JP7053167B2 - Adsorbent aggregate and its manufacturing method and adsorption method - Google Patents

Description

The present invention relates to an adsorbent aggregate that adsorbs valuable substances and harmful substances contained in a fluid to be treated, a method for producing the same, and an adsorption method.

In recent years, rare metal recycling technology has been attracting attention. Rare metals, also called rare metals or rare metals, are titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), gallium (Ga), cerium (Se), It refers to non-ferrous metals such as molybdenum (Mo), palladium (Pd) and indium (In) and rare earth elements such as lanthanum (La) and cerium (Ce). In countries where rare metals cannot be produced, there is no choice but to rely on imports from foreign countries, and there is an urgent need to develop technology for efficient collection and reuse.

Valuable metals such as gold (Au), platinum (Pt), palladium (Pd), nickel (Ni), and cobalt (Co) that are dissolved or contained in the waste liquid of plating factories, electronic parts manufacturing factories, metal refining factories, etc. Recovery and reuse are essential for building a sound material-cycle society and realizing a sustainable environment. In addition, arsenic (As), cadmium (Cd), lead (Pb), etc. contained as harmful metals in factory wastewater have exclusion standard values set by the Water Pollution Control Law, and wastewater is discharged into rivers without proper treatment. Cannot be released to. A metal trapping technique that efficiently removes and recovers specific precious metals, valuable metals, and toxic metals that dissolve in wastewater and maintains the life of the removal and recovery action is desired.

As a technique for recovering and removing a metal that is neutralized in a solution and / or a metal that dissolves by forming a complex, a metal-containing material to be treated is passed through a metal adsorbent such as an ion exchange resin or a chelate resin to obtain a metal. The technique of capturing is known. Solvation is a state in which metal ions ionized by a metal and solvent molecules are bonded by electrostatic force or hydrogen bonds, and the metal is diffused into the solvent. The metal adsorbent adsorbs at a surface position having a large number of micropores, or adsorbs a specific metal in a liquid to be treated by an adsorptive substance blended inside the metal adsorbent.

On the other hand, granular or powdery chelate resins and ion exchange resins can be used not only for liquid treatment but also for adsorption and removal of specific substances in gas. For example, removal of nitrogen oxides, sulfur oxides, formaldehyde, etc., which are substances that cause air pollution, removal of harmful substances such as volatile organic compounds, formalin, formaldehyde, etc. derived from building materials, removal of harmful or odorous components in factory exhaust, deodorization or It is used for various purposes such as removing harmful substances with a poison-proof mask filter.

Granular or powdery chelate resins and ion exchange resins can be transformed into any shape by filling in a container and used depending on the treatment amount and application of the fluid to be treated and the installation environment of the treatment equipment. Further, the particle size and the filling amount can be selected, and the adsorption rate and the adsorption rate of the substance to be treated can be adjusted.

However, the fine granules or powders of the chelate resin and the ion exchange resin may violently fly up and scatter when the container is filled, and the operator may suck the granules or powders or put them in the eyes. In addition, after filling the container, the voids of the filled granules or powders are clogged by the self-load, vibration during transportation, flow or pressure of the fluid during use, and the entire filling is compressed. When compressed, the permeability of the fluid is reduced and the treatment amount is significantly reduced, and long-term use causes early clogging and clogging. Further, since a large number of granules or powders filled in the container are not fixed to each other, they flow out to the outside of the container together with the processing fluid and the adsorption characteristics are deteriorated. Therefore, in order to prevent compression of the granular or powdered material filling, it is necessary to handle it with sufficient care such as vibration during transportation after filling. In addition, it was necessary to reduce the treatment speed to prevent the outflow of granules or powders.

On the other hand, a metal-adsorbent sintered body in which adsorbent particles are fused and fixed to thermoplastic resin powder is known (Reference 1). Further, a technique for removing gaseous organic substances by a molded body including a polymer-based adsorbent and a porous binder is known (Reference 2). In each case, the adsorbent is fused and fixed to the binder resin, so that the strength is high and the voids can be maintained in the state at the time of manufacture. Therefore, the void volume between the adsorbents does not decrease even with vibration, pressure, or long-term use.

FIG. 11 schematically shows a conventional adsorbent assembly 60 to which a large number of substantially spherical adsorbents 51 are fixed. The adsorbent aggregate 60 is formed between the adsorbent 51 that adsorbs a specific substance such as a metal in the fluid to be treated, the resin structure 52 that fixes the adsorbent 51, and the resin structure 52, and the fluid to be treated is formed. It has a space 53 through which it passes. The resin structure 52 is provided with a gap 52a that fluidly connects a plurality of spaces 53 to each other, and the fluid is introduced into the space 53 through the gap 52a and comes into contact with the adsorbent 51.

In the method for producing the adsorbent aggregate 60 of FIG. 11, first, the adsorbent 51 made of a substantially spherical chelate resin or ion exchange resin absorption and the thermoplastic binder resin are mixed. The adsorbent 51 is in a dry state. Next, the mixture is heated at a temperature at which the binder resin is sufficiently dissolved, and the adsorbent 51 and the resin structure 52 are firmly fused through the joint portion 51a.

