer contained in the polyvinyl chloride film eluted and reacted with benzophenone.

Examples 6-7
While 100 mg each of benzophenone was used as in Example 1, n-docosane was changed to 100 mg of n-octadecane (Example 6) or n-triacontane (nC ₃₀ H ₆₂ ) (Example 7), The same experiment as in Example 1 was performed by changing the sample dish to polytetrafluoroethylene having a thickness of 0.2 mm, and almost the same magnetic separation results were obtained.

The sample stage used in Example 1 is shown. (A) Plan view (upper left figure), (B) is a side view (upper right figure, AA cross section is shown by a one-dot chain line), and (C) B. It is -B sectional drawing (lower figure). The x mark in the figure indicates the center of the magnetic field, and the mixed organic material to be separated is placed at a position 100 mm away from the magnetic field center. (A) of the sample pan used in Example 1 is a top view (upper figure), and (B) is sectional drawing (lower figure). (A) of the apparatus used in Example 1 is a graph showing the relationship between the strength of the magnetic field and the distance from the magnetic field center, (B) is a graph showing the relationship between the magnetic field gradient and the distance from the magnetic field center, and (C) is It is a graph which shows the relationship between (magnetic field strength) x (magnetic field gradient) which is an index of magnetic force, and the distance from the magnetic field center.

Explanation of symbols

1 Sample stand 2 Sample pan

Claims (2)

  A method for separating and purifying an organic substance, in which a magnetic force is applied to a molten organic substance mixture to separate the purified organic substance on a smooth curved surface.   The method for separating and purifying an organic substance according to claim 1, wherein the purified organic substance is then solidified.

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