WO2011052008A1 - 吸着材、その製造方法及びその利用 - Google Patents
吸着材、その製造方法及びその利用 Download PDFInfo
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- WO2011052008A1 WO2011052008A1 PCT/JP2009/005727 JP2009005727W WO2011052008A1 WO 2011052008 A1 WO2011052008 A1 WO 2011052008A1 JP 2009005727 W JP2009005727 W JP 2009005727W WO 2011052008 A1 WO2011052008 A1 WO 2011052008A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
- B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/106—Selenium compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Definitions
- the present invention relates to an adsorbent, a manufacturing method thereof, and use thereof.
- Arsenic is present in various wastewater, river water, well water, etc. Furthermore, since arsenic is also present in the soil, there is a problem when some river water and groundwater are used as tap water. Since arsenic is highly toxic, strict standard values (environmental standard 0.01 ppm, drainage standard 0.1 ppm) are set, and development of a technique for removing trace amounts of arsenic in water is drawing attention.
- a precipitation method, an adsorption method, and the like have been proposed.
- a method for treating arsenic by coagulation precipitation using an iron salt or an aluminum salt is widely used.
- filtration separation after the precipitation treatment and a large amount of waste treatment are problems, and it is difficult to remove a trace amount of arsenic at low concentration in water.
- activated alumina in the adsorption method, activated alumina, strong basic anion exchange resin or the like is used.
- a strongly basic ion exchange resin when used, there is a problem that the effect of removing arsenic is significantly reduced by coexisting ions.
- activated alumina When activated alumina is used, it has a high affinity for arsenic, but dissolves in an acidic region. And problems such as being unable to be used repeatedly.
- these adsorbents have a major problem that trivalent arsenic cannot be directly adsorbed.
- pentavalent arsenic arsenate ions
- arsenate ions that are relatively easy to adsorb trivalent arsenic by a pretreatment step in which an oxidizing agent is added.
- rare earth metals particularly cerium
- arsenic have a high affinity for arsenic, and its application to treatment of water to be treated containing these has been studied.
- Tetravalent cerium is already known as a component of adsorbent for removing trivalent arsenic in groundwater because it effectively adsorbs trivalent arsenic in water.
- water-soluble rare earth metal salts are added.
- a method for generating and removing a substance to be removed and an insoluble salt is known.
- a water-insoluble rare earth metal usually exists as an oxide of a fine powder, and therefore has a drawback that it is difficult to handle in ion exchange operations such as adsorption and elution regeneration.
- the method of supporting the rare earth metal on the carrier is mainly classified into two types depending on the water solubility of the rare earth metal reagent used during the supporting step.
- One is a method in which fine particles of water-insoluble rare earth metal oxide are dispersed in a binder polymer resin material through an appropriate organic solvent, and then the binder resin is formed into particles in a poor solvent.
- a zirconium-supported adsorbent has a low adsorptivity to trivalent arsenic and is difficult to use for the treatment of groundwater containing a large amount of trivalent arsenic.
- the present invention has been made in view of the above problems, and an object of the present invention is to realize an adsorbent having a high adsorption capability for trivalent arsenic and a method for producing the same.
- the present inventor has the ability to adsorb trivalent arsenic if tetravalent cerium having higher affinity for arsenic than zirconium can be supported on a carrier such as a chelate resin. We thought that a high adsorbent could be manufactured.
- the present inventor does not directly support tetravalent cerium on the chelate resin, but first supports trivalent cerium and then oxidizes the supported cerium to tetravalent, so that tetravalent cerium is supported. Has been found to be supported on a chelate resin, and the present invention has been completed.
- the manufacturing method of the adsorbent according to the present invention includes a cerium supporting step of supporting trivalent cerium on a carrier having a functional group capable of supporting cerium, and the supported cerium. And a cerium oxidation step that oxidizes the cerium into a tetravalent valence.
- tetravalent cerium can be easily supported on a carrier without using a tetravalent cerium aqueous solution having very strong oxidizing power and strong acidity. For this reason, there is an effect that an adsorbent having a high adsorption capability for trivalent arsenic can be easily produced without causing any significant damage to the carrier.
