The present invention relates to a mixture separation method and a mixture separation apparatus for separating, by type, a mixture containing two types of particles, or for separating a specific type of particle from such a mixture.
JP 2002-59026A (Patent Document 1) discloses a mixture separation method using a magneto-Archimedes effect. The mixture separation method disclosed in Patent Document 1 is characterized in that a magnetic field having a magnetic field gradient (referred to as “gradient magnetic field” hereinafter) is applied to a plastic mixture including a plurality of types of diamagnetic solid plastic particles that floats or sinks in a paramagnetic supporting liquid to float the plastic particles at positions corresponding to the types of particle.
On the other hand, a high gradient magnetic separation (HGMS) method as disclosed in JP 2004-533915A (Patent Document 2) is known as a method for adsorbing and separating particles of paramagnetic materials (feeble magnetic materials) in liquid or gas. In the HGMS method, a high gradient magnetic field is generated by applying a high magnetic field to a magnetic filter formed of fine wires of a ferromagnetic material to adsorb paramagnetic particles in liquid or gas on the magnetic filter.
Patent Document 1: JP 2002-59026A
The magneto-Archimedes effect can be used to float paramagnetic particles at a position or height corresponding to their magnetic susceptibility and density in the supporting liquid. Accordingly, a gradient magnetic field is applied to paramagnetic particles and diamagnetic particles in the supporting liquid, and the magneto-Archimedes effect can be used to float these particles at different heights and separate them.
When the magneto-Archimedes effect is used to float paramagnetic particles in the paramagnetic supporting liquid, the difference between the magnetic susceptibility of the supporting liquid and the magnetic susceptibility of the paramagnetic particles is small compared to the case of floating diamagnetic particles, and therefore, it is required to apply a gradient magnetic field having a very large magnetic field and/or magnetic field gradient thereto. However, when generating the gradient magnetic field required to float the paramagnetic particles, the load on the apparatus that generates the magnetic field is increased.
When the concentration of a paramagnetic material (e.g., paramagnetic inorganic salt) that is dissolved in the supporting liquid is increased to increase the magnetic susceptibility of the supporting liquid, the magnitude of a magnetic field and/or magnetic field gradient required to float the paramagnetic particles can be reduced. However, increasing in the paramagnetic material concentration is not preferable because the viscosity of the supporting liquid is increased and it takes a long time to separate the mixture. Particularly, if the particle size of the mixture is small, the influence of the viscosity of the supporting liquid markedly appears in the separation process. Furthermore, a supporting liquid in which a paramagnetic material has been dissolved in a high concentration is not preferable because it becomes difficult to recycle or dispose of the supporting liquid. For these reasons, a separation method using the magneto-Archimedes effect is not used to separate a mixture containing paramagnetic particles.
On the other hand, even if a mixture containing paramagnetic particles and diamagnetic particles is treated using the HGMS method, the paramagnetic particles are caught with the magnetic filter, but the diamagnetic particles remain suspended in the medium. Accordingly, if the diamagnetic particles need to be collected from the medium, a process of separating and collecting the diamagnetic particles needs to be separately performed before or after the separation process by the HGMS method, and therefore, an apparatus for separating and collecting diamagnetic particles is separately required in addition to the apparatus for the HGMS method.
The present invention solves the above-described problems and provides a mixture separation method and a mixture separation apparatus for separating, by type, a mixture containing two types of particles, or for separating a specific type of particle from such a mixture, the mixture separation method and the mixture separation apparatus reducing the load on the apparatus configuration and being capable of preforming processes efficiently in a short time compared to conventional methods.
The mixture separation method of the present invention is a mixture separation method for one of separating, by particle type, a mixture of first particles and second particles of different types by applying a gradient magnetic field to a paramagnetic supporting liquid containing the mixture, and separating, by applying a gradient magnetic field to a paramagnetic supporting liquid containing a mixture of first particles and second particles of different types, the first particles or the second particles from the mixture, wherein a magnetic susceptibility of the first particles is lower than a magnetic susceptibility of the supporting liquid, and a magnetic susceptibility of the second particles is higher than the magnetic susceptibility of the supporting liquid, and the mixture separation method comprises applying the gradient magnetic field to the supporting liquid in a separation tank provided with a magnetic filter means and stirring the supporting liquid, floating the first particles in the supporting liquid by a magneto-Archimedes effect and catching the second particles in the supporting liquid with the magnetic filter means excited by the gradient magnetic field.
The mixture separation apparatus of the present invention is a mixture separation apparatus for one of separating, by particle type, a mixture of first particles and second particles of different types by applying a gradient magnetic field to a paramagnetic supporting liquid containing the mixture, and separating, by applying a gradient magnetic field to a paramagnetic supporting liquid containing a mixture of first particles and second particles of different types, the first particles or the second particles from the mixture, wherein a magnetic susceptibility of the first particles is lower than a magnetic susceptibility of the supporting liquid, and a magnetic susceptibility of the second particles is higher than the magnetic susceptibility of the supporting liquid, and the mixture separation apparatus comprises a separation tank in which the supporting liquid is stored or to which the supporting liquid is sent, a magnetic field generating means for generating the gradient magnetic field, a magnetic filter means provided in the separation tank and a stirring means for stirring the supporting liquid in the separation tank, wherein the gradient magnetic field is applied to the supporting liquid in the separation tank and the supporting liquid is stirred, the first particles float in the supporting liquid by a magneto-Archimedes effect, and the second particles in the supporting liquid are caught with the magnetic filter means excited by the gradient magnetic field.
In the mixture separation method and separation apparatus of the present invention, the gradient magnetic field may be applied so that the first particles float in the supporting liquid or at the liquid surface thereof by the magneto-Archimedes effect, at least over the magnetic filter means.
In the mixture separation method and separation apparatus of the present invention, a horizontal magnetic force may act on the first particles by the gradient magnetic field, and the first particles may travel to a region lateral to or outward from the magnetic filter means by the magnetic force and be gathered in the region.
In the mixture separation method and separation apparatus of the present invention, the first particles may be gathered so as to be positioned at the substantially same height in the supporting liquid.
In the mixture separation method and separation apparatus of the present invention, the gradient magnetic field may be axially symmetrical about a central axis in a vertical direction, a magnetic field gradient of the gradient magnetic field may have a component of a vertical direction and a component of a radial direction, and a magnetic force in a radial direction may be applied to the first particles so that the first particles move away from the central axis by applying the gradient magnetic field to the supporting liquid.