In the adsorbent assembly 60 of FIG. 11, since the adsorbent 51 is completely fixed to the resin structure 52, the adsorbent 51 does not separate from the adsorbent aggregate 60 together with the treated fluid even when the fluid to be treated is treated at high speed. However, the adsorbent 51 of the adsorbent aggregate 60 has a joint portion 51a with the resin structure 52. Since the joint portion 51a forms a dead space (non-adsorption region) that causes adsorption loss and significantly reduces the contact area with the fluid, the adsorption performance of the adsorbent aggregate 60 in FIG. 11 is clearly reduced.

On the other hand, as in the case of the adsorbent aggregate 60'in FIG. 12, if the adsorbent 51 is increased in quantity and the adsorbent 51 is densely filled and fixed in the space 53, the above-mentioned problem of reducing the contact area can be improved. In this case, the high adsorption capacity is maintained at the initial stage of use, but the pressure loss gradually increases, clogging occurs early, and the processing speed drops sharply. Therefore, a new adsorbent aggregate that can stably maintain the processing speed without causing a decrease in adsorption capacity due to the joint portion between the adsorbent and the resin structure is desired.

Further, in the adsorbent aggregates 60, 60'in which the adsorbent 51 shown in FIGS. 11 and 12 is fixed to the resin structure 52, the adsorbent 51 maintains a fixed state through the joint portion 51a, so that the adsorbent 51 maintains a fixed state before reuse. Even if the cleaning fluid flows at high speed in the opposite direction, it is difficult to desorb valuable or harmful substances that have penetrated into the details of the adsorbent 51 and adsorbed. Further, in the adsorbent aggregate 60'in FIG. 12, the acid or alkaline cleaning liquid may not sufficiently permeate into the gaps and details between the plurality of adsorbents 51, and a sufficient amount of valuable metal may not be recovered. In this case, incineration of the adsorbent aggregates 60,60'is the only means for recovering valuable metals, which increases the cost of the incinerator process and the purchase of a new adsorbent aggregate. Therefore, it is desired to develop an adsorbent aggregate that is easy to desorb harmful and valuable substances and can be reused.

Further, in the adsorbent aggregates 60, 60'of FIGS. 11 and 12, if the adsorbent 51 and the resin structure 52 are not sufficiently adhered, the adsorbent 51 is made of resin from the gap 52a by long-term use. There is a risk of leaving and flowing out between the structures 52. When the adsorbent 51 separates and flows out 55, the adsorption performance deteriorates and the adsorbent 51 is mixed in the processing fluid, which is not preferable. Further, the harmful metal adsorbed on the adsorbent 51 may flow out to the processing fluid together with the adsorbent 51. Therefore, it is necessary to form an adsorbent aggregate in which the adsorbent does not separate from the resin structure and flow out.

JP-A-2010-254841 Japanese Unexamined Patent Publication No. 11-147983

Therefore, an object of the present invention is to provide an adsorbent aggregate which efficiently adsorbs a substance to be treated contained in a fluid to be treated and maintains the adsorption performance for a long period of time, a method for producing the same, and a method for adsorbing the adsorbent. Another object of the present invention is to provide an adsorbent aggregate which improves and maintains the adsorbent performance and the processing speed by a structure in which the adsorbent is movably accommodated in a movable region of the resin structure, a method for producing the adsorbent, and a method for adsorbing the adsorbent. Another object of the present invention is to provide an adsorbent aggregate in which the adsorbent does not separate from the resin structure, a method for producing the same, and a method for adsorbing the adsorbent. Furthermore, it is an object of the present invention to provide a reusable adsorbent aggregate that easily separates an adsorbent from an adsorbent, a method for producing the same, and a method for adsorbing the adsorbent.

The adsorbent aggregate (10) of the present invention has a resin structure having a three-dimensional network structure in which a granular or powdery adsorbent (1) and an adsorbent (1) are at least partially enclosed and a polyethylene resin is solidified. Equipped with body (2). The adsorbent (1) is a spherical ethylenediamine-containing chelate resin or a spherical anion exchange resin, and the resin structure (2) has a gap (2a) through which a fluid passes and the surface (2c) is tufted. A large number of movable adsorbents (1) formed by the partition wall (4) and the partition wall (4) so that the adsorbent (1) can freely move to the tufted surface (2c) of the partition wall (4) in a non-bonded or non-fixed state. It has an area (3). The diameter (1d) of the spherical adsorbent (1) is larger than the maximum value of the diameter (1d) of the opening (2b) of the gap (2a).

The resin structure (2) of the adsorbent aggregate (10) forms a three-dimensional network structure, and the adsorbent (1) is not fixed to the resin structure (2) and can move freely (3). Is housed in. That is, since the adsorbent (1) can freely move in the movable region (3), the adsorbent that is not fixed to the resin structure (2) when the fluid to be treated is passed through or aerated through the adsorbent aggregate (10). Since (1) is in contact with the fluid to be treated on the entire spherical adsorption surface, there is no non-adsorption region and the adsorption area is significantly larger than that of the conventional adsorbent aggregate (60,60') having a joint (51a). Can be increased and the adsorption efficiency can be improved.