- the adsorbent according to the present invention is obtained by the above method according to the present invention, and is characterized in that the carrier is chelated with tetravalent cerium.
- the adsorbent according to the present invention includes a carrier having a functional group capable of carrying cerium and tetravalent cerium carried on the carrier, and the carrier is chelated with tetravalent cerium. It is a feature.
- the carrier is chelated with tetravalent cerium, an adsorbent having a high adsorption ability for trivalent arsenic can be provided.
- the adsorption treatment method according to the present invention is a method for adsorption treatment of arsenic existing in water, and is characterized by using the adsorbent according to the present invention.
- the adsorbent according to the present invention which has a high adsorption ability for trivalent arsenic, is used, there is an effect that trivalent arsenic can be efficiently adsorbed.
- the adsorbent according to the present invention includes a cerium supporting step of supporting trivalent cerium on a support having a functional group capable of supporting cerium, oxidizing the supported cerium, and A cerium oxidation step for converting the number to tetravalent, and the carrier is chelated with tetravalent cerium.
- main component means a component having the largest content in terms of mass among the contained components, and “A to B” indicating the range is A or more and B Unless otherwise specified, “ppm” means a value obtained in terms of mass.
- the term “supported on a carrier” means “attached to a carrier and provided on the carrier”, and the bond may be a covalent bond or an ionic bond.
- a chelate bond carrying cerium at two or more locations is preferred.
- Examples of the functional group capable of supporting cerium include an iminodiacetic acid group, a phosphoric acid group, a sulfonic acid group, and a phosphonic acid group from the viewpoint of chelating the carrier with cerium.
- the functional group capable of supporting cerium is more preferably an iminodiacetic acid group from the viewpoint of the ease of reaction for supporting cerium.
- the production method according to the present invention may further include a carrier preparation step for producing the carrier.
- a carrier preparation step for producing the carrier may further include a carrier preparation step for producing the carrier.
- Carrier production step may be any method as long as the carrier can be produced.
- the carrier examples include a carrier in which a functional group capable of supporting cerium is bonded to a graft chain of a particulate cellulose-based substrate, and a graft chain of a petroleum-based plastic substrate such as polypropylene, polyethylene, and ethylene-vinyl alcohol copolymer.
- a carrier having a functional group capable of supporting cerium bonded thereto can be used.
- a carrier in which a functional group capable of supporting cerium is bonded to the graft chain of the particulate cellulose substrate for example, a particulate cellulose group mainly composed of cellulose having a crystallinity of 80% or more.
- a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more as the base material, an adsorbent excellent in mechanical strength can be obtained because the crystallinity is high. it can.
- cellulose is the most hydrophilic natural product present in nature, it has a low environmental burden, and can provide an inexpensive adsorbent and is hydrophilic. For this reason, the adsorption
- conventional adsorption towers for ion exchange / chelating resin spheres, regeneration facilities, etc. can be used as they are.
- Examples of the carrier preparation step in the present embodiment include a method described in JP-A-2009-13204.
- a carrier preparation step including an activation step, a graft chain introduction step, and a functional group binding step will be described.
- a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more is activated.
- cellulose spherical particles are previously placed in a thin plastic bag, this bag is purged several times with an inert gas such as nitrogen and sealed, and then cooled with dry ice in a nitrogen atmosphere. It can be performed by irradiating ionizing radiation under conditions to generate radical active sites.
- an inert gas such as nitrogen and sealed
- the particulate cellulose base material is not particularly limited as long as it is a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more. That is, the particulate cellulose-based substrate is preferably composed only of cellulose having a crystallinity of 80% or more, but may contain other components as long as it does not adversely affect the adsorption performance. More specifically, “main component” means that cellulose having a crystallinity of 80% or more in the particulate cellulose base material is 90% or more, more preferably 95% or more, and still more preferably 99%. % Should be included.
- components that can be included are not particularly limited, and examples thereof include hemicellulose, lignin, and starch.
- the cellulose that is the main component of the particulate cellulose-based substrate is particulate cellulose having a crystallinity of 80% or more.