In the mixture separation method and separation apparatus of the present invention, the first particles may be formed of a diamagnetic material or a paramagnetic material, the second particles may be formed of a paramagnetic material or an antiferromagnetic material, and the supporting liquid may be an aqueous solution of a paramagnetic inorganic salt.
In the mixture separation method and separation apparatus of the present invention, the magnetic filter means may include a net plate formed of a ferromagnetic material, and the gradient magnetic field may be applied substantially orthogonally to the net plate.
In the present invention, gathering the first particles using the magneto-Archimedes effect and catching the second particles with the magnetic filter means are performed in a separation tank at the same time, and therefore, the mixture is efficiently separated in a short time. Furthermore, in the present invention, since the magnetic filter means is excited by the gradient magnetic field generated to cause the magneto-Archimedes effect, the apparatus configuration is simplified compared to the case of performing the separation treatment using a conventional method. Gathering the first particles using the magneto-Archimedes effect and catching the second particles with the magnetic filter means are promoted or assisted by stirring the supporting liquid.
In the present invention, if the first particles are gathered in a region lateral to or outward from the magnetic filter means for catching the second particles, the first particles and the second particles can be separated by type without largely increasing the distance in the vertical direction between the first particles and the second particles. Accordingly, the magnetic susceptibility of the supporting liquid can be reduced compared to a conventional separation method and separation apparatus using the magneto-Archimedes effect. As a result, the viscosity of the supporting liquid, that is, the resistance by the particles in the supporting liquid can be reduced to quickly or efficiently perform the separation treatment. Furthermore, in this case, the first particles are gathered in a region spaced from the magnetic filter means for catching the second particles, and therefore, compared to a conventional separation method and separation apparatus using the magneto-Archimedes effect, the distance between the regions for gathering particles can be increased to enhance the capability of separation and the accuracy of separation.
A mixture to be treated by the mixture separation method and the mixture separation apparatus of the present invention contains first particles and second particles that are different in type (more specifically, formed of different materials), and is subjected to a separation treatment in a state where the mixture is suspended in the supporting liquid. The magnetic susceptibility (more specifically, volume magnetic susceptibility; the same applies hereinafter) of the first particles is lower than that of the supporting liquid used for the present invention, and the magnetic susceptibility of the second particles is higher than that of the supporting liquid.
In the present invention, the supporting liquid is paramagnetic, and, for example, an aqueous solution of paramagnetic inorganic salt is used as the supporting liquid of the present invention. Examples of the paramagnetic inorganic salt used for the supporting liquid of the present invention include manganese chloride, cobalt chloride, nickel chloride, ferrous chloride, cobalt nitrate, nickel nitrate, gadolinium nitrate, dysprosium nitrate, and terbium nitrate. There is no limitation or restriction on the concentration of the paramagnetic salt in the supporting liquid as long as the effect of the present invention can be obtained.
The first particles of the mixture to be treated by the present invention may be formed of a diamagnetic material. For example, the first particles may be formed of glass (silica) or plastics (e.g., nylon and polyethylene terephthalate). Also, the first particles may be formed of a paramagnetic material such as aluminum.
The second particles of the mixture to be treated in the present invention may be formed of a paramagnetic material or antiferromagnetic material. For example, the second particles may be formed of titanium (paramagnetic material) or nickel oxide (antiferromagnetic material). Also, the second particles may be formed of a ferromagnetic material such as iron, nickel or maghemite.
In the present invention, it should be noted that as long as the magnetic susceptibility of the first particles is lower than that of the supporting liquid and the magnetic susceptibility of the second particles is higher than that of the supporting liquid (and additionally, if both of the densities of the first particles and the second particles are greater or smaller than that of the supporting liquid), there is no limitation on the materials of which the first particles and the second particles are formed. Although the first particles are formed of a diamagnetic material and the second particles are formed of a paramagnetic material or an antiferromagnetic material in the first to fifth examples described later, the present invention is also applicable to a case where, for example, the first particles are formed of a paramagnetic material (e.g., titanium) and the second particles are formed of a ferromagnetic material (e.g., maghemite). If the magnetic susceptibility of the first particles is lower than that of the supporting liquid and the magnetic susceptibility of the second particles is higher than that of the supporting liquid, both of the first particles and the second particles may be paramagnetic.
Although there is no limitation on the particle size or the average particle size of the first particles and the second particles in the present invention, the particle size or the average particle size of these particles is likely to be set to approximately several micrometers to several centimeters. Moreover, there is no limitation on the shapes of the particles in the present invention. The mixture may be produced by crushing or pulverizing a mass containing a plurality of materials, and the shapes of the particles contained in the mixture need not be uniform or identical.
When a gradient magnetic field is applied to the supporting liquid in which the mixture containing the first particles and the second particles is suspended, the apparent weight per unit volume of these particles is given by the following expression;
(ρi−ρ)g+(χi−χ)μ0·B∂B/∂z
where ρi is the density of the first particles or the second particles (i=1 or 2), χi is the magnetic susceptibility (volume magnetic susceptibility) of the first particles or the second particles (i=1 or 2), ρ is the density of the supporting liquid, χ is the magnetic susceptibility (volume magnetic susceptibility) of the supporting liquid, g is the acceleration of gravity, μ0 is the permeability in vacuum, B is the magnetic field (magnetic flux density), ∂B/∂z is the magnetic field gradient, and z is a coordinate in a vertical direction (downward direction is taken as positive).
If (ρ1−ρ)>0 (i.e., in the case where the first particles settle in the supporting liquid when a gradient magnetic field is not applied), the magnetic susceptibility of the supporting liquid is given such that (χ1−χ)<0 and the product of the magnetic field and the magnetic field gradient is a large positive number, so that the apparent weight represented by the above expression is negative and the first particles levitate or float in the supporting liquid. For example, when a magnet is provided under a tank storing the supporting liquid and a gradient magnetic field in which the magnetic field increases in the vertically downward orientation is applied to the supporting liquid, the first particles levitate in the supporting liquid. At the balanced height or position where the apparent weight represented by the above expression is zero, the first particles stably float by the magneto-Archimedes effect (i.e., by a magnetic force in a vertical direction resulting from a gradient magnetic field (the second term in the above expression) acting on the first particles in the supporting liquid). The balanced height depends on the density and magnetic susceptibility of the first particles. If the liquid surface of the supporting liquid is lower than the balanced height where the apparent weight represented by the above expression is zero, the first particles are disposed at the liquid surface of the supporting liquid.