In the movable region (3), unlike the conventional adsorbent aggregate (60'), the adsorbent (1) is not tightly filled and the adsorbent (1) can flow in a relatively large free space. When the fluid passes through the aggregate (10), the pressure loss does not increase, the gap (2a) of the resin structure (2) is less likely to be clogged and the movable region (3) is less likely to be clogged, and it continues for a long period of time. The substance to be adsorbed in the fluid can be adsorbed. Further, since the adsorbent (1) freely flows in the movable region (3), the valuable substances captured by the adsorbent (1) can be easily attached and detached. The adsorbent aggregate (10) having high adsorption ability can be reused many times without deterioration even after repeated use of adsorption and desorption. The adsorbent (1) freely flows in the movable region (3), but is surrounded by the resin structure (2), so that the adsorbent (1) can be prevented from flowing out to the outside.

In the method for producing the adsorbent aggregate (10) of the present invention, a plurality of granular or powdery adsorbents (1) selected from a spherical ethylenediamine-containing chelate resin or an anion exchange resin are immersed in an alcohol solution and expanded. After that, a step of forming an adsorbent mixture by mixing with a plurality of powdery, granular or pellet-like polyethylene resins as the thermoplastic resin (2), and a step higher than the softening point of the thermoplastic resin (2) and adsorbing. A resin that heats the adsorbent mixture at a temperature lower than the melting point of the material (1), fuses a plurality of thermoplastic resins (2) in a three-dimensional network, and at least partially surrounds the adsorbent (1). It includes a step of forming the structure (2) and a step of cooling and solidifying the resin structure (2). The cooled and solidified resin structure (2) has a gap (2a) through which a fluid passes, and the surface (2c) is formed by a tufted partition wall (4) and a partition wall (4). The tufted surface (2c) of 4) is provided with a large number of movable regions (3) through which the adsorbent (1) can freely move in a non-bonded or non-fixed state, and the diameter (1d) of the spherical adsorbent (1). Is greater than the maximum value of the diameter (2d) of the opening (2b) of the gap (2a).

Since the adsorbent mixture is heated at a temperature higher than the softening point of the thermoplastic resin and lower than the melting point of the adsorbent (1), only the thermoplastic resin melts and the adsorbent (1) does not melt. As a result, the powdery, granular or pelletized thermoplastic resins are three-dimensionally fused to each other to form a resin structure (2) having a movable region (3) for accommodating the adsorbent (1).

The adsorption method of the present invention passes through the process of preparing the adsorbent aggregate (10) and the gap (2a) provided in the partition wall (4) of the resin structure (2) of the adsorbent aggregate (10). , The process in which the fluid flowing from the outside to the inside of the movable region (3) comes into contact with the entire surface of the adsorbent (1) operably contained in the movable region (3), and the adsorbent (1) in contact with the fluid. Includes a process in which the fluid adsorbs the substance to be treated in the fluid and a process in which the fluid in the movable region (3) flows out from the inside of the movable region (3) through the gap (2a). In the present invention, after each process of inflow, contact, adsorption and outflow is executed in the movable region (3), each process of inflow, contact, adsorption and outflow is similarly repeated in the other movable region (3). As a result, the fluid and the operable adsorbent (1) can be in contact with each other many times in a plurality of movable regions (3), and a large amount of the substance to be treated in the fluid can be adsorbed and captured with high efficiency.

In the present invention, since the adsorbent does not have a joint with the resin structure, the filled adsorbent efficiently adsorbs the substance to be treated and the adsorption performance can be maintained for a long period of time. Further, since the adsorbent is idle, the pressure loss does not increase and a predetermined processing speed can be maintained, enabling stable and continuous processing operation. Since valuable substances or harmful substances can be easily and inexpensively desorbed from the adsorbent and can be reused many times, the adsorbent does not need to be replaced and the processing cost can be significantly reduced. Further, the adsorbent does not flow out even in high-speed treatment, a safe treatment fluid can always be stably obtained, and high adsorption performance can be maintained for a long period of time.

Partial schematic cross-sectional view showing the adsorbent aggregate according to the present invention. Electron micrograph showing raw material resin Schematic cross-sectional view showing the manufacturing method of the adsorbent aggregate according to the present invention. Schematic cross-sectional view showing the manufacturing method of the adsorbent aggregate according to the present invention. Electron micrograph showing the adsorbent aggregate according to the present invention An electron micrograph of an aggregate of adsorbents according to the present invention. Schematic diagram showing an adsorption test device Schematic cross-sectional view showing a state in which the adsorbent is idle Schematic cross-sectional view showing a state in which the adsorbent is idle Graph showing the result of metal adsorption rate by the liquid flow test Partial schematic cross-sectional view showing a conventional adsorbent aggregate Partial schematic cross-sectional view showing a conventional adsorbent aggregate

The adsorbent aggregate according to the present invention, a method for producing the same, and an embodiment of the adsorption method will be described below with reference to FIGS. 1 to 10. 1, FIG. 3, FIG. 4, FIG. 8 and FIG. 9 show the adsorbent aggregate (10) of the present invention in a schematic and simplified manner in order to facilitate understanding of the invention.