- the particulate cellulose having a degree of crystallinity of 80% or more is not limited as long as the mass fraction of the crystalline portion in the particulate cellulose particles is 80% or more. It is meant to include cellulose particles having a crystallinity of 80% or more, cellulose particles comprising 80% or more of microcrystalline cellulose, and the like.
- the microcrystalline cellulose is one obtained by removing the non-crystalline part of normal cellulose and purifying, and the crystallinity is close to 100%.
- the crystallinity can be measured by an X-ray diffraction method.
- the cellulose that is the main component of the particulate cellulose-based substrate may have a crystallinity of 80% or more, more preferably 90% or more, and 95% or more. More preferred is 99% or more.
- Examples of the particulate cellulose base material having a crystallinity of 99% or more include an aggregate of 100% microcrystalline cellulose.
- Specific examples of the microcrystalline cellulose include, for example, microcrystalline cellulose that is commercially available for pharmaceutical use.
- Examples of the microcrystalline cellulose include Asola Kasei Chemicals' SEOLUS (registered trademark), SELFIA (registered trademark), and the like. Can be mentioned.
- the shape of the particulate cellulose-based substrate is not particularly limited as long as it is particulate, and may be a sphere, an ellipse, an indefinite crushed shape, or the like. Among these, the shape of the particulate cellulose-based substrate is more preferably spherical from the viewpoint of mechanical strength.
- the average particle size of the particulate cellulose base material may be 30 to 800 ⁇ m in a dry state, more preferably 50 to 500 ⁇ m, and further preferably 100 to 300 ⁇ m.
- the average particle diameter means a value determined by the following method. First, samples are collected from several locations of a collection of particles as samples. Each sample is observed with an electron microscope, and the entire sample collected from several locations is the largest in diameter of one target particle, that is, the shape of the particle, for a total of 100 or more particles. Measure the dimension in the larger dimension. Among the 100 or more measured values, an average of 60% of measured values excluding 20% in the upper and lower directions is defined as an average particle diameter in the present invention.
- the particulate cellulose-based substrate may be porous cellulose.
- the obtained cerium-supported particulate adsorbent has functional groups capable of supporting tetravalent cerium and tetravalent cerium introduced in the pores, and the adsorption target is fine. It can flow in the hole. Therefore, it is possible to obtain a cerium-supported particulate adsorbent that is superior in adsorption performance.
- the activation is not particularly limited as long as a radical active site can be generated so that the graft chain can be introduced in the subsequent graft chain introduction step.
- a method of chemically activating using a radical polymerization initiator a method of activating by irradiating with ionizing radiation, a method of activating by irradiating with ultraviolet rays, and activating by ultrasonic waves
- the method, the method of activating by plasma irradiation, etc. can be used.
- the method of irradiating with ionizing radiation has the advantage that the manufacturing process is simple, safe and low pollution.
- the graft chain can be introduced from the surface to the inside of the particulate cellulose-based substrate, and an adsorbent excellent in adsorption capacity can be obtained.
- spherical cellulose particles with high crystallinity are typical radiation-decomposable polymers, so doses of ionizing radiation that do not damage particulate cellulose-based substrates Irradiate.
- a dose is preferably 1 to 25 kGy, more preferably 10 to 20 kGy.
- the dose of ionizing radiation is 1 kGy or more
- a radical active site necessary for a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more can be generated.
- the dose of ionizing radiation is 25 kGy or less, it is possible to suppress damage applied to the particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more. For this reason, the mechanical strength does not decrease, and an adsorbent excellent in chemical stability can be produced.
- energy can be saved and the irradiation time can be shortened, so that the manufacturing cost can be reduced.
- Examples of the ionizing radiation include ⁇ -rays, ⁇ -rays, ⁇ -rays, electron beams, and X-rays.
- ⁇ -rays from the viewpoint of industrial productivity, for example, ⁇ -rays from cobalt-60, electrons generated by an electron beam accelerator. Lines, X-rays, etc. can be used more suitably.
- an electron beam accelerator capable of performing irradiation of a thick material as an electron beam accelerator.
- An accelerator can be used suitably.
- the particulate cellulose base material can be preferably activated.
