JPH09290151A - Chemical substance adsorbing material and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fix an organometallic complex to a base material without using a binder, and to prevent an adsorption capacity from being hindered by sticking the organometallic complex which can adsorb chemical substances to the base material having voids through which fluid can pass. SOLUTION: A chemical substance adsorbing agent used in a fluid treatment apparatus which is contacted with fluid such as liquid and gas and separates and removes a specified component contained in the fluid by physical and chemical actions such as adsorption which is made by sticking an organometallic complex which can adsorb chemical substances to a base material having voids through which fluid can pass is produced by a method in which the base material having voids through which fluid can pass is immersed in a reaction solution which can form the organometallic complex which can adsorb chemical substances to form the complex on the surface of the base material. In this process, a metal complex used for the adsorbent is preferably an organometallic complex having one-dimensional or three-dimensional channel structure and is made to be able to receive and adsorb a chemical substance to be removed in a void in a molecule based on the channel structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used in a fluid processing apparatus which is brought into contact with a fluid such as a liquid or gas to separate and remove a specific component contained in the fluid by a physical or chemical action such as adsorption. The present invention relates to a chemical substance adsorbent.

[0002]

2. Description of the Related Art Conventionally, as a method for separating and removing a specific component from a fluid mixed with a plurality of components by an action such as adsorption, a method of bringing a fluid to be treated into contact with an adsorbent represented by activated carbon has been adopted. Was there. When the adsorbent is a powder, the adsorbent is formed into a granular shape and packed in a column or the like, and is attached to a processing apparatus, or the adsorbent is adhered to a substrate by using an appropriate binder as a powder and the processing apparatus is used. The method of attaching it to is adopted.

[0003]

When an organometallic complex is used as an adsorbent, it can be used in the same manner as activated carbon, but it requires separate steps and operations. INDUSTRIAL APPLICABILITY The present invention is to produce a chemical substance adsorbent in which an organometallic complex is attached to the surface of a substrate by immersing a substrate having a fluid-permeable void in the reaction solution when producing the organometallic complex, and treating the fluid. The purpose is to provide the equipment. INDUSTRIAL APPLICABILITY The chemical substance adsorbing material according to the present invention can be used as a filter, a chemical substance separating material, and the like, and more specifically, it can be used as an air purifier, an air conditioner filter, a water purifier filter, and the like.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a chemical substance adsorbent in which an organometallic complex capable of adsorbing a chemical substance is attached to a substrate having voids through which a fluid can pass. By installing such a chemical substance adsorbent in the fluid passage of the fluid treatment device, a specific component contained in the fluid to be treated is removed. Since no binder is used to attach the adsorbent to the chemical substance adsorbent, the surface of the adsorbent particles is not covered with the binder, and the adsorption ability of the organometallic complex is not impeded at all. . Further, by fitting the shape of the chemical substance adsorbent of the present invention to the mounting portion of the fluid treatment device, mounting and replacement can be easily performed.

The organometallic complex used in the chemical substance adsorbent of the present invention is preferably an organometallic complex having a one-dimensional or three-dimensional channel structure. These channel structures are formed in the entire metal complex, and the chemical substance to be removed is stored and adsorbed in the voids in the molecule based on this channel structure. Depending on the type of metal ion, the counterion of the metal ion in the metal salt that is the starting material of the complex, and the type of organic ligand, the channel structure and the size of the voids are determined, and the adsorbed molecules are determined. The chemical substance to be adsorbed and removed is specified.

The chemical substance adsorbing material of the present invention is obtained by immersing a base material having voids through which a fluid can pass in a reaction solution capable of forming an organometallic complex capable of adsorbing a chemical substance, and applying the metal complex to the surface of the base material. It is manufactured by forming. In general, crystals grow around a core substance, but the present invention takes advantage of this characteristic to form a substrate having a fluid-permeable void in a reaction solution capable of forming an organometallic complex capable of adsorbing a chemical substance. An organic metal complex is attached to the surface to produce a chemical substance adsorbent. According to this manufacturing method, it is possible to manufacture the chemical substance adsorbent after the organometallic complex is manufactured, without separately providing a step of adhering to the base material. The reaction solution capable of forming the organometallic complex capable of adsorbing the chemical substance may be a mixture of the solution of the organic ligand and the solution of the metal ion as described in claim 4. The organometallic complex used in the present invention is produced from this solution.

In a preferred embodiment, a base material having a heat-sealing layer on at least the surface portion is used as the base material having a fluid-permeable void used in the present invention. Using a material having a heat-sealing layer on the surface of the base material, the organometallic complex is adhered to the surface of the base material, and then heated and deposited to fuse the adhered complex with the base material to form a complex. Can be more firmly fixed to the substrate. In this case, since the fusion bonding surface is a very small portion, the influence on the surface area of the organometallic complex is small, and its adsorption capacity remains unchanged.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a chemical substance adsorbent in which an organometallic complex capable of adsorbing a chemical substance is attached to a base material having voids through which a fluid can pass, and a method for producing the same.