If (ρ1−ρ)<0 (i.e., in the case where the first particles float at the liquid surface of the supporting liquid when a gradient magnetic field is not applied), the magnetic susceptibility of the supporting liquid is given such that (χ1−χ)<0 and the product of the magnetic field and the magnetic field gradient is a large negative number, so that the apparent weight represented by the above expression is positive and the first particles settle in the supporting liquid. For example, when a magnet is provided over a tank storing the supporting liquid and a gradient magnetic field in which the magnetic field increases in the vertically upward orientation is applied to the supporting liquid, the first particles settle in the supporting liquid. At the balanced height or position where the apparent weight represented by the above expression is zero, the first particles stably float by the magneto-Archimedes effect. If the bottom face of the separation tank storing the supporting liquid is higher than the balanced height where the apparent weight represented by the above expression is zero, the first particles are disposed on the bottom face of the separation tank.
Since the magnetic susceptibility of the second particles is higher than that of the supporting liquid, (χ2−χ)0>0 in the above expression representing the apparent weight. As a result, a gradient magnetic field is applied as described above in the case where (ρ2−ρ)>0 (i.e., a gradient magnetic field is applied such that the first particles levitate in the case where (ρ1−ρ)>0), so that the apparent weight of the particles is not zero (and remains positive) and the second particles settle in the supporting liquid. Moreover, a gradient magnetic field is applied as described above in the case where (ρ2−ρ)<0 (i.e., a gradient magnetic field is applied such that the first particles settle in the case where (ρ1−ρ)<0), so that the apparent weight of the particles is not zero (and remains negative) and the second particles float at the liquid surface of the supporting liquid. Thus, the first particles and the second particles in the supporting liquid are vertically separated.
The present invention uses a magnetic filter means to catch the second particles in the supporting liquid. A magnetic filter means is conventionally used to adsorb paramagnetic materials and ferromagnetic materials in the HGMS method. One or more net plates formed of fine wires of a ferromagnetic material, an expanded metal or a punching metal, or a large number of prisms and spheres formed of a ferromagnetic material can be used as a magnetic filter means of the present invention, and a shape suitable for an apparatus for carrying out the present invention may be selected. If a gradient magnetic field acts on the second particles so as to settle them, a magnetic filter means is provided on the bottom face of the separation tank or in the vicinity thereof. If a gradient magnetic field acts on the second particles so as to float them at the liquid surface of the supporting liquid, a magnetic filter means is provided at the liquid surface of the supporting liquid or in the vicinity thereof.
In the present invention, by applying a gradient magnetic field to the supporting liquid in the separation tank, the first particles are floated in the supporting liquid (or at the liquid surface of the supporting liquid) by the magneto-Archimedes effect, or the first particles are sunk on the bottom face of the separation tank by the magneto-Archimedes effect as described above, so that the first particles are arranged at a substantially constant height in a vertical direction. Furthermore, as described below, the first particles may be gathered in the regions spaced laterally or outward from the magnetic filter means in the separation tank by supplying a magnetic force in a lateral direction or a horizontal direction resulting from a gradient magnetic field. The second particles are caught with a magnetic filter means as described above.
In the present invention, the magnetic field gradient of the gradient magnetic field may have a component of a horizontal direction (∂B/∂x and/or ∂B/∂y) in addition to a component of a vertical direction (∂B/∂z) (x and y are coordinates in horizontal directions that are orthogonal to each other). Moreover, in the present invention, a gradient magnetic field may have a component of a horizontal direction. When the magnetic field gradient of the gradient magnetic field has a component of a horizontal direction in addition to a component of a vertical direction, or a gradient magnetic field has a component of a horizontal direction, a magnetic force in a horizontal direction expressed in a similar manner to the second term of the above expression representing the apparent weight acts on the first particles, so that the first particles travel in a horizontal direction. A floating height of the first particles may vary as the first particles travel horizontally. For example, if the magnetic field gradient of the gradient magnetic field has a horizontal component (∂B/∂x) in addition to a vertical component (∂B/∂z), the first particles float or sink by the magneto-Archimedes effect, travel along the x axis, and are finally gathered on the wall surface of the separation tank at a substantially constant height in a vertical direction, that is, at the balanced height where the apparent weight is zero, at the liquid surface of the supporting liquid, or on the bottom face of the separation tank (the first particles may be gathered on or below a shelf or the like provided in the separation tank). For example, a magnetic filter means is arranged on the opposite side to the wall surface in the separation tank, so that the first particles travel in a lateral direction so as to move away from the magnetic filter means. A magnetic force in an opposite direction to a force applied to the first particles (at the same position as the second particles) is applied to the second particles by applying a gradient magnetic field to the second particles, and therefore, the second particles travel in the opposite direction of the first particles, approach the magnetic filter means and are caught. Thus, the first particles and the second particles are horizontally separated.
For example, if a gradient magnetic field is axially symmetrical about its central axis in a vertical direction and a magnetic field gradient or a magnetic field gradient has a component of a radial direction in addition to a component of a vertical direction, the first particles float or sink in the supporting liquid by the magneto-Archimedes effect, travel in a radial direction (i.e., radially from the central axis) with a magnetic force in a radial direction, and are finally disposed on the wall surface of the separation tank. The first particles are arranged on the wall surface at the balanced height, at the liquid surface of the supporting liquid, or on the bottom face of the separation tank. In order to increase the distance between the region for gathering the first particles and a magnetic filter means for catching the second particles (and, additionally, to strongly excite a magnetic filter means with a gradient magnetic field) and enhance the accuracy of separation, it is desirable to arrange the magnetic filter means in the vicinity of the central axis of the gradient magnetic field, or so as to intersect with or cross orthogonally to the central axis.
In the present invention, a solenoid superconducting electromagnet, a superconducting bulk magnet, a non-superconducting electromagnet, or a permanent magnet may be used as a magnetic field generating means for generating a gradient magnetic field, and there is no limitation thereon as long as the effect of the present invention can be obtained. It is preferable that a magnetic filter means is arranged in proximity to a magnetic pole of the magnetic field generating means or in the region where the gradient magnetic field is large. The magnetic field generating means may include a plurality of magnets and a gradient magnetic field may be obtained by composition of magnetic fields generated by these magnets. For example, the magnetic field generating means may include a first magnet that applies a gradient magnetic field in a vertical direction for floating or sinking the first particles by the magneto-Archimedes effect and exciting the magnetic filter means, and a second magnet that applies a gradient magnetic field in a horizontal direction for causing the first particles to travel in a lateral direction. Furthermore, the second magnet may generate a gradient magnetic field intermittently or in a predetermined cycle.
