WO2019172359A1 - Dissolved matter removal device, filtration aid used therewith, and dissolved matter removal method - Google Patents

Abstract

Provided are a dissolved matter removal device, a filtration aid used therewith, and a dissolved matter removal method with which it is possible to more efficiently remove hard-to-remove dissolved matter. As such, this dissolved matter removal device 1 comprises a spring-shaped filter 2 and a filtration aid 3 disposed around the spring-shaped filter 2. The filtration aid 3 contains a polymeric material comprising a graft chain to which is bonded a chelate group and/or an ion exchange group. The grafting rate of the graft chain in the polymeric material is at least 10% and less than 150%.

Description

SOLUTION REMOVAL DEVICE, FILTER AID USED FOR SAME, AND SOLUTION REMOVAL METHOD

The present invention relates to a lysate removal apparatus, a filter aid used therefor, and a lysate removal method.

Boron is used in various applications such as heat-resistant glass, glass fiber, new ceramics, amorphous alloys, glazes, fertilizers, nuclear power, personal computer TFT displays, and is widely present in the environment.

Moreover, although boron is an essential element for human beings, it has been pointed out that continuous ingestion of an excessive amount of boron of several mg or more per day may cause health problems such as a decrease in reproductive function. Therefore, as a regulation for boron drainage, the drainage standard is set to 10 mg / L by the Water Pollution Control Law, and the environmental standard value is set to 1 mg / L or less, which is 1/10 of the standard value.

In addition to boron, cadmium, lead, hexavalent chromium, arsenic, mercury, selenium, fluorine, and the like are also harmful elements (metals and metalloids) that can cause serious health problems such as kidney damage.

By the way, as a general treatment of the above harmful elements, a coagulation precipitation method and a resin adsorption method are known. However, these methods are slow in processing speed, and the coagulation sedimentation method has problems such as generation of sludge in the processing process, and development of new wastewater treatment technology is strongly demanded.

However, as described above, the coagulation sedimentation method has a problem that the coagulant added after the treatment becomes industrial waste as it is.

In response to the above problem, for example, Patent Document 1 below discloses a functional polymer using graft polymerization to remove dissolved substances.

On the other hand, a technique for removing a substance mixed in a fluid such as water using a spring-like filter is described in Patent Document 2 below, for example.

JP 2012-214966 A JP 2013-184151 A

However, the technique described in Patent Document 1 discloses a functional polymer, and what kind of apparatus is used for this, and what kind of processing is to be performed on the material is also being studied. There remains room. In addition, the graft ratio is as high as 150% or more, and there remains a problem to be examined in terms of performance such as durability and specific surface area reduction.

In addition, the technique described in Patent Document 2 is physical filtration using a gap between wire rods, and is mainly intended to remove a substance (insolubilized material) that does not dissolve in a fluid and is mixed. In order to remove the dissolved matter by the technique described in Patent Document 2, there is still room for examination.

By the way, when removing the lysate to be removed (hereinafter also referred to as “the lysate to be removed”), the cost required for this is preferably low. In particular, when a large amount of a liquid in which a removal target dissolved material and an insolubilized material are mixed (hereinafter referred to as “processing target liquid”) is simultaneously handled, there is a concern that the cost required for installation and operation of the apparatus system may increase. In order to achieve a cost commensurate with this, it is necessary to increase the processing speed, to be able to perform a large amount of continuous processing, that is, to save space in the processing facility. Furthermore, in order to remove the dissolved substance efficiently, a fine adsorbent (having an auxiliary in the present invention) having a high specific surface area is required. However, the above Patent Documents 1 and 2 still have a problem in this respect.

Therefore, in view of the above problems, the present invention has an object to provide a lysate removal apparatus that can more efficiently remove lysate that is difficult to remove, a filter aid used therefor, and a lysate removal method. And

As a result of diligent investigations on the above problems, the present inventors have studied on the premise that the auxiliary agent handled by the spring-like filter is intended to be insolubilized, and even to investigate the subject to the dissolved matter. It was not reached. As a result of further investigations, it was found that by using a polymer compound as a filter aid and bonding a graft chain to this, it is possible to provide removal performance not only for insolubilization but also for removal of dissolved matter. It discovered and came to complete this invention.