A porous film, a foam or a non-woven fabric can be used as a substrate having a fluid permeable void used in the present invention, and it is called an open-cell polyurethane foam, particularly Scott foam. The use of polyurethane foam, non-woven fabric or the like is preferable because the pressure loss at the time of fluid permeation is small. Each of these is used as a dust filter without any treatment, and is typical as a base material having voids through which a fluid can pass. When the cross-sectional area of the fluid to be treated is large, these members need to be reinforced in order to withstand the load, and are preferably fixed to the skeleton member before or after the metal complex is attached.

As a material used for the heat-sealing layer provided on at least the surface of these base materials, a resin that melts and softens at a relatively low temperature is preferable, for example, ethylene-vinyl acetate copolymer (EVA) and polyester. Examples thereof include resins and polyurethane resins. Further, as means for providing these heat-fusible materials on the surface of the base material, a base material such as polyurethane foam or nonwoven fabric is impregnated with a solution of these heat-fusible materials, an aqueous dispersion or the like, or by spray coating or the like. Examples thereof include a treatment method, and in the case of a base material using fibers such as a nonwoven fabric, a method in which the fibers themselves have a two-layer structure.

The organometallic complex having a one-dimensional or three-dimensional channel structure used in the present invention is described below in (a)-
It is preferably selected from those shown in (c). (A) A complex formed by a metal ion and a dicarboxylic acid having two carboxyl groups arranged at point symmetrical positions in the molecule. (B) A complex formed by a bidentate coordinating organic ligand having atoms capable of coordinating with a metal ion at both ends of a rigid skeleton and a divalent metal ion. (C) A complex formed by a bidentate coordinating organic ligand having atoms capable of coordinating with a metal ion at both ends of a rigid skeleton, 2,3-pyrazinedicarboxylic acid, and a divalent metal ion. These complexes can be obtained by mixing and reacting a solution of an organic ligand and a solution of a metal salt as a raw material.

From the analysis of X-ray diffraction patterns, it is found that the organometallic complexes (a) to (c) have a one-dimensional or three-dimensional channel structure. For example, when copper terephthalate is used as an example of the complex of (a), copper has a plane 4-coordination, and two copper ions are arranged so that four molecules of terephthalic acid surround each 90 °, and two copper ions are formed. The oxygen atoms of are coordinated to different copper ions. That is, terephthalic acid molecules are arranged in a lattice, and two copper ions exist at the lattice points. And the crystal | crystallization is comprised in the form in which the layer formed from a copper ion and a dicarboxylic acid was laminated | stacked. As a result, the lattices are stacked to form a one-dimensional channel.

As the complex of (b), a complex having a composition of [Ni (bpy) _1.5 (ClO ₄ ) ₂ ] (bpy = 4,4′-bipyridyl) will be described. In every 90 °, 4,4'-bipyridyl is coordinated by 4 molecules of N atoms, and 4,4'-bipyridyl is coordinated by different N atoms to different Ni ions, respectively, to form a planar lattice. A crystal is formed by stacking the lattices so that Ni ions are linearly arranged, and the lattices are continuously formed by stacking to form a one-dimensional channel as in the example of (a).

As the complex of (c), [Cu (bpy) (pyzzdc) ₂ ] (bpy = 4,4′-bipyridyl, pyzdc = 2,3)
-Pyrazinedicarboxylic acid), a complex having a composition of 2,3-
Pyrazinedicarboxylic acid is coordinated with copper ions to form a planar structure, and this plane is coordinated with copper ions 4,4′-
Crystals are formed by laminating bipyridyl in a form in which they are bonded to each other, and a channel structure is formed between the layers.

Examples of the dicarboxylic acid having two carboxyl groups arranged at point symmetry positions in the molecule, which are organic ligands constituting the complex (a), include terephthalic acid, fumaric acid, and 1,4- Examples are trans-cyclohexanedicarboxylic acid and 4,4′-biphenyldicarboxylic acid.
In addition, as metal ions, copper ions, chromium ions,
Examples thereof include molybdenum ion, rhodium ion, palladium ion and tungsten ion, and a complex is formed in combination with the dicarboxylic acid.

As the organic ligand constituting the complex of (b), pyrazine, 4,4'-bipyridyl, trans-1,
Those selected from 2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4,4′-dicyanobiphenyl, 1,2-dicyanoethylene, and 1,4-bis (4-pyridyl) benzene are preferred. , Divalent metal ions are used as the metal ions, specifically, Co, Ni,
It is preferable to use one selected from Cu and Zn.

The organic ligand constituting the complex (c) is
One of the organic ligands used in (b) and pyrazinedicarboxylic acid are used in combination, and the same metal ion as in (b) is used.