If a difference between the magnetic susceptibility of the second particles χ2 and the magnetic susceptibility of the supporting liquid χ is small (e.g., the second particles are paramagnetic or antiferromagnetic), the influence of the term depending on a gradient magnetic field in the apparent weight represented by the above expression is small. A magnetic force in a horizontal or a radial direction for causing the second particles to travel in a lateral direction is also small. Furthermore, if the particle size of the second particle is small, the motion of the second particles in the supporting liquid is easily affected by hydrodynamic effects. Since a strong magnetic force acts on the second particles only in the vicinity of the magnetic filter means, some of the second particles with a small particle size may remain suspended in the supporting liquid without being caught with the magnetic filter means even if a gradient magnetic field is applied thereto. Furthermore, some of the second particles precipitated on the bottom face of the separation tank at a site spaced from the magnetic filter means may remain stationary at that site.
In the present invention, the second particles suspended or precipitated at a site spaced from the magnetic filter means may be introduced to the magnetic filter means by stirring the supporting liquid in a state of applying a gradient magnetic field thereto. This enables a period of time required for the separation treatment to be shortened or the region where the second particles are distributed in the supporting liquid to be narrowed. Examples of a method for stirring the supporting liquid include mechanical stirring, vibration stirring, jet stream stirring, stirring by blowing gas, and ultrasonic stirring, and a plurality of methods may be used together. It is preferable that a flow toward the magnetic filter means is generated in the supporting liquid by stirring. In the present invention, in addition to a gradient magnetic field, a flow of the supporting liquid in the separation tank may be used to separate and collect the first particles and the second particles. For example, when a gradient magnetic field that is axially symmetrical about its central axis in a vertical direction is used to gather the first particles on the inner wall of a cylindrical separation tank (see the first embodiment and the like described below), a flow may assist to gather the first particles by generating a circulating flow directed to the bottom face along the inner wall in the supporting liquid in the separation tank (to an extent that the gathered particles are not diffused). Moreover, the first particles may be collected from the separation tank by generating a flow of the supporting liquid that is orthogonal with respect to a magnetic force in a horizontal direction for acting on the gathered first particles or a flow in a circumferential direction in the supporting liquid that is orthogonal with respect to a magnetic force in a radial direction for acting on the gathered first particles (see the fifth embodiment described below).
There is no limitation on the depth of the supporting liquid in the separation tank (a distance from the bottom face of the separation tank to the supporting liquid) as long as the effect of the present invention can be obtained. When the first particles are caused to travel to a region lateral to or outward from the magnetic filter means by a magnetic force in a horizontal direction due to a gradient magnetic field and gathered therein (e.g., see the first to fifth embodiment described below), it is possible to largely increase the distance between the region where the first particles are gathered and the region where the second particles are caught in a lateral, horizontal, or radial direction. Accordingly, in this case, the first particles and the second particles need not be separated in a vertical direction, and therefore, the depth of the supporting liquid in the separation tank may be relatively small (e.g., the first particles may travel in a horizontal direction while floating at the liquid surface of the supporting liquid). Furthermore, when the first particles are caused to travel to a region lateral to or outward from the magnetic filter means by a magnetic force in a horizontal direction due to a gradient magnetic field and gathered therein, the first particles need not be levitated at a high position or sunk in a low position, and therefore, the volume magnetic susceptibility of the supporting liquid need not be enlarged compared to a conventional method. Accordingly, with the present invention, the concentration of paramagnetic salt in the supporting liquid, and the viscosity of the supporting liquid as well can be reduced to shorten a period of time required for the separation treatment of the mixture.
The mixture separation method of the present invention may be performed by continuous processing or batch processing, and the mixture separation apparatus of the present invention may be a continuous type or a batch type.
In
In the present embodiment, the supporting liquid in which the first particles and the second particles are suspended is released from an outlet provided in the vicinity of the center of the separation tank (7) bottom face into the separation tank (7). A magnetic filter means (9) is horizontally arranged over the outlet of the supporting liquid. In the present embodiment, two rectangular net plates formed of fine wires of a ferromagnetic material are used as the magnetic filter means (9). These net plates are arranged, for example, on the bottom face of the separation tank (7) in a vertically overlapped state. The number of net plates may be changed as appropriate.
A magnetic field generating means (11) for generating a gradient magnetic field is provided under the separation tank (7). In the present embodiment, a solenoid superconducting magnet is used as the magnetic field generating means (11), and the coil central axis A (indicated by a dashed line in
In the present embodiment, a stirring means (13) for stirring the supporting liquid is provided in the separation tank (7). A stirring blade that is immersed in the supporting liquid stored in the separation tank (7) is used as the stirring means (13). The stirring blade is rotated by a driving means (not shown) and generates a flow directed toward the magnetic filter means (9) in the supporting liquid in the separation tank (7). For example, an ultrasonic generating apparatus may be used as the stirring means (13) to stir the supporting liquid using ultrasonic waves.
One end of the channel for collecting the supporting liquid is immersed in the supporting liquid in the separation tank (7), and the channel has a second valve (15) that is opened and closed as appropriate depending on the process to be performed by the separation apparatus and a second pump (17) for letting the supporting liquid flow, connecting the separation tank (7) and the storage tank (1). The channel is used to return the supporting liquid from which the first particles and the second particles are (to some extent or substantially) removed to the storage tank (1). While the supporting liquid circulates between the storage tank (1) and the separation tank (7), the inflow of the supporting liquid into the separation tank (7) and the outflow therefrom are adjusted so that the amount of the supporting liquid in the separation tank (7) is substantially constant.
As shown in
An inlet of a channel for collecting the first particles is provided on the inner wall of the separation tank (7). The channel includes a third valve (19) that is opened and closed as appropriate depending on the process to be performed by the separation apparatus and a third pump (21) for sucking the first particles, and is used to suck the first particles and send them to a storage tank (not shown). While the first valve (3) and the second valve (15) are open and the supporting liquid circulates between the storage tank (1) and the separation tank (7), the third valve (19) is closed. When the supporting liquid circulates between the storage tank (1) and the separation tank (7), the first particles accumulated on the edge of the bottom face of the separation tank (7) increase over time.