That is, a melt removal apparatus according to an aspect of the present invention that solves the above problems includes a spring-like filter and a filter aid disposed around the spring-like filter. The agent includes a polymer material having a graft chain to which at least one of a chelate group and an ion exchange group is bonded, and the graft ratio of the graft chain in the polymer material is 10% or more and less than 150%.

In addition, a method for removing a lysate according to another aspect of the present invention includes a polymer material including a polymer material having a graft chain in which at least one of a chelate group and an ion exchange group is bonded around a spring-like filter. A grafting agent with a graft chain ratio of 10% or more and less than 150% is placed in, soaked in the liquid to be treated containing the lysate to be removed, and removed from the liquid to be treated by passing the liquid to be treated through a spring-like filter. The target lysate is removed.

The filter aid for a spring-like filter according to another aspect of the present invention includes a polymer material having a graft chain to which at least one of a chelate group and an ion exchange group is bonded, and the graft chain in the polymer material The graft ratio is 10% or more and less than 150%.

As described above, according to the present invention, it is possible to provide a lysate removing apparatus that can more efficiently remove lysate that is difficult to remove, a filter aid used therefor, and a lysate removal method.

It is the schematic of the melt removal apparatus which concerns on embodiment. It is the schematic of the spring-like filter which concerns on embodiment. It is a fragmentary sectional view of the spring-like filter concerning an embodiment. It is the elements on larger scale when the filter aid of the spring-shaped filter which concerns on embodiment is arrange | positioned. It is a figure shown about the image of the form of a polymeric material. It is an image figure at the time of washing | cleaning of the spring-shaped filter which concerns on embodiment. It is an image figure at the time of back washing | cleaning of the spring-shaped filter which concerns on embodiment. It is a photograph figure of the shape of the polymeric material produced by the Example. It is a figure which shows the image of the simple-type melt removal apparatus formed in the Example. It is a figure which shows the result of the boron removal characteristic in an Example. It is a figure which shows the condition of the adhesion to the filter aid addition amount of arsenic and a spring-like filter in an Example. It is a figure which shows the adsorption | suction performance of arsenic in an Example.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and should not be construed as limited to the specific examples of the embodiments and examples shown below.

FIG. 1 is a diagram showing an outline of a melt removal apparatus (hereinafter referred to as “the present apparatus”) 1 according to the present embodiment. As shown in the figure, the present apparatus includes a spring-like filter 2 and a filter aid 3 disposed around the spring-like filter 2. Further, in this apparatus 1, the spring-like filter 2 and the filtration filter are provided. The auxiliary agent 3 is disposed in the housing 4 at the time of removing the dissolved matter. Further, in the present apparatus 1, the spring-like filter 2 is connected to the processing liquid tank 61 via the path member 51. The space 41 in the housing 4 is connected to the stock solution tank 62 and the precoat tank 63 via a path member 52. Further, the space 41 of the housing 4 is also connected to a waste liquid tank 64 via a path member 53.

In the present apparatus 1, the spring-like filter 2 is literally a spring-like filter. For example, the outline is shown in FIG. 2, the partial cross-sectional view is shown in FIG. 3, and the filter aid is arranged in FIG. The partial enlarged view is shown.

As shown in these drawings, the spring-like filter 2 is a filter having a spring shape in which the wire 22 is wound in an annular shape and overlaps with a predetermined gap. Moreover, although not necessarily limited, it is preferable that the wire 21 of the spring-like filter 2 in the apparatus 1 is provided with a protrusion 21 for securing the predetermined distance from the adjacent wire portion. By doing so, it is possible to stably ensure the average gap length of the spring-like filter, more specifically, the distance between the wires.

In addition, the average gap length of the spring-like filter (average of the interval between the wire rods) in the apparatus 1 can be adjusted as appropriate, but is preferably in the range of 5 μm to 200 μm, more preferably 10 μm to 150 μm. It is a range. By setting this range, it is possible to efficiently remove the dissolved matter (removal target dissolved matter) to be removed in the liquid while efficiently removing the insolubilized matter to be removed in the liquid.

The material of the spring-like filter 2 in the device 1 is not limited as long as the shape can be maintained and the device 1 can achieve a desired effect. For example, a single metal such as copper, iron, chromium, nickel, etc. Metal materials such as alloys such as stainless steel, and resin materials such as polystyrene, polypropylene, and polyvinyl chloride can be exemplified as the material for the spring filter.