The adsorbent aggregate (10) according to the present invention shown in FIG. 1 is a substantially spherical adsorbent (1) formed of a granular or powdery material and a resin structure that at least partially surrounds the adsorbent (1). It is equipped with (2). The adsorbent (1) can selectively adsorb and capture a specific substance to be adsorbed contained in a liquid or gas, and is a chelate resin containing ethyleneamine and an ion containing at least one amine, sulfonic acid and carboxylic acid. It is selected from one or two or more of the exchange resins. Since ethyleneamine, amine, sulfonic acid and carboxylic acid of the adsorbent (1) are hydrophilic groups, it is relatively difficult to fuse with the resin of the hydrophobic resin structure (2). The metals that can be adsorbed by the adsorbent (1) are scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, yttrium, zirconium, molybdenum, ruthenium, palladium, silver, cadmium, etc. One or more metals selected from the indium, hafnium, tungsten, rhenium, platinum, gold, lead, lanthanoid series and actinoid series.

Ethyleneamine in the chelating resin is ethylenediamine (H ₂ NC ₂ H ₄ NH ₂ ), diethylenetriamine (H (NHC ₂ H ₄ ) ₂ NH ₂ ), triethylenetetramine (H (NHC ₂ H ₄ ) ₃ NH ₂ ), tetra. Ethylenepentamine (H (NHC ₂ H ₄ ) ₄ NH ₂ ), pentaethylenehexamine (H (NHC ₂ H ₄ ) ₅ NH ₂ ), tetraethylenetriamine (C ₈ H ₁₇ N ₃ ) and ethyleneimine (secondary) Amine) (NHCH ₂ CH ₂ ) and one or more of its derivatives are selected. The ion exchange resin containing at least one of amine, sulfonic acid and carboxylic acid contains one or more of strongly acidic, weakly acidic, strongly basic and weakly basic ion exchange resins, and specifically includes ethylenediamine. Includes dimethylaminoethanol ((CH ₃ ) ₂ NCH ₂ CH ₂ OH), succinic acid (HOOC (CH ₂ ) ₂ COOH), acetic acid, sulfuric acid and one or more of their functional groups.

The resin structure (2) forms a large number of movable regions (3) for movably accommodating or enclosing the adsorbent (1) by the partition wall (4) formed in a mesh pattern. In the embodiment of FIG. 1, one and two adsorbents (1) are accommodated in each movable region (3), but three or more adsorbents (1) are accommodated in each movable region (3) as long as they can be idled. ) May be housed. The resin structure (2) contains one or more thermoplastic resins selected from polypropylene (PP), polyethylene (PE), polyvinylidene fluoride (PVDF) and ethylene vinyl acetate (EVA) copolymers. Since a thermoplastic resin is used, the shape of the adsorbent aggregate (10) can be easily deformed by heating according to the application.

The resin structure (2) fluidly connects a large number of movable regions (3) to each other and provides a gap (2a) through which the fluid to be processed passes in the partition wall (4). The gap (2a) is a gap or space in which the plurality of resins are not fused to each other, and FIG. 1 schematically shows a plurality of substantially linear gaps (2a) penetrating the partition wall (4). The gap (2a) improves the liquid permeability and air permeability of the fluid to be treated, and the fluid to be treated efficiently contacts the adsorbent (1) existing in the movable region (3) between the resin structures (2). Therefore, the substance to be treated can be effectively adsorbed. Further, the gap (2a) may be a large number of through holes formed in the partition wall (4) of the resin structure (2).

The adsorbent (1) has a particle size (1d) larger than the maximum value of the diameter (2d) of the opening (2b) of the gap (2a). The fluid passes through the gap (2a) of the resin structure (2), but the adsorbent (1) cannot pass through the diameter (2d) of the opening (2b). Therefore, when the fluid to be treated is passed through the adsorbent aggregate (10), the adsorbent (1) is retained in the movable region (3) even if it freely floats in the movable region (3), and other Movable area (3) or adsorbent aggregate (10) does not flow out. Since the adsorbent (1) does not flow out, the adsorption capacity of the adsorbent aggregate (10) does not decrease even after long-term use. In addition, it is possible to prevent harmful or valuable metals adsorbed on the adsorbent (1) from flowing out from the movable region (3) together with the adsorbent (1).

In the embodiment of the present invention, the surface (2c) of the resin structure (2) facing the adsorbent (1) is formed in a tufted, uneven or undulating shape. That is, it is not formed in a plane. As a result, the resin structure (2) makes point contact with the adsorbent (1) instead of surface contact, so that the resin structure (2) and the adsorbent (1) are prevented from being in close contact with each other or fixed, and are movable. Promotes free movement, rotation or vibration of the adsorbent (1) in region (3). The surface (2c) of the resin structure (2) may be formed in a porous form.

The adsorbent aggregate (10) can be formed as a fired body or a sintered body. As a result, the adsorbent aggregate (10) can be maintained at high strength. In addition, even if the resin structure (2) is used for a long period of time under vibration and pressure, the resin structure (2) is not damaged, and the movable region (3) is not collapsed or shrunk, and the shape and space volume at the time of manufacture are maintained. Breathability or liquid permeability can be stably maintained for a long period of time.

Next, an embodiment of the method for producing the adsorbent aggregate (10) according to the present invention will be described with reference to FIGS. 2 to 6.