The present embodiment is configured so that the supporting liquid sent from the storage tank (1) to the separation tank (7) flows toward the magnetic filter means (9). Many of the second particles that are contained in the supporting liquid sent from the storage tank (1) to the separation tank (7) are trapped by the magnetic filter means (9). At that time, the second particles that are not trapped by the magnetic filter means (9) are returned to the magnetic filter means (9) and trapped by stirring the supporting liquid with the stirring means (13) so that a flow directed toward the magnetic filter means (9) is generated, or are returned to the storage tank (1) together with the supporting liquid. The supporting liquid is stirred by the stirring means (13) to an extent that the second particles caught do not separate from the magnetic filter means (9) and the first particles gathered separate from the edge of the bottom face of the separation tank (7). When the supporting liquid circulates between the storage tank (1) and the separation tank (7), the second particles caught with the magnetic filter means (9) increase over time. Moreover, the stirring means (13) stirs the supporting liquid so as to generate a flow directed toward the magnetic filter means (9), so that the second particles that sink on the bottom face of the separation tank (7) are trapped by the magnetic filter means (9). In the present embodiment, the magnetic filter means (9) is arranged over the outlet of the supporting liquid, but there is no limitation on the flow direction of the supporting liquid that is released into the separation tank (7) with respect to the magnetic filter means (9) in the embodiments of the present invention.
For example, a channel connected to the storage tank (1) via the first valve (3) and the first pump (5) may be configured so that the supporting liquid is released toward the magnetic filter means (9) from above the magnetic filter means (9).
When the above-described processing has been performed for a predetermined period of time, for example, the first valve (3) and the second valve (15) are closed and the circulation of the supporting liquid between the storage tank (1) and the separation tank (7) is stopped. Then, as shown in
After the stirring means (13) has stopped, as shown in
After the process of collecting the second particles is performed, the fourth valve (23) is closed and the second valve (15) in addition to the first valve (3) is opened, so that the above-described separation process is repeatedly performed. The separation apparatus of the present embodiment may be configured so that the process of collecting the second particles is performed when the process of collecting the first particles has been performed a predetermined number of times.
In the separation process, the collecting member (31) is mounted on the bottom face of the separation tank (7), and as shown in
In the separation process, the second particles (indicated by white circles) are trapped by the magnetic filter means (9). The first particles (indicated by black triangles) are caused to travel toward the right side wall surface of the separation tank (7) due to the magnetic force F in a horizontal direction, and float at the balanced height on the wall surface or at the liquid surface of the supporting liquid, or are gathered on the edge of the bottom face of the separation tank (7) at the lower end of the wall surface.
An annular magnetic filter means (9) that is arranged so as to fit around the inner wall (73) is placed on the bottom portion (71). For example, a belt-like net or punching metal of a ferromagnetic material with an annular external shape is used for the magnetic filter means (9), and the width thereof is shorter than that of the annular belt-like bottom portion (71). The magnetic filter means (9) may be formed in a cylindrical shape and arranged so as to fit around the inner wall (73).
The separation tank (7) includes an inlet tube (61) for introducing the supporting liquid in which the mixture containing the first particles (indicated by black triangles) and the second particles (indicated by white circles) is suspended and an outlet tube (63) for discharging the supporting liquid from the separation tank (7). The supporting liquid is stored between the inner wall (73) and the outer wall (75). A storage tank for storing the supporting liquid (including the mixture), a pump for sending out the supporting liquid, and the like (not shown) are provided on the upstream side of the inlet tube (61). The amount of supporting liquid stored in the separation tank (7) is maintained constant, for example, by adjusting the flow rate of the supporting liquid sent out from the inlet tube (61).
In the present embodiment, both of the inlet tube (61) and the outlet tube (63) are arranged so as to penetrate the outer wall (75) of the separation tank (7) and be in contact with the inner surface of the outer wall (75). In addition, the inlet tube (61) is arranged in proximity to the bottom portion (71) and the outlet tube (63) is arranged above the inlet tube (61). The inlet tube (61) and the outlet tube (63) are arranged so that an annular flow of the supporting liquid is generated in the separation tank (7) and, additionally, the supporting liquid coming from the inlet tube (61) does not directly flow into the outlet tube (63).
The magnetic field generating means (11) applies a gradient magnetic field as described in the first embodiment to the supporting liquid in the separation tank (7). The gradient magnetic field causes the first particles in the supporting liquid coming out of the inlet tube (61) to be floated at the balanced height where the apparent weight is zero by the magneto-Archimedes effect in the separation tank (7), and to be disposed or gathered at the inner surface of the outer wall (75) by the action of the magnetic force F in a radial direction (where the first particles behind the inner wall (73) is indicated by white triangles in
The second particles in the supporting liquid in the separation tank (7) are caught with the magnetic filter means (9). The second particles caught with the magnetic filter means (9) are collected, for example, by being sucked with a suction tube (not shown). When the second particles are collected, it is preferable that the magnetic filter means (9) is demagnetized, for example, by rising the magnetic filter means (9) after supply of the supporting liquid to the separation tank (7) is stopped (or supporting liquid containing no mixture is introduced to the separation tank (7)) and the first particles are collected from the separation tank (7).
When the first particles sent to the separation tank (7) are disposed not at the balanced height but on the bottom portion (71) of the separation tank (7), the first particles are separated and collected by introducing the supporting liquid from the outlet tube (63) to the separation tank (7) and discharging the supporting liquid together with the first particles from the inlet tube (61) (by switching the functions of the inlet tube (61) and the outlet tube (63)).
The first to fifth embodiments described above are suitable for a case where the densities of the first particles and the second particles are larger than that of the supporting liquid. The first to fifth embodiments are changed as appropriate in a case where the densities of the first particles and the second particles are smaller than that of the supporting liquid. For example, in the first to fifth embodiments, the magnetic field generating means (11) is provided above the liquid surface of the supporting liquid stored in the separation tank (7) to apply a gradient magnetic field to the supporting liquid so that the first particles are sunk, and the magnetic filter means (9) is arranged in the vicinity of the lower end of the magnetic field generating means (11) in the supporting liquid in the separation tank (7).
In the first to fourth embodiments, the stirring means (13) is arranged in the vicinity of the bottom face of the separation tank (7). The arrangement and shape of the channel, suction tube (27) and collecting member (31) for collecting the first particles and the second particles are changed as appropriate. In the fifth embodiment, the supporting liquid will be introduced from the outlet tube (63) to the separation tank (7), and discharged from the inlet tube (61).