The spring-like filter 2 in the device 1 can be easily realized by winding a single wire 22 so as to draw an annular spiral. For example, a plurality of annular wires with protrusions are provided. A similar structure can be realized by forming a laminated annular laminate. Even in this case, the apparatus 1 is included in the spring-like filter. That is, in the present apparatus 1, the spring-like filter includes any structure of a wound body or a laminated body.

Further, as shown in the above figure, the spring-like filter 2 is preferably provided with a core rod 23 at the center of the wire rod 22 and a pair of metal fittings 24 for restraining near both ends of the core rod 23. . By doing in this way, a wire can be held more stably.

Further, as described above, the filter aid 3 for the spring-like filter is disposed around the spring-like filter 2 in the apparatus 1 when removing the dissolved substance and the insolubilized substance. And a polymer material having a graft chain to which at least one of a chelate group and an ion exchange group is bonded, and the graft ratio of the graft chain in the polymer material is 10% or more and less than 150%.

Further, the filter aid 3 in the present apparatus 1 contains a polymer material as described above, and is layered around the spring filter 2 by the force of the spring filter 2 sucking the liquid. Thereby, the polymer material can function as a filter layer for removing the dissolved matter.

Here, the polymer material is a material containing a polymer compound as a base material, and the base material is not limited, but polyolefins such as polyethylene, polypropylene, etc. and derivatives thereof, polyvinyl chloride, polyvinyl acetate. And halogenated polyolefins such as polyethylenetetrafluoroethylene and derivatives thereof, halogenated olefin copolymers such as ethylene vinyl alcohol and derivatives thereof, cellulose and the like, and cellulose derivatives having a cellulose skeleton, and the like.

Further, the form of the polymer material here is not limited, but is preferably a powder form. More specifically, it is preferably a collection of elongated fibers (typically short fibers) or powder (powder) as shown in FIG.

In this case, the aspect ratio of the polymer material (ratio of the average major axis length to the average minor axis length) is preferably 1 or more and 5000 or less, more preferably 1000 or less, still more preferably 500 or less, and still more preferably. 100 or less, more preferably 50 or less, and still more preferably 20 or less. On the other hand, in the case of an elongated fiber, it is preferably 1.5 or more, more preferably 2 or more, and further preferably 3 or more. By setting it within this range, even when it is smaller than the gap of the spring-like filter, it becomes easy to entangle each other, and it is easy to obtain a bridge effect, and it is possible to sufficiently achieve a function as a filter aid by securing a large surface area. Become.

In the case of the fibrous material, the average short axis length of the polymer material is preferably in the range of 0.1 μm or more and 500 μm or less, more preferably 0.5 μm or more, and further preferably 2.5 μm or more. It is preferable that As described above, when the average gap length of the spring-like filter is 5 μm or more and 200 μm or less, it is preferable for the bridge effect to be in the range of about 1/8 or more of the average gap length. It is. The upper limit is not particularly limited, but is preferably 500 μm or less, more preferably 300 μm or less, from the viewpoint of sufficiently realizing the function as a filter aid for removing the insolubilized material in the spring filter. More preferably, it is 200 micrometers. Here, the “average minor axis length” refers to the observation of arbitrary 10 objects that can be clearly measured from photographs taken with an electron microscope to determine the respective minor axis lengths, and further observe 10 photographed photographs. It represents the average value of the short axis length.

Further, in the filter aid in the present apparatus 1, a graft chain containing at least one of a chelate group and an ion exchange group is bonded to the base material, and the graft ratio is 10% or more and less than 150%.

Here, the chelate group refers to a functional group having a plurality of coordination sites and capable of capturing metal ions (including metalloids) by the plurality of coordination sites. The chelating group is not particularly limited as long as desired ions (for example, metal ions and metalloid ions) can be captured, but for example, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) ), Polyethyleneamines such as tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA), bipyridine, phenanthroline, ethylenediaminetetraacetic acid, porphyrin, crown ether and the like, but are not limited thereto. What is necessary is just to select the chelate group which can capture | acquire the melt | dissolution (typically metal ion) of the removal object suitably. In particular, as will be apparent from later examples, boron can be captured more efficiently with a glucamine group, mercury with an amino group, and arsenic with a zirconium group.