- the irradiation with ionizing radiation is more preferably performed in an inert gas atmosphere such as nitrogen gas, neon gas, or argon gas. This is preferable because the graft chain can be effectively introduced.
- the ionizing radiation is irradiated under cooling conditions of ⁇ 20 to 0 ° C. This is preferable because the graft chain can be effectively introduced.
- ⁇ Graft chain introduction process The particulate cellulose base material activated in the activation step is brought into contact with the ethylenically unsaturated monomer in the graft chain introduction step, and the ethylenically unsaturated monomer is graft polymerized to the particulate cellulose base material. Let Thereby, a graft chain is introduced into the particulate cellulose base material.
- the ethylenically unsaturated monomer refers to a monomer having an ethylenically unsaturated group, that is, a carbon-carbon double bond.
- an ethylenically unsaturated monomer is not particularly limited.
- an epoxy group-containing ethylenically unsaturated monomer, or a styrene derivative containing an epoxy group, such as styrene or chlorostyrene is preferably used.
- an epoxy group-containing ethylenically unsaturated monomer can be more suitably used.
- the epoxy group-containing ethylenically unsaturated monomer is not particularly limited.
- the following general formula (1) the following general formula (1)
- a monomer having a structure represented by can be suitably used.
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a substituted or unsubstituted saturated hydrocarbon group or a hydrogen atom.
- the saturated hydrocarbon group some carbon atoms may be substituted with O, N, P, S, or Si.
- the substituent that can be substituted with the saturated hydrocarbon group is not particularly limited, and examples thereof include an aryl group, an alkyl group, an alkanoyl group, and an oxo group ( ⁇ O).
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are more preferably each independently an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
- A represents a substituted or unsubstituted saturated hydrocarbon chain, that is, a substituted or unsubstituted divalent saturated hydrocarbon group.
- the saturated hydrocarbon chain some carbon atoms may be substituted with O, N, P, S, or Si.
- the substituent that can be substituted with the saturated hydrocarbon chain is not particularly limited, and examples thereof include an aryl group, an alkyl group, an alkanoyl group, and an oxo group.
- n is 0 or 1.
- A is more preferably a saturated hydrocarbon chain having 1 to 2 carbon atoms, or one containing at least one oxy group (—O—) in the saturated hydrocarbon chain. Moreover, it is more preferable that it has an oxo group etc. as a substituent.
- examples of the ethylenically unsaturated monomer include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl vinyl ether, 2-vinyloxirane, 2-methyloxiranylmethyl (meth) acrylate, and itacon.
- examples thereof include diglycidyl acid, glycidyl pentenoate, glycidyl hexenoate, and glycidyl heptenoate.
- the above ethylenically unsaturated monomers may be used alone or in combination of two or more.
- the ethylenically unsaturated monomer having one ethylenically unsaturated group is graft-polymerized on the particulate cellulose base material, but other monomers are further graft-polymerized. It may be.
- a structure in which graft chains are crosslinked can be obtained. Thereby, the swelling degree of the surface of an adsorbent can be adjusted.
- polyfunctional monomer having two or more ethylenically unsaturated groups examples include polyethylene glycol diacrylate having a number average molecular weight of 400 to 1000 (polyethylene glycol # 400 to 1000 diacrylate), and ethoxylated bisphenol A diacrylate. Divinylbenzene and the like can be preferably used.
- the amount used is 1 to 20 mol% with respect to the ethylenically unsaturated monomer having one ethylenically unsaturated group. It is preferably 3 to 10 mol%.
- the graft ratio of the graft chain introduced by graft polymerization of the ethylenically unsaturated monomer to the particulate cellulose base material is preferably 100% or more.
- the graft ratio is 100% or more, the supporting ratio of cerium in the obtained adsorbent can be increased. For this reason, an adsorbent with high adsorption capability can be obtained.
- the graft ratio refers to the amount (mass percentage) of the ethylenically unsaturated monomer introduced by graft polymerization with respect to the particulate cellulose-based substrate, and is calculated by the method described in the examples described later. Value.
- the graft ratio is more preferably 150% or more, and particularly preferably 200% or more.