First, a substantially spherical adsorbent raw material made of a chelate resin or an ion exchange resin is immersed in alcohol to sufficiently swell it, and then filtered under reduced pressure at -30 kPa or less to remove excess alcohol. Next, the adsorbent (1) is prepared so that the dry weight loss is 10% or less by air drying or the like (the degree of swelling is larger than 1). A plurality of prepared granular or powdery substantially spherical adsorbents (1) and a plurality of powdery, granular or pellet-like thermoplastic resins are mixed until substantially uniform to form an adsorbent mixture. The adsorbent (1) is classified into a range of an average particle size of 20 to 200 μm and used. When the average particle size is less than 20 μm, the adsorbent (1) flows out from the gap (2a) of the resin structure (2). If the average particle size is too small, it is difficult to handle, the liquid passage and aeration resistance increase, and the treatment efficiency deteriorates at an early stage. When the average particle size exceeds 200 μm, the contact area with the fluid to be treated decreases and the treatment efficiency decreases. The polyethylene surface of the powdery thermoplastic resin used in this embodiment is shown by an electron micrograph (FIG. 2). As shown in FIG. 2, the surface (2c) of the polyethylene resin is an aggregate of a plurality of tufts.

Next, the adsorbent mixture is inserted into a mold, for example, and heated at a temperature higher than the softening point of the thermoplastic resin and lower than the melting point of the adsorbent (1). Specifically, the adsorbent mixture is heated to 90 to 180 ° C., and only the thermoplastic resin is melted and sintered. Since the melting point of the adsorbent (1) is 20 ° C. or higher higher than the softening point of the thermoplastic resin, the adsorbent (1) does not melt. At this time, the thermoplastic resin is not completely melted to the inside, but only the surface is melted, and a plurality of thermoplastic resins are fused and fixed in a three-dimensional network while surrounding the adsorbent (1). As a result, a resin structure (2) having a movable region (3) in which the adsorbent (1) moves freely is formed. Further, as shown in FIG. 2, since the thermoplastic resin has a tufted surface, it does not face-bond when it is heated and melted, but it is point-bonded to each other, and a bonding portion that bonds between the resins and a void portion that does not bond are formed. It forms a three-dimensional fused shape that is intricately intertwined. This void finally becomes a gap (2a) of the resin structure (2) through which the fluid passes.

The degree of swelling of the adsorbent (1) is larger than 1 and 2 or less, preferably 1.1 to 1.8. The degree of swelling is a value peculiar to a substance expressed by the rate of change in volume before and after the substance absorbs a liquid. When the adsorbent mixture is heated at a temperature higher than the softening point of the thermoplastic resin and lower than the melting point of the adsorbent (1), the thermoplastic resin melts and the partition wall (4) of the resin structure (2) becomes the adsorbent (4). It is formed close to 1) (Fig. 3). Although they approach each other, the surface (2c) of the partition wall (4) and the adsorbent (1) are not fixed. An adsorbent (1) containing water or alcohol with a swelling degree of 1.8, which is placed close to the partition wall (4), gradually loses water or alcohol by heating and shrinks to a volume of swelling degree 1 ( Gradually separate from the partition wall (4) until S). Eventually, there is a certain distance (L) between the adsorbent (1) that has shrunk (S) and become smaller, and the partition wall (4), and the movable region (3) is a gap through which the adsorbent (1) can move. ) Is formed (Fig. 4). That is, the adsorbent (1) secures a space in which it moves by self-shrinking (S) due to heating. Further, when the adsorbent (1) is heated, the adsorbent (1) containing water or alcohol evaporates water or alcohol, so that the surface temperature of the adsorbent (1) is lower than the heating temperature and faces the adsorbent (1). The surface temperature of the close portion (2f) of the thermoplastic resin is also lowered, which hinders the melting of the close portion (2f) of the thermoplastic resin, thereby preventing the adhesion to the adsorbent (1). Further, the hydrophilic adsorbent (1) and the hydrophobic thermoplastic resin have poor binding compatibility with each other due to their low affinity and low binding property, and do not repel each other and bind to each other. Therefore, the adsorbent (1) and the resin structure (2) are separated from each other without sticking to each other.

Finally, the resin structure (2) is cooled and solidified to obtain the adsorbent aggregate (10) of the present invention shown in the electron micrographs of FIGS. 5 and 6. From the enlarged photograph of FIG. 6, the spherical adsorbent (1) is operably housed in the movable region (3) between the white tufted resin structures (2) while maintaining its original shape without melting. Further, it can be seen from FIG. 6 that the tufted surface (2c) of the resin structure (2) and the adsorbent (1) are in a non-bonded state. Further, the resin structure (2) of the plurality of tufted surfaces (2c) fuses with each other while having a gap (2a) through which the fluid passes, and the resin structure (1) surrounds the adsorbent (1) at least partially. Form the partition wall (4) of the body (2). The dark portion of the photograph of FIG. 6 in which the spherical adsorbent (1) is arranged between the tufted partition walls (4) of FIG. 6 represents the movable region (3). From the above configuration, the adsorbent aggregate (10) of the present invention has the effect of allowing liquid passage and aeration with low pressure loss without impairing the adsorption capacity of the adsorbent (1).