Also, the ion exchange group means a functional group that releases ions previously held inside and takes in other ions, that is, ion exchange. The ion exchange group is not limited as long as ion exchange can be performed, and examples thereof include a sulfone group, a carboxyl group, a phosphate group, and an amino group. What is necessary is just to select suitably the ion exchange group which can exchange the ion as a removal object melt | dissolution.

Further, as is clear from the illustration of the functional group of the apparatus 1, the lysate to be removed is not particularly limited and can be various. For example, if it is an ion such as boron, fluorine, arsenic and its oxonium ion, or a cationic species such as mercury, lead, chromium, cadmium, etc., which is harmful to the human body or regulated by the environment It will be very effective. Moreover, it can be applied to valuable metals that can be resources such as noble metals such as silver, gold, and platinum, and rare earth elements such as molybdenum, vanadium, and uranium, which are very effective. In particular, it can be suitably applied to the removal of ions dissolved in water (typically metal ions or metalloid ions).

Moreover, in this polymer material, the graft ratio is 10% or more and less than 150%. Here, the graft ratio is a ratio indicating how much graft chain is introduced with respect to the cellulose of the base material, and is a value that can be calculated by a weight difference before and after the graft reaction. It can be calculated by an equation.

Graft ratio [%] = (W ₁ −W ₀ ) / W ₀ × 100
(In the above formula, W ₀ means the weight of the base material before graft polymerization, and W ₁ means the weight of the graft product after graft polymerization.)

In this polymer material, it is important that the graft ratio is 10% or more. By setting the graft ratio to 10% or more, durability against acids and alkalis can be ensured. On the other hand, it is important that the graft ratio is in a range not exceeding 150%. By setting the graft ratio to less than 150%, durability against graft chain breakage and the like can be secured, and repeated characteristics can be secured (deterioration of performance due to repeated use can be suppressed). In other words, when the graft ratio is 150% or more, the ratio of the graft chain in the graft polymer material is excessive, and the dropping of the graft chain becomes remarkable. For this reason, it tends to be difficult to obtain desired mechanical strength that can withstand use (typically repeated use). On the other hand, when the graft ratio is as high as 150% or more, the auxiliary agent (graft polymer material) diameter is large, the specific surface area is low, and good effects cannot be obtained. This effect becomes more remarkable when the graft ratio is in the range of 30% to 120%.

By the way, the binding of the graft chain to the polymer compound is not particularly limited as long as it can be stably performed, but it is preferably realized by so-called graft polymerization. In the graft polymerization, active sites are formed on the surface of the polymer compound, and at least one of the chelate group and the ion exchange group, or a monomer having a functional group convertible thereto is used as a graft chain by graft polymerization reaction. This can be realized by combining them. In this case, the active sites may be formed by any of a catalytic method, a plasma method, a heating method, and a radiation method. From the viewpoint of ease of production and reduction in the amount of solvent used, a method of production by a radiation method (so-called radiation graft polymerization method) in which an electron beam or gamma ray is irradiated is preferred. That is, a radiation graft polymer material can be suitably used as the filter aid disclosed herein.

Further, as described above, the graft chain may be further converted to a functional group having a necessary function after being bonded to the polymer compound. By doing in this way, after combining a graft chain on preferable conditions, it can be set as an optimal functional group further according to the objective. For example, the following table shows examples of the adsorption functional group.

In the present apparatus 1, the polymer material is preferably in the form of powder. As a method for making this powder, the polymer compound (base material) in the form of long fibers or pellets is pulverized and powdered. The graft chain may be bonded after forming into a powder form, and after the graft chain is bonded to the long fiber or pellet base material, the graft polymer is pulverized into a powder form. It may be what you did.

Further, in the present apparatus 1, as described above, the spring-like filter 2 and the filter aid 3 are disposed in the housing 4 when the dissolved matter is removed.

In the present apparatus 1, the casing 4 includes the cavity 41 therein as described above, and the spring-like filter 2 is fixedly disposed therein, and when the dissolved matter is removed, the filter is filtered around the spring-like filter 2. Auxiliary agent 3 is placed. This arrangement method will be described again in the description of the method for removing the dissolved matter.

Further, in the present apparatus 1, the cavity 41 inside the housing 4 is connected to the stock solution tank 62 via the path member 52 as described above. Here, the stock solution tank 62 is a tank that stores a liquid (process target liquid) containing a dissolved product and an insolubilized product to be processed. It should be noted that at least one of the path members 51 to 53 is provided with a pump, and each of the path members 51 to 53 is provided with a valve, and the liquid can be sent by opening and closing the valve and operating the pump as necessary. it can.