In the first to fifth embodiment described above, a gradient magnetic field to be applied to the supporting liquid in the separation tank (7) is applied so that the first particles float in the supporting liquid or at the liquid surface thereof at least over the magnetic filter means (9) by the magneto-Archimedes effect. Furthermore, it is preferable that the gradient magnetic field is applied so that the first particles float in the supporting liquid or at the liquid surface thereof in a region where the first particles are gathered (and, additionally, in a region in the vicinity thereof) by the magneto-Archimedes effect. When the densities of the first particles and the second particles are lighter than that of the supporting liquid, the configurations of the apparatuses of these embodiments are changed so that the first particles are floated in the supporting liquid or disposed on the bottom face of the separation tank by the magneto-Archimedes effect, at least under the magnetic filter means (9). Furthermore, it is preferable that the gradient magnetic field is applied so that the first particles are floated in the supporting liquid or sunk to the bottom face of the separation tank by the magneto-Archimedes effect, in a region where the first particles are gathered (and, additionally, in a region in the vicinity thereof).
In the first to fifth embodiments of the present invention, the first particles are caused to travel to a region lateral to or outward from the magnetic filter means (9) due to the magnetic force in a horizontal direction or a radial direction and gathered in the region, but the first particles may be gathered in a state of floating over the magnetic filter means (9).
In
In the same manner as the above-described embodiments, the supporting liquid in which the first particles and the second particles are suspended is released from an outlet provided on the side wall of the separation tank (7) in the vicinity of the bottom face thereof into the separation tank (7). The magnetic filter means (9) including two net plates in the same manner as the above-described embodiments is horizontally arranged in proximity to the bottom face of the separation tank (7) so as to cover the bottom face of the separation tank (7) above the outlet of the supporting liquid.
The magnetic field generating means (11) for generating a gradient magnetic field is provided under the separation tank (7). In the present embodiment, a superconducting bulk magnet in a column shape or a disk shape is used as the magnetic field generating means (11) and, for example, a gradient magnetic field in a downward direction where the magnitude thereof monotonously decreases in an upward direction is applied to the supporting liquid in the separation tank (7). The separation tank (7) is formed of nonmagnetic materials, and planes formed by the two net plates serving as the magnetic filter means (9) are arranged so as to be substantially orthogonal with respect to the gradient magnetic field.
The present embodiment differs from the above-described embodiments in that it is not required to cause the magnetic force in the horizontal direction or the radial direction resulting from the gradient magnetic field to act on the first particles. Accordingly, a component of a horizontal or a radial direction of the magnetic field and a component of a horizontal or a radial direction of the magnetic field gradient thereof are caused to be zero or extremely minute in the separation tank (7). However, even in the sixth embodiment, the magnetic force in a horizontal direction or a radial direction may act on the first particles. In this case, the first particles will be gathered in an annular shape along the inner wall of the separation tank (7).
In the same manner as the above-described embodiments, the stirring blade that is immersed in the supporting liquid stored in the separation tank (7) is used as the stirring means (13). The stirring blade is rotated by a driving means (not shown) and generates a flow directed toward the magnetic filter means (9). It is preferable that the stirring blade is provided at a position vertically spaced from the floating position or the balanced position of the first particles. In the present embodiment, the stirring blade is arranged between the liquid surface of the supporting liquid stored in the separation tank (7) and the balanced position of the first particles described below. The supporting liquid may be stirred by causing the stirring blade to generate a rotational flow in the supporting liquid in the separation tank.
An inlet of a channel for collecting the supporting liquid is provided on the upper portion of the side wall of the separation tank (7). The channel includes a second valve (15) that is opened and closed as appropriate depending on the process to be performed by the separation apparatus and a second pump (17) for letting the supporting liquid flow from the separation tank (7) to the storage tank (1), and is used to return the supporting liquid from which the first particles and the second particles are (to some extent or substantially) removed to the storage tank (1). While the supporting liquid circulates between the storage tank (1) and the separation tank (7), the inflow of the supporting liquid into the separation tank (7) and the outflow therefrom are adjusted so that the amount of the supporting liquid in the separation tank (7) is substantially constant.
As shown in
When the supporting liquid circulates between the storage tank (1) and the separation tank (7), the first particles gathered at the balanced height in the supporting liquid stored in the separation tank (7) increase over time. The stirring means (13) stirs the supporting liquid to induce the first particles in a region significantly spaced from the balanced height to the balanced height and gather them. Some of the first particles are returned to the storage tank (1) together with the supporting liquid. The degree of stirring of the supporting liquid by the stirring means (13) is adjusted so that the first particles induced to the balanced height remain at the substantially same height or are restrained in the vicinity of the height.
In the sixth embodiment, the first particles in the supporting liquid are floated at the balanced height or position corresponding to the magnetic susceptibility and the density of the first particles in the supporting liquid by the magneto-Archimedes effect, and gathered. If the particle size of the first particle is small or the viscosity of the supporting liquid is high, the motion of the first particles in the supporting liquid in the separation tank (7) is easily affected by hydrodynamic effects. Accordingly, if the particle size of the first particle is small or the viscosity of the supporting liquid is high, the first particles in a region significantly spaced from the balanced height where the apparent weight is zero tend to maintain a state of being suspended in the supporting liquid. It will take a very long time for the first particles in such a region travel to the vicinity of the balanced height by spontaneous sedimentation and obtain the magneto-Archimedes effect.
In the sixth embodiment, the stirring means (13) stirs the supporting liquid in the separation tank (7) in a state where a gradient magnetic field is applied thereto to induce the first particles suspended in a position spaced from the balanced position where the apparent weight is zero to a height region or range (including the balanced height) where the Archimedes effect works effectively, and restrain the first particles. Thereby, the period of time required for the separation treatment is shortened. Furthermore, stirring the supporting liquid is effective in suppressing aggregation of the first particles and second particles.
If the supporting liquid is strongly or vigorously stirred, the first particles that have traveled to the vicinity of the balanced height move away from the balanced height. Accordingly, the stirring means (13) stirs the supporting liquid so as not to prevent the first particles from being gathered by the magneto-Archimedes effect. When stirring is stopped, the gathered first particles are fixed at the substantially balanced height in the supporting liquid (in fact, a slight gap occurs in the heights of the particles due to contact between the particles or the like, as well as other factors). It is possible to gather the first particles at the substantially balanced height or restrain the first particles in a certain height region including the balanced height in the supporting liquid even during stirring by adjusting the stirring strength, such as the number of rotations of the stirring blade.