In the above embodiment, the substantially spherical adsorbent (1) of a granular or powdery material is exemplified, but a fibrous adsorbent can also be used.

Hereinafter, embodiments in which the adsorption method of the present invention is applied to the adsorption of a metal that is solvated in the liquid to be treated and / or a metal that forms a complex and dissolves will be described with reference to FIGS. 7 to 9.

FIG. 7 shows a tubular adsorption test apparatus (20) in which the adsorbent aggregate (10) is arranged inside. For example, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, yttrium, zirconium, molybdenum, ruthenium, palladium, silver, cadmium, indium, hafnium, tungsten, rhenium, platinum, A liquid to be treated (15) containing one or more metal components selected from gold, lead, a lanthanoid series, and an actinoid series is passed through an adsorption test apparatus (20) at a space velocity of 5 to 500 h ^-1 . The metal is adsorbed by the adsorbent aggregate (10), and the liquid after the adsorption is used as the treatment liquid (16). A chelate resin containing ethyleneamine is used as the adsorbent (1) of the adsorbent aggregate (10).

The liquid to be treated (15) passed through the gap (2a) provided in the partition wall (4) of the adsorbent aggregate (10) shown in FIG. 8 passes from the outside to the inside of the movable region (3). When it flows in, it comes into contact with the adsorbent (1) contained in the movable region (3) and adsorbs the metal component by the chelate resin. The adsorbent (1) is slightly swollen by the liquid to be treated (15), but the liquid to be treated (15) is adsorbed because it freely moves in the movable region (3) without being fixed to the resin structure (2). Evenly contact the entire spherical surface of the material (1).

Even in a situation where the adsorbent (1) is likely to block the opening (2b) of the gap (2a) (FIG. 8), the adsorbent (1) freely moves in the movable region (3), so that the liquid to be treated (15) ), For example, as shown in FIG. 9, the adsorbent (1) is movable (17). That is, since the adsorbent (1) is not fixed to the resin structure (2), it does not stay in a fixed place and secures the flow path of the gap (2a) without closing the opening (2b). Further, even in a situation where the adsorbent (1) is arranged near the gap (2a) and is likely to flow out from the opening (2b) of the gap (2a), the diameter (1d) of the adsorbent (1) is the same as that of the gap (2a). Since it is larger than the maximum value of the diameter (2d) of the opening (2b), the adsorbent (1) does not separate from the movable region (3) through the gap (2a).

The liquid (15) to be treated in the movable region (3) flows out from the inside of the movable region (3) through the gap (2a). As long as the liquid to be treated (15) flows into the movable region (3), the adsorbent (1) flows without stopping as shown in FIGS. 8 and 9, so that even if the metal is adsorbed on the adsorbent (1). , The movable region (3) and the gap (2a) are not blocked, and the pressure loss of the adsorbent aggregate (10) does not increase. In the adsorbent aggregate (10) of the present invention, a sufficient specific surface area can be secured for continuous operation without deteriorating the adsorption performance, and a sufficient amount of metal can be adsorbed on the entire surface of the adsorbent (1). The adsorbed metal can be easily desorbed from the entire surface with a cleaning agent such as acid by the floating of the adsorbent (1), and the valuable metal can be recovered. In addition, the harmful metal adsorbed on the surface of the adsorbent (1) can be removed in the same manner.

In the above-described embodiment, the embodiment of the method of adsorbing a metal that is solvated in a liquid to be treated and / or a metal that forms a complex and dissolves is shown, but the method is not limited to the metal treatment of a liquid, and is, for example, a treatment. The adsorption method according to the present invention can also be applied to the removal of harmful substances in a gas.

An example in which a liquid passing test was performed on the adsorbent aggregate (10) of the present invention will be described below. An ethylenediamine-containing chelate resin was used as the adsorbent (1) (first example).

<First Example>
[Manufacturing of Adsorbent Aggregate (10) Sintered Body (Example 1)]
First, 30 parts of an ethylenediamine-containing chelate resin is immersed in an alcohol solution to swell about 1.2 times, and then mixed with 70 parts of a powdered polyethylene resin (polymerization degree: about 180,000) as a thermoplastic resin to form an adsorbent mixture. Formed. The adsorbent mixture was inserted into a mold and heated at about 125 ° C. to melt the polyethylene resin. Further, it was cooled and solidified to produce a sintered body (Example 1) of the adsorbent aggregate (10) of the present invention (FIGS. 5 and 6).

[Manufacturing of Adsorbent Aggregate (60) Sintered Body (Comparative Example 1)]
30 parts of the dried ethylenediamine-containing chelate resin and 70 parts of the powdery polyethylene resin (polymerization degree: about 180,000) were mixed to form an adsorbent mixture. The adsorbent mixture was inserted into a mold and heated at about 125 ° C. to melt the polyethylene resin. Further, it was cooled and solidified to produce a sintered body (Comparative Example 1) of the adsorbent aggregate (60) of the prior art.