Further, in the present apparatus 1, the cavity 41 inside the housing 4 is connected to the precoat tank 63 via the path member 52 as described above. Here, the precoat tank 63 is a tank that can store a liquid mixed with the filter aid, and serves as a supply source for introducing the filter aid into the housing when removing the dissolved matter.

However, the precoat tank 63 can be omitted. In this case, it is possible to add a filter aid directly to the liquid stored in the processing liquid tank 62.

Further, in the present apparatus 1, a path member 51 is connected to the internal space of the spring-like filter 2 disposed in the housing 4, and this path member 51 is further connected to the processing liquid tank 61.

Here, the processing liquid tank 61 is a tank that can store a liquid (processing liquid) filtered through the spring-like filter 2 and the filter aid 3. Although this treatment liquid can be discharged out of the apparatus as it is, it can be used as a cleaning liquid at the time of reverse cleaning, as will be apparent from the following description. In the case where the processing liquid is discharged directly to the outside of the apparatus, the processing liquid tank 61 can be omitted. However, in this case, it is necessary to provide a liquid supply source for performing the reverse cleaning.

Further, in the present apparatus 1, a drain tank 64 is connected by a route member 53 disposed in the housing 4. Specifically, the drainage tank 64 is a tank for storing the used filter aid 3 discharged from the housing 4 by backwashing. By providing the drainage tank 64, the filter aid 3 can be efficiently recovered and discarded or reused as necessary. The path member 53 can be shared with the path member 52 by connecting via a valve or the like.

(Dissolved material removal method)
Here, a dissolved material removal method (hereinafter referred to as “the present method”) using the present apparatus will be described. This method includes (1) a polymer material having a graft chain in which at least one of a chelate group and an ion exchange group is bound around a spring-like filter, and the graft ratio of the graft chain in the polymer material is 10% or more. A filter aid that is less than 150% is placed, (2) the solution to be removed is removed from the solution to be removed by immersing it in the solution to be treated containing the solution to be removed and passing the solution to be treated through a spring-like filter. Is. This will be specifically described below.

First, in this method, (1) the graft ratio of the graft chain in the polymer material is 10 including a polymer material having a graft chain in which at least one of a chelate group and an ion exchange group is bound around the spring-like filter. A filter aid that is at least% and less than 150% is placed. The specific configuration of the filter aid has already been described above.

In this stage, first, the spring-like filter is fixedly arranged in the housing, and the liquid to be treated is put into the stock solution tank 62. Further, the filter aid is dispersed in the liquid and stored in the precoat tank 63.

Then, liquid supply means such as a pump is used to supply the liquid and filter aid in the precoat tank 63 into the housing 4 via the path member 52, and the inside of the spring-like filter 2 is sucked into the spring-like filter. The liquid passed between the wires is discharged out of the casing. Through this process, the filter aid 3 is formed as a layer around the spring-like filter 2. In this case, the liquid may be discharged to the stock solution tank or the precoat tank by providing another path member.

After the filter aid is sufficiently formed as a layer around the spring-like filter, (2) the liquid to be treated is immersed in the liquid to be treated containing the dissolved substance to be removed, and the liquid to be treated is passed through the spring-like filter. Remove the lysate to be removed. Specifically, the supply source is switched from the precoat tank 63 to the stock solution tank 62 to supply the liquid to be processed from the stock solution tank 62 into the housing 4, and the liquid passed through the spring-like filter 2 is supplied to the treatment solution tank 61. Let it drain. Also in this case, it is preferable to use liquid feeding means such as a pump.

As a result, the liquid stored in the stock solution tank passes through the spring filter and the filter aid, and after the dissolved matter is removed, it is discharged out of the casing. An image in the vicinity of the spring-like filter in this case is shown in FIG. In this stage, it goes without saying that the insolubilized material can also be removed by the physical gap of the filter aid.