The production of these organometallic complexes is carried out by preparing a solution of an organic ligand and a solution of a metal salt as a raw material, mixing these and reacting them. The solvent used is not particularly limited as long as it does not react with an organic ligand or a metal ion or form a complex. The counter ion of the metal ion is not particularly limited as long as it does not inhibit the solubility of the metal salt in the solvent and the formation of the one-dimensional channel structure of the resulting complex. In the production of the complex (a), it is preferable to add an organic acid to the solution of dicarboxylic acid to adjust the pH, and formic acid, acetic acid, trifluoroacetic acid, propionic acid or the like can be used.

When a porous film, a foam or a non-woven fabric, especially an open-cell polyurethane foam or a non-woven fabric, is immersed as a substrate having voids through which a fluid can permeate into the above-mentioned solution for forming an organometallic complex, the base is formed. An organic metal complex is formed by adhering to the surface of the material, and the chemical substance adsorbent of the present invention is obtained.

[0020]

Embodiments of the present invention will be described below. (Organometallic complex forming solution 1) Methanol 100 cm ³ ,
2.53 g of 1,4-trans-cyclohexanedicarboxylic acid is dissolved in a mixed solvent of 14 cm ³ of formic acid and cooled to room temperature. A solution prepared by dissolving 3.3 g of copper formate in 100 cm ³ of methanol was added dropwise to the obtained 1,4-trans-cyclohexanedicarboxylic acid solution to obtain an organometallic complex-forming solution 1. Copper 1,4-trans-cyclohexanedicarboxylate is produced from this production solution 1.

(Organometallic complex forming solution 2) 0.25 g of biphenyldicarboxylic acid was dissolved in a mixed solvent of dimethylformamide (DMF) 90 cm ³ and formic acid 0.5 cm ³ . A solution prepared by dissolving 0.5 g of copper formate in 25 cm ³ of methanol was added dropwise to this solution at room temperature with stirring to obtain an organometallic complex-forming solution 2. Copper biphenyldicarboxylate is produced from this production solution.

(Production of Chemical Adsorbent) Polyester fiber non-woven fabric (manufactured by Unitika Ltd.), glass fiber non-woven fabric, open-cell polyurethane foam, and cellulose fiber filter paper are used as the fluid-permeable substrate. It was immersed in the organometallic complex-forming solutions 1 and 2 and allowed to stand. Since the polyurethane swells with DMF, the combination of the organometallic complex forming solution 2 and the open-cell polyurethane foam was excluded. One day later, powdery crystals were deposited and adhered to the substrate taken out from the solution. The base material having the complex adhered thereto was thoroughly washed with water and ethanol, and dried at 100 ° C. for 4 hours to obtain a chemical substance adsorbent.

When immersed in the organometallic complex-forming solution 1, crystals were scraped off from the chemical substance adsorbing material to which the complex was attached and analyzed, the metal complex was copper 1,4-trans-cyclohexanedicarboxylate, and the specific surface area was 480 m. ² / g, and the pore size was 4.7Å. In addition, when it was immersed in the organometallic complex forming solution 2 and the crystals were scraped off from the chemical substance adsorbent to which the complex was attached and analyzed, the metal complex was copper biphenyldicarboxylate, the specific surface area was 1200 m ² / g, and the pore diameter was It was 7.8Å.

When the above-described chemical substance adsorbing material to which the organometallic complex is attached is used as a filter, hydrocarbons such as methane and ethane, amines such as ammonia and methylamine, aldehydes such as acetaldehyde, carbon monoxide,
It was confirmed that nitrogen oxide, sulfurous acid gas, and mercaptans such as methyl mercaptan and butyl mercaptan were well adsorbed.

Claims (6)

[Claims] 1. A chemical substance adsorbent in which an organometallic complex capable of adsorbing a chemical substance is attached to a base material having voids through which a fluid can pass. 2. The organometallic complex is an organometallic complex having a one-dimensional or three-dimensional channel structure.
The chemical adsorbent described. 3. A chemical substance adsorbent for forming a metal complex on a substrate surface by immersing a substrate having a fluid-permeable void in a reaction solution capable of forming an organometallic complex capable of adsorbing a chemical substance. Production method. 4. A method for producing a chemical substance adsorbent according to claim 3, wherein a solution of a metal salt and a solution of an organic ligand are mixed and a base material having a fluid permeable void is immersed in the mixed solution. . 5. The method for producing a chemical substance adsorbent according to claim 3, wherein a base material having a heat-sealing layer on at least a surface portion is used as the base material having voids through which a fluid can pass. 6. A solution of a metal salt and a solution of an organic ligand are mixed, and a base material having a fluid-permeable void is immersed in the mixed solution to form a metal complex on the surface of the base material, The method for producing a chemical substance adsorbent according to claim 5, comprising a step of heating and fusing the organic metal complex to the base material by a heat fusion layer.