[Liquid flow test method]
The obtained sintered body of the adsorbent aggregate (10) (Example 1) was filled in the adsorption test apparatus (20) of FIG. 7, and the space velocity was adjusted to about 300 h ^-1 , and the known metal concentration [mg] was adjusted. A liquid flow test of 100 ml of the liquid to be treated (15) of / l] was carried out. The pH value of the liquid to be treated (15) was set to 2, 3, 4, 5, 6, 7, 8 and 9, and the liquid passing test was performed 8 times per metal, and the metal concentration of the treated liquid (16) after passing the liquid [16]. mg / l] was measured respectively.

On the other hand, the sintered body (Comparative Example 1) of the conventional adsorbent aggregate (60) was filled in the adsorption test device (20) of FIG. 7, and the space velocity was adjusted to about 300h ^-1 , and the known metal concentration [ A liquid flow test of 100 ml of the liquid to be treated (15) of mg / l] was carried out. Similarly, the pH value of the liquid to be treated (15) is set to 2, 3, 4, 5, 6, 7, 8 and 9, and the liquid passing test is performed 8 times per metal, and the liquid to be treated (16) is passed. The metal concentration [mg / l] of each was measured.

For Example 1 and Comparative Example 1, the results of the adsorption rates of arsenic, molybdenum, titanium, lead, manganese and nickel are shown in the graphs (a) to (f) of FIG. 10, respectively. The horizontal axis of FIG. 10 shows the pH value, and the vertical axis shows the adsorption rate [%]. The percentage of the value obtained by dividing the metal concentration of the treated liquid (16) by the metal concentration of the liquid to be treated (15) was defined as the adsorption rate [%].

As shown in the graphs of FIGS. 10A to 10F, Example 1 showed a higher adsorption rate than Comparative Example 1 for all metal elements. In particular, for molybdenum (b) and titanium (c), the adsorption rate of Example 1 was significantly higher than that of Comparative Example 1 in a wide range of pH 2-9. The adsorption rate of arsenic (a) in Example 1 is higher than that in Comparative Example 1 in the range of pH 4 to 9. Manganese (e) has a higher adsorption rate of Example 1 than Comparative Example 1 in the range of pH 2 to 7. Further, in the pH range of 3 to 9, the manganese adsorption rate of Example 1 was almost 100%. At pH 2 of lead (d) and nickel (f), the adsorption rate of Example 1 was much higher than that of Comparative Example 1. In Example 1 with respect to lead (d) and nickel (f), a high adsorption rate was exhibited in a wide range of pH 2 to 9, and in particular, the absorption rate of lead (d) according to Example 1 was almost 100%.

Based on the above, the sintered body of the adsorbent aggregate (10) of the present invention (Example 1) is a sintered body of the conventional adsorbent aggregate (60) using the same amount of ethylenediamine-containing chelate resin (Comparative Example). Compared with 1), the adsorption capacity could be significantly improved. That is, in the adsorbent aggregate (10) of the present invention, the adsorbent (1) and the resin structure (2) do not bind (FIGS. 5 and 6), and metal is adsorbed by the entire surface of the adsorbent (1). Therefore, it was confirmed that higher adsorption performance can be exhibited as compared with the conventional adsorbent aggregate (60).

Next, a second embodiment using an ion exchange resin as the adsorbent (1) will be described.

<Second Example>
[Manufacturing of Adsorbent Aggregate (10) Ion Exchange Resin Sintered Body (Example 2)]
25 parts of anion exchange resin (adsorbent (1)) immersed in an alcohol solution and swollen about 1.6 times and 25 parts of powdered polyethylene resin (polymerization degree: about 180,000) as a thermoplastic resin are mixed. The adsorbent mixture was filled into the cavity of the vibrating sintering mold. The mold filled with the adsorbent mixture was heated and sintered in a constant temperature bath at 125 ° C. The mold was taken out from the constant temperature bath and cooled and solidified to produce an ion exchange resin sintered body (Example 2) of a cylindrical adsorbent aggregate (10).

[Manufacturing of Comparative Example 2]
Comparative Example 2 containing only an unsintered anion exchange resin containing no thermoplastic resin was prepared.

[Flow velocity test method and results]
The ion exchange resin sintered body of Example 2 and the same amount of unsintered anion exchange resin (Comparative Example 2) were inserted into the cartridges, and pure water was passed under a reduced pressure of -30 kPa to perform a flow velocity test. Did. As a result, in Example 2 and Comparative Example 2, the values were 32 ml / min and 31 ml / min, respectively. Example 2 according to the present invention can be treated at a flow rate equal to or higher than that of unsintered Comparative Example 2, the ion exchange resin does not adhere to the resin and does not block the movable region (3), and the liquid flow region is sufficient. I was able to confirm the securing.

[Adsorption test method and results of Example 2]
A caffeine solution diluted with an ammonium acetate solution (20) in the test apparatus (cartridge) (20) of FIG. 7 filled with an ion exchange resin sintered body (Example 2) using the adsorbent aggregate (10) of the present invention. 5 μg / ml) (15) 10 ml was used as a solution to be treated, and the solution was passed at a flow rate of 5, 10, 20 and 30 ml / min. Further, 10 ml of an acetaminophen solution (5 μg / ml) (15) diluted with an ammonium acetate solution was used as a liquid to be treated, and the liquid was passed at a flow rate of 5, 10, 20 and 30 ml / min. After passing the liquid, the cartridge was eluted with methanol and the concentrations of caffeine and acetaminophen were measured. The recovery rate is the percentage [%] of the value obtained by dividing the measured concentration by the concentration of the liquid to be treated (15), and the results are shown in the table below. A value exceeding 100% of the recovery rate is a test error and is a reasonable value.