It is preferable that the spring-like filter 2 is back-washed after the polymer material has sufficiently removed and adhered the dissolved material. Specifically, the processing liquid accommodated in the processing liquid tank connected to the inside of the spring-like filter 2 is supplied via the path member. Then, since the liquid is now supplied from the inside to the outside of the spring-like filter, the filter aid 3 disposed around the spring-like filter is peeled off from the wire of the spring-like filter 2. An image in this case is shown in FIG. And as above-mentioned, this polymeric material can be easily collect | recovered by being discharged | emitted via the route member 53 from the discharge port provided in the housing | casing 4 lower part. The recovered polymer material can be discarded as it is, and can be recycled by performing a predetermined treatment. Here, the treatment liquid is not limited as long as it can be back-washed, but is preferably a liquid that does not contain a lysate to be removed, and more specifically water. preferable.

By the way, the flow rate and flow rate of the liquid used in the present method are not limited as long as the purpose and effect of the present method can be achieved, and specifically, the dissolved matter dissolved in the liquid and removed together with this. The concentration can be adjusted appropriately depending on the concentration of the insolubilized material, the number of spring-like filters, the gap length, the number of spring-like filters, the amount of the filter aid, and the like, for example, in the range of 0.1 L / min to 30.0 L / min. More preferably, it is the range of 0.6 L / min or more and 20.0 L / min or less, More preferably, it is the range of 1.0 L / min or more and 10.0 L / min or less.

As described above, the present apparatus and method are a lysate removal apparatus that can more efficiently remove a lysate that is difficult to remove, a filter aid and a lysate removal method used therefor. More specifically, according to the present apparatus, by using the polymer material having the predetermined structure as a filter aid, it is possible to filter insoluble impurities mixed in water as a normal spring filter. In addition, since a graft chain is provided on the surface of the polymer material, the dissolved impurities themselves can be captured by the graft chain (typically, a functional group of the graft chain). In particular, durability and the like can be stably maintained by keeping the graft ratio within the above range. Further, when cellulose is used as a polymer material (typically a polymer compound as a base material), the cellulose itself is harmless and does not contaminate the fluid even if it is brought into contact with the fluid. It can even be used for water treatment. In addition, a polymer material (typically a polymer compound as a base material) is generally inexpensive and is advantageous from the viewpoint of cost. Moreover, about the polymeric material after filtering, it is good also as taking out only the ion which carried out the chemical process and was capture | acquired, and is good also as taking out the captured substance by burning as it is. Cellulose itself naturally exists, and even if it is burned, it only discharges carbon dioxide and water, so the burden on the environment is small. As a result, it is possible to reduce the object to be removed to at least the environmental regulation value and further to the object dissolved substance to ppt (concentration of 1 trillion).

Moreover, functional groups (chelate groups, ion exchange groups, etc.) can be arbitrarily selected and introduced into the polymer material used in the apparatus 1 according to the lysate to be removed. Furthermore, the introduction amount of functional groups (functional group density) can be adjusted by controlling the graft ratio or the conversion ratio of functional groups (chelate groups, ion exchange groups, etc.). By increasing the introduction amount (mmol / g) of the functional group of the graft polymer material, the removal efficiency of the dissolved product per unit weight of the graft polymer material increases. More specifically, the same functional group or different functional groups of the same type are introduced into the material of the spring-like filter for the insolubilized material by the same means for introducing a functional group (chelate group, ion exchange group, etc.) into the graft polymer material. Can be introduced. Thereby, the processing speed of a removal target object improves markedly. In particular, in this apparatus, the processing speed for handling the fluid to be processed is remarkably fast, so that the processing time can be reduced and the cost can be reduced.

(Application examples)
By the way, in this apparatus 1, although it has the structure which can also remove a melt | dissolution thing by arrange | positioning the filter aid 3 to the spring-like filter 2, use of the filter aid 3 to which the graft chain was combined is used. Regardless of the presence or absence, for example, a configuration in which a resin material is used for the spring-like filter 2 and the graft chain is directly bonded to the resin material can be considered. By doing so, when the liquid passes between the wire rods of the spring-like filter 2, the melt can be removed by this graft chain, and the performance of the apparatus can be further improved.

Here, actually, a filter aid and a lysate removing device were produced and their effects were confirmed. This will be specifically described below.

Example 1
(1) Production of polymer material using electron beam First, an electron beam was irradiated to cellulose powder, which is a polymer compound serving as a base material for the graft polymer material, so that the total absorbed dose was 20 kGy at 2 MeV and 2 mA. Thereafter, graft chains were introduced by a graft polymerization reaction using glycidyl methacrylate (GMA). The graft ratio derived from the weight difference before and after the graft polymerization reaction was 60%.