In the same manner as the above-described embodiments, the supporting liquid sent from the storage tank (1) to the separation tank (7) flows through the magnetic filter means (9), so that many of the second particles that are contained in the supporting liquid sent from the storage tank (1) to the separation tank (7) are trapped by the magnetic filter means (9). At that time, the second particles that are not trapped by the magnetic filter means (9) are returned to the magnetic filter means (9) and trapped by stirring the supporting liquid with the stirring means (13), or are returned to the storage tank (1) together with the supporting liquid. When the supporting liquid circulates between the storage tank (1) and the separation tank (7), the second particles caught with the magnetic filter means (9) increase over time.
When the above-described process has been performed for a predetermined period of time, the first valve (3) and the second valve (15) are closed and the circulation of the supporting liquid between the storage tank (1) and the separation tank (7) is stopped. After that, as shown in
After the process of collecting the first particles, a process of collecting the second particles is performed. After the third valve (19) is closed, as shown in
Moreover, as shown in
After the process of collecting the second particles as shown in
The sixth embodiment is suitable for a case where the densities of the first particles and the second particles are larger than that of the supporting liquid. The separation apparatus as shown in
In the first to sixth embodiments described above, the mixture contains the first particles and the second particles, but a different type of particles from these particles, that is, the third particles may be contained in the mixture in the mixture separation apparatus of the present invention. The third particles may be formed of, for example, a diamagnetic material. The third particles may be disposed over or under the first particles by the magneto-Archimedes effect and gathered separately from the first particles. Moreover, the third particles may be a ferromagnetic material and trapped by the magnetic filter means (9) together with the second particles.
The embodiments for separating, by type, a mixture containing the first particles and the second particles have been described, but it is clear from the above description that the present invention is applicable to a case where either the first particles or the second particles are separated and collected from the mixture. When one or more different types of particles from the first particles and the second particles are contained in the mixture, it is clear that, by the above-described method, the first particles or the second particles are gathered or caught separately from the other particles and either the first particles or the second particles can be separated and collected from the mixture.
Hereinafter, examples in which the mixture separation method of the present invention was used to separate the mixture will be described.
A mixture of titanium particles and glass particles was adjusted by mixing 0.1 g of titanium powder with a particle size of 45 μm or less (manufactured by Wako Pure Chemical Industries, Ltd.; magnetic susceptibility (SI unit system): +1.80×10−4, density: 4.5 g/cm3) and 0.05 g of glass (silica) powder with a particle size of 1 to 2 μm (manufactured by RARE METALLIC Co., Ltd.; magnetic susceptibility (SI unit system): −1.66×10−4, density: 2.2 g/cm3).
Two wire nets in a square shape (10 mm×10 mm, 30 mesh, wire diameter: 0.6 mm) formed of SUS430 serving as a ferromagnetic material were vertically stacked on the bottom of a glass laboratory dish with an inner diameter of 60 mm and a height of 5 mm, and a 5 wt % aqueous solution of manganese chloride (magnetic susceptibility (SI unit system): +3.94×10−5) to be used as the supporting liquid was placed into the center of the laboratory dish. After this, the adjusted mixture described above was placed into the laboratory dish and the supporting liquid was stirred. Thereby, as shown in
Next, the laboratory dish containing the supporting liquid in which the titanium particles and the glass particles were suspended as shown in
When the gradient magnetic field was applied to the supporting liquid in the laboratory dish, the glass particles traveled toward the inner wall surface of the laboratory dish and were immediately (in less than 1 second) gathered in an annular shape on the edge of the bottom face of the laboratory dish. Furthermore, when the supporting liquid in the laboratory dish was stirred with a stirring rod for 5 to 10 seconds, as shown in
It was confirmed that a gradient magnetic field is thus applied to the paramagnetic supporting liquid in which the mixture of diamagnetic particles (glass particles) and paramagnetic particles (titanium particles) is suspended based on the present invention, so that the diamagnetic particles can be gathered in a region spaced from the magnetic filter means (wire net) and the paramagnetic particles can be caught with the magnetic filter means excited by the applied gradient magnetic field. Furthermore, it was confirmed that diamagnetic particles or paramagnetic particles can be separated from such a mixture based on the present invention. Moreover, it was confirmed that diamagnetic particles and paramagnetic particles can be separated by type, or diamagnetic particles or paramagnetic particles can be separated from the mixture by the present invention even if a 5 wt % aqueous solution of manganese chloride, which has a relatively low concentration, is used as the supporting liquid and the supporting liquid is stored at a very shallow depth of approximately 5 mm.
The two wire nets used in the first example were stacked on the bottom of a glass vial with an inner diameter of 20 mm and a height of 50 mm, and 25 ml of a 10 wt % aqueous solution of manganese chloride (magnetic susceptibility (SI unit system): +8.57×10−5) to be used as the supporting liquid was placed into the vial. The same mixture as in the first example was placed into the vial and the supporting liquid was stirred. Thereby, as shown in
Next, the vial containing the supporting liquid in which the titanium particles and the glass particles were suspended as shown in
When the gradient magnetic field was applied to the supporting liquid in the vial, it was confirmed that the glass particles floated in the supporting liquid and gathered at a position approximately 20 mm above the upper end surface of the vacuum chamber (magnitude of the magnetic field: approximately 1.2 T, magnitude of the magnetic field gradient: approximately 70 T/m). When the supporting liquid in the vial was stirred with a stirring rod for 3 minutes (it was confirmed that the glass (silica) particles were gathered at the above-described position while stirring), as shown in
As shown in
A mixture of titanium particles and glass particles was adjusted by mixing 0.1 g of the above-described titanium powder and 0.15 g of glass (silica) beads with a particle size of approximately 2 mm (manufactured by AS ONE Corporation; magnetic susceptibility (SI unit system): −1.66×10−4, density: 2.2 g/cm3). The same treatments as in the second example were performed, except that the supporting liquid was stirred for 2 minutes.
Before a gradient magnetic field was applied to the vial, the titanium particles and the glass particles were suspended and the supporting liquid was also cloudy black in the third example as in the initial state of the second example shown in
A mixture of nickel oxide particles and glass particles was adjusted by mixing 0.1 g of nickel oxide powder with a particle size of 20 μm or less (manufactured by Wako Pure Chemical Industries, Ltd.; magnetic susceptibility (SI unit system): +4.50×10−4, density: 6.7 g/cm3) and 0.05 g of glass (silica) granules used in the first example. The same treatments as in the second example were performed, except that the vial was mounted through an acrylic plate with a thickness of 2 mm on the upper end surface of the above-described vacuum chamber housing a superconducting bulk magnet.