From Table 1, the recovery rate of caffeine and acetaminophen exceeded 95% in the entire flow rate range of 5 to 30 ml / min. That is, even in the adsorbent aggregate (10) of the present invention using an ion exchange resin as the adsorbent (1), a high recovery rate could be realized due to the high adsorption characteristics of the substance to be adsorbed.

The adsorbent aggregate of the present invention and its manufacturing method and adsorbing method include recycling of rare metals and valuable metals, factory wastewater treatment, drinking water production, pure water production, underground contaminated water purification, air pollution purification, factory exhaust treatment, deodorization or detoxification. It can also be applied to filters.

(1) ・ ・ Adsorbent, (2) ・ ・ Resin structure, (2a) ・ ・ Gap, (2b) ・ ・ Opening, (2c) ・ ・ Surface (2c), (3) ・ ・ Movable area, ( 10) ・ ・ Adsorbent aggregate,

Claims (11)

Granular or powdery adsorbents and
It comprises a resin structure having a three-dimensional network structure in which the adsorbent is at least partially enclosed and the polyethylene resin is solidified.
The adsorbent is a spherical ethylenediamine-containing chelate resin.
The resin structure is formed by a partition wall having a gap through which a fluid passes and having a tufted surface, and a large number of adsorbents that can freely move freely on the tufted surface of the compartment wall in a non-bonded or non-fixed state. With a movable area of
An adsorbent aggregate characterized in that the diameter of the spherical adsorbent is larger than the maximum diameter of the opening of the gap. Granular or powdery adsorbents and
It comprises a resin structure having a three-dimensional network structure in which the adsorbent is at least partially enclosed and the polyethylene resin is solidified.
The adsorbent is a spherical anion exchange resin,
The resin structure is formed by a partition wall having a gap through which a fluid passes and having a tufted surface, and a large number of adsorbents that can freely move freely on the tufted surface of the compartment wall in a non-bonded or non-fixed state. With a movable area of
An adsorbent aggregate characterized in that the diameter of the spherical adsorbent is larger than the maximum diameter of the opening of the gap. The adsorbent aggregate according to claim 1 or 2, wherein the average particle size of the adsorbent is 20 to 200 μm. The resin structure comprises a reticulated partition wall that forms a large number of movable areas.
The adsorbent aggregate according to claim 1 or 2, wherein the partition wall has a gap for introducing a fluid from the outside to the inside of the movable region. The adsorbent aggregate according to claim 1 or 2, which is formed of a sintered body. The adsorbent aggregate according to claim 1, wherein the metal adsorbed on the adsorbent is selected from arsenic, molybdenum, titanium, lead, manganese and nickel. The adsorbent aggregate according to claim 2, wherein the substance adsorbed on the adsorbent is selected from caffeine and acetaminophen. A plurality of granular or powdery adsorbents selected from a spherical ethylenediamine-containing chelate resin or an anion exchange resin are immersed in an alcohol solution and expanded, and then as a plurality of powdery, granular or pellet-shaped thermoplastic resins. To form an adsorbent mixture by mixing with the polyethylene resin of
The adsorbent mixture is heated at a temperature higher than the softening point of the thermoplastic resin and lower than the melting point of the adsorbent, and the plurality of thermoplastic resins are fused in a three-dimensional network to enclose the adsorbent at least partially. The process of forming the resin structure and
Including the process of cooling and solidifying the resin structure
The cooled and solidified resin structure is formed by a partition wall having a tufted surface and a partition wall having a gap through which a fluid passes, and the adsorbent is free in a non-bonded or non-fixed state to the tufted surface of the partition wall. Equipped with a large number of movable areas that can be freely moved to
A method for producing an adsorbent aggregate, wherein the diameter of the spherical adsorbent is larger than the maximum diameter of the opening of the gap. The adsorbent according to claim 8, wherein the step of forming the resin structure includes a step of heating the adsorbent mixture at a temperature higher than the softening point of the thermoplastic resin and lower than the melting point of the adsorbent to shrink the adsorbent. How to make an aggregate. The process of forming the resin structure is
The process of inserting the adsorbent mixture into the mold and
The method for producing an adsorbent aggregate according to claim 8, further comprising a step of heating the adsorbent mixture to 90 to 180 ° C. in a mold to melt the thermoplastic resin and sintering the resin. The process of preparing the adsorbent aggregate according to any one of claims 1 to 7, and the process of preparing the adsorbent aggregate.
The process in which the fluid flowing from the outside to the inside of the movable region comes into contact with the entire surface of the adsorbent operably contained in the movable region through the gap provided in the partition wall of the resin structure of the adsorbent aggregate.
The process by which the adsorbent in contact with the fluid adsorbs the substance to be treated in the fluid,
An adsorption method comprising a process in which a fluid in a movable region flows out from the inside of the movable region through a gap.

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