Subsequently, N-methyl-D-glucamine (NMDG) is introduced by a ring-opening reaction to the epoxy group in the molecule of GMA introduced as a graft chain, and a polymer material having NMDG as a chelate-forming group (functional group) Got. The density (conversion rate) of NMDG introduced into the polymer material, that is, the ratio of NMDG in the polymer material was 1.9 mmol / g.
FIG. 8 shows a shape photograph of the base material before the graft polymerization reaction and the polymer material produced above.

According to this photograph, it was confirmed that the polymer material had an elongated shape, the average minor axis length was 6 μm, and the average major axis length was 10 μm. As a result, it was confirmed that the aspect ratio was 1.7.

(2) Boron removal Then, the spring filter already prepared is installed in a hollow pressure-resistant container (housing), and a circulation path is formed with the treatment liquid tank via the route member, so that simple dissolution removal is possible. A device was made. This image is shown in FIG.

First, 20 g of the polymer material prepared above is added to the treatment liquid tank and introduced into the pressure vessel, while suction is circulated from the inside of the spring filter to cover the periphery of the spring filter with the polymer material. I let them.

Thereafter, the treatment liquid tank was replaced with 4 L of a 50 mg / L boron solution and circulated at a liquid flow rate of 1.6 L / min. After separating the target fluid liquid in the container in which the solution at the system outlet and the target fluid liquid are stored at regular intervals, the boron concentration was quantified to evaluate the boron removal characteristics. The result is shown in FIG.

As a result, in the boron removal test, the boron concentration at the system outlet of the sample collected within 5 minutes from the start of liquid passage was 0 (zero), and it was confirmed that all the boron that passed through the polymer material could be removed. In all the collected samples, the boron concentration could be reduced to 4 mg / L or less. In particular, from this result, it was also found that the treatment speed with the polymer material is a space velocity of 10 h ⁻¹ or more.

Further, as the treatment method, 20 g of a polymer material based on the cellulose powder prepared above was added to a treatment liquid tank previously containing 4 L of a 50 mg / L boron solution and dispersed in the boron solution. The solution was sucked into the spring filter at a rate of 6 L / min, and the solution at the system outlet was collected at regular intervals, and then the boron concentration was quantified to confirm the boron removal characteristics.

As a result, from the start of liquid flow until all boron solutions pass through the system and are discharged (2 minutes 30 seconds), the boron concentration in all the collected samples is equivalent to 1/30 of the initial concentration 1 0.6 mg / L.

As described above, the effect could be confirmed from the examples.

(Example 2)
(1) Production of polymer material A cellulose non-woven fiber having a basis weight of 30 g / m ² is used as a base material of a graft polymer material. It was immersed in the phosphoric acid monomer aqueous solution, and the graft polymerization reaction was advanced. The graft ratio of the obtained grafted cellulose fiber into which phosphate groups were introduced was 120%, and the density of phosphate groups was 4.0 mmol / g.

Then, the cellulose nonwoven fiber graft polymer material obtained above was immersed in an aqueous zirconium sulfate solution for 5 hours to carry a zirconium residue on the end of the phosphate group. Then, the obtained zirconium-type non-woven fiber was freeze-pulverized to several tens of microns and processed into an auxiliary shape for a spring-like filter.

Moreover, when the electron micrograph of the cellulose nonwoven fabric graft | grafting polymer material was confirmed similarly to the said Example 1, average minor axis length is 10 micrometers and 20 micrometers, respectively, and average major axis length is 100 micrometers and 110 micrometers. confirmed.

(2) Arsenic removal Using the same apparatus as in Example 1 above, the processed graft polymer material is introduced into the target fluid liquid in which arsenic is dissolved, and the amount of filter aid added and the state of adhesion to the spring filter I investigated. The result is shown in FIG.

As a result, it was confirmed that as the amount of filter aid added increased, the amount of filter aid adhered to the spring-like filter increased, and the flow rate decreased. However, as shown in FIG. 12, it was confirmed that the adsorption performance of arsenic shows a constant adsorption capacity regardless of the liquid flow rate. This result shows a capacity about 10 times higher than that of a commercially available cross-linked resin having a diameter of several hundred microns (when zirconium is similarly supported on a phosphoric acid resin manufactured by Mitsubishi Chemical Corporation). Yes.