Before a gradient magnetic field was applied to the vial, the nickel oxide particles and the glass particles were suspended and the supporting liquid was cloudy green as shown in
A mixture of nickel oxide particles and glass particles was adjusted by mixing 0.1 g of nickel oxide described above and 0.15 g of glass (silica) beads used in the third example. The same treatments as in the fourth example were performed, except that the supporting liquid was stirred for 1 minute.
Before a gradient magnetic field was applied to the vial, the nickel oxide particles and the glass particles were suspended and the supporting liquid was also cloudy green in the fifth example as in the initial state of the fourth example shown in
It was actually confirmed by the second example that when the second particles are formed of a paramagnetic material and the first particles are formed of a diamagnetic material, the mixture containing these first and second particles can be separated by type using the present invention. Furthermore, it was actually confirmed by the fourth example that when the second particles are formed of an antiferromagnetic material and the first particles are formed of a diamagnetic material, the mixture containing these first and second particles can be separated by type using the present invention. Moreover, it can be understood that the present invention is applicable to particles of various sizes or mixture of particles of various sizes with reference to the third and fifth examples in addition to the second and fourth examples.
Hereinafter, comparative examples implemented using conventional technologies in order to compare the conventional technologies and the present invention will be described.
A mixture of titanium particles and glass particles was adjusted in the same manner as in the second example. The mixture was placed into a vial containing 25 ml of a 10 wt % aqueous solution of manganese chloride serving as the supporting liquid and stirred. It should be noted that the above-described wire net was not arranged in the vial. After being stirred, in the same manner as in the second example, a gradient magnetic field was applied to the supporting liquid in the vial in which the titanium particles and the glass particles were suspended, and the vial was allowed to stand for 3 minutes. Then, it was confirmed that the glass particles gathered at a position 20 mm above the upper end surface of the vacuum chamber. However, although those titanium particles which had a large particle size sunk to the bottom face of the vial, most of the titanium particles (and some of glass particles) remained suspended in the supporting liquid, and the supporting liquid remained cloudy black as in the initial state shown in
A mixture of titanium particles and glass particles was adjusted in the same manner as in the second example. The mixture was placed into a vial in which 25 ml of a 10 wt % aqueous solution of manganese chloride serving as the supporting liquid was contained and the two above-described wire nets were arranged on the bottom portion, and stirred. After that, in the same manner as in the second example, a gradient magnetic field was applied to the supporting liquid in the vial in which the titanium particles and the glass particles were suspended, and the vial was allowed to stand for 5 minutes. Then, it was confirmed that the glass particles gathered at a position 20 mm above the upper end surface of the vacuum chamber as shown in
A mixture of nickel oxide particles and glass particles was adjusted in the same manner as in the fourth example. The mixture was placed into a vial containing 25 ml of a 10 wt % aqueous solution of manganese chloride serving as the supporting liquid and stirred. It should be noted that the above-described wire net was not arranged in the vial. After being stirred, in the same manner as in the fourth example, a gradient magnetic field was applied to the supporting liquid in the vial in which the nickel oxide particles and the glass particles were suspended, and the vial was allowed to stand for 2 minutes. Then, it was confirmed that the glass particles were gathered at a position 20 mm above the upper end surface of the vacuum chamber. However, although those titanium particles which had a large particle size sunk to the bottom face of the vial, most of the titanium particles remained suspended in the supporting liquid, and the supporting liquid remained cloudy green as in the initial state shown in
A mixture of nickel oxide particles and glass particles was adjusted in the same manner as in the second example. The mixture was placed into a vial in which 25 ml of a 10 wt % aqueous solution of manganese chloride serving as the supporting liquid was contained and the two above-described wire nets were arranged on the bottom portion, and stirred. After that, in the same manner as in the fourth example, a gradient magnetic field was applied to the supporting liquid in the vial in which the titanium particles and the glass particles were suspended, and the vial was allowed to stand for 5 minutes. Then, it was confirmed that the glass particles gathered at a position 20 mm above the upper end surface of the vacuum chamber. However, although a certain amount of the titanium particles adsorbed on the wire nets, a significant amount of the titanium particles (and part of glass particles) remained suspended in the supporting liquid, and the supporting liquid was cloudy. Thus, in the fourth comparative example in which the magneto-Archimedes method and the HGMS method were used, the mixture containing the paramagnetic particles and the diamagnetic particles could not be favorably separated in a short time as in the fourth example.
It is found from the result of the first comparative example that it is difficult to separate the same mixture as in the second example by the magneto-Archimedes effect using the same supporting liquid and gradient magnetic field as in the second example, that is, with the present invention, a mixture containing paramagnetic particles and diamagnetic particles can be separated without increasing the magnetic susceptibility of the supporting liquid or enlarging the gradient magnetic field compared to conventional technologies. Moreover, it is found from the result of the third comparative example that it is not possible to separate the same mixture as in the fourth example by the magneto-Archimedes effect using the same supporting liquid and gradient magnetic field as in the fourth example, that is, with the present invention, a mixture containing antiferromagnetic particles and diamagnetic particles can be separated without increasing the magnetic susceptibility of the supporting liquid or enlarging the gradient magnetic field compared to conventional technologies. Furthermore, it can be understood from the results of the second and fourth comparative examples that the period of time required for the separation treatment of the mixture is significantly shortened or the mixture can by favorably separated by stirring the supporting liquid.
Since it is possible to separate, by type, a mixture containing two types of particles and separately collect the particles from the mixture, or to separate a specific type of particle from such a mixture, the present invention is applicable to recycle processing of industrial wastes and household garbage. Particularly, since the present invention is suitable for separating a mixture containing diamagnetic particles and paramagnetic particles, the present invention is applicable to collection of rare earth from household electric appliances or the like.
The description above has been given for illustrating the present invention, and should not be construed as limiting the invention described in the claims or as restricting the claims. Furthermore, it will be appreciated that the constituent elements of the invention are not limited to those in the foregoing examples, and various modifications can be made without departing from the technical scope described in the claims.
Number | Date | Country | Kind |
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2011-183958 | Aug 2011 | JP | national |
2011-235397 | Oct 2011 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP2012/071391 | 8/24/2012 | WO | 00 | 2/19/2014 |