- the graft chain introducing step brings the ethylenically unsaturated monomer into the particles by bringing the activated particulate cellulose base material into contact with an emulsion containing the ethylenically unsaturated monomer. It is preferable to introduce a graft chain by graft polymerization to a cellular cellulose base material.
- the monomer In emulsion polymerization of an aqueous solvent, the monomer is dispersed in the micelle and the affinity of the monomer with respect to the substrate is improved. Therefore, the radical utilization rate and the polymerization rate are higher than those in solution polymerization with an organic solvent. Thereby, the irradiation dose required for generating radicals in the substrate can be lowered, and the reaction time can be greatly reduced. As a result, an adsorbent with high mechanical strength can be provided.
- the amount of the ethylenically unsaturated monomer contained in the emulsion is preferably 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 60% by mass or less, based on the total amount of the emulsion, 45 More preferably, it is at least 55% by mass.
- an ethylenically unsaturated monomer can be graft-polymerized at a high graft ratio on a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more. Furthermore, the contact time of the activated particulate cellulose base material and the emulsion containing an ethylenically unsaturated monomer can also be shortened.
- the amount of the ethylenically unsaturated monomer is preferably 80% by mass or less based on the total amount of the emulsion, so that the emulsion can be prepared well, can be uniformly dispersed, and is highly stable, which is preferable. .
- the emulsion is more preferably an aqueous emulsion, that is, an emulsion containing the ethylenically unsaturated monomer and water.
- aqueous emulsion that is, an emulsion containing the ethylenically unsaturated monomer and water.
- ion-exchange water a pure water, an ultrapure water etc. as water used here.
- the ethylenically unsaturated monomer is dispersed in small micelles, and the utilization rate of radicals and the polymerization rate are increased, so that the particulate cellulose-based base material mainly composed of cellulose having a crystallinity of 80% or more.
- the ethylenically unsaturated monomer can be graft polymerized with a high graft ratio.
- an organic solvent is not used in the graft chain introduction step, it is preferable from the viewpoints of reducing process costs, reducing environmental burden, and improving process safety.
- the emulsion further preferably contains 3 to 10% by mass, more preferably 3 to 8% by mass of a surfactant with respect to the ethylenically unsaturated monomer.
- the ethylenically unsaturated monomer can be graft-polymerized at a high graft ratio onto a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more.
- the contact time between the particulate cellulose-based substrate, the activated particulate cellulose-based substrate and the emulsion containing the ethylenically unsaturated monomer can be shortened.
- the particularly preferable composition of the emulsion according to the present embodiment is that the surfactant is in the range of 3 to 8% by mass and the monomer is in the range of 30 to 80% by mass.
- the surfactant 5 It can be made into mass%, monomer 50 mass%, and water 45 mass%.
- the surfactant is not particularly limited, and surfactants usually used in emulsion polymerization can be suitably used.
- surfactants include alkyl polyoxyethylene ether, S-alkyl polyoxyethylene ether, alkylphenyl polyoxyethylene ether, N, N′-di (alkanol) alkanamide, amine oxide, and the like.
- Nonionic surfactants soap, alkylbenzene sulfonate, alkyl diphenyl ether sulfonate, alkane sulfonate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid methyl, alkyl sulfate, alkyl sulfate (polyoxyethylene) salt
- Ionic surfactants such as alkyl phosphate salts, N-acyl amino acid salts, dialkyldimethylammonium chlorides and monoalkyltrimethylammonium chlorides; amphoteric surfactants such as sulfobetaines and betaines.
- the method for contacting the activated particulate cellulose-based substrate and the emulsion containing the ethylenically unsaturated monomer is not particularly limited.
- the activated particulate cellulose-based substrate is The method etc. which are immersed in an emulsion are mentioned.
- the contact time between the activated particulate cellulose-based substrate and the emulsion containing an ethylenically unsaturated monomer is 5 minutes to 8 hours, more preferably 30 minutes to 60 minutes when the immersion method is used as the contact method. It is. That is, a high graft rate can be achieved with a short contact time.
- the reaction temperature that is, the temperature at which the activated particulate cellulose-based substrate and the emulsion containing the ethylenically unsaturated monomer are brought into contact is 40 to 80 ° C. when the immersion method is