As described above, the effect was confirmed by this example.

(Example 3)
(1) Production of polymer material A graft chain was introduced into a cellulose nonwoven fabric substrate having a fiber diameter of 30 μm by a graft reaction using GMA in the same manner as in Example 2. The graft ratio was 120%. To the epoxy group of the GMA graft chain, 2.1 mmol / g or 2.2 mmol / g of ethylenediamine or diethylenetriamine was introduced, respectively.

In addition, as in Example 1 above, the electron micrographs of the polymer material were confirmed, and the graft polymer material into which ethylenediamine was introduced had an average minor axis length of 20 μm and an average major axis length of 100 μm. It was confirmed that the introduced graft polymer material had an average minor axis length of 25 μm and an average major axis length of 90 μm.

(2) Mercury removal Subsequently, the polymer material prepared above was used in an apparatus similar to the above, and contacted with about 30 ppb (μg / L) of mercury, and the amount of residual mercury was quantified after a certain period of time. The results are shown in the table. According to this result, an adsorption rate (removal rate) of 95% or more was shown in only 30 minutes. The distribution ratio (ratio between residual mercury concentration and mercury concentration trapped in the auxiliary agent) was 30,000 or more. It was confirmed that this value showed a capacity improvement of 800 times at maximum as compared with a commercially available resin ability (manufactured by Mitsubishi Chemical Corporation, Diaion).

As described above, the effect was confirmed by this example.

Example 4
(Synthesis of polyethylene resin powder)
Moreover, the polyethylene resin pellet was used as the base material of the graft polymer (graft polymer material), and this was irradiated with a high frequency of 10 MHz for 5 hours. Next, graft polymerization reaction was performed in a methanol solution of 20% glycidyl methacrylate (GMA) obtained by deoxygenating the irradiated pellets to introduce graft chains. The graft ratio of the obtained GMA pellets was 90%. Here, the pellet-like graft product (graft polymer material) obtained by graft polymerization of GMA was pulverized and adjusted so that the average major axis length was 10 μm. Further, 10 μm powdery GMA pellets were converted in a diethylenetriamine-isopropanol solution. The amine group density was 2.8 mmol / g.

INDUSTRIAL APPLICABILITY The present invention has industrial applicability as a lysate removal apparatus, a filter aid used therefor, and a lysate removal method.

Claims (9)

1. A spring-like filter,
   A lysate removing device provided with a filter aid disposed around the spring-like filter,
   The filter aid includes a polymer material having a graft chain bonded with at least one of a chelate group and an ion exchange group, and the graft ratio of the graft chain in the polymer material is 10% or more and less than 150%. Melt removal device.
2. The melt removal apparatus according to claim 1, wherein the polymer material has an aspect ratio of 1 or more and 5000 or less.
3. The average gap length of the spring-like filter is in the range of 5 μm to 200 μm,
   The melt removal apparatus according to claim 1, wherein the polymer material has an average minor axis length of 0.1 μm to 500 μm.
4. A polymer material having a graft chain to which at least one of a chelate group and an ion exchange group is bonded around a spring-like filter, and the graft ratio of the graft chain in the polymer material is 10% or more and less than 150% Place a filter aid,
   A lysate removal method for removing the lysate to be removed from the liquid to be treated by immersing it in a liquid to be treated containing a lysate to be removed and passing the liquid to be treated through the spring-like filter.
5. The melt removal method according to claim 4, wherein the polymer material has an aspect ratio of 1 or more and 5000 or less.
6. The average gap length of the spring-like filter is in the range of 5 μm to 200 μm,
   The melt removal method according to claim 4, wherein the average short axis length of the polymer material is 0.1 μm or more and 500 μm or less.
7. A filtration for a spring-like filter, comprising a polymer material having a graft chain to which at least one of a chelate group and an ion exchange group is bonded, wherein the graft ratio of the graft chain in the polymer material is 10% or more and less than 150%. Auxiliary agent.
8. The filter aid for a spring filter according to claim 7, wherein the polymer material has an aspect ratio of 1 or more and 5000 or less.
9. The filter aid for a spring-like filter according to claim 7, wherein the polymer material has an average minor axis length of 0.1 µm to 500 µm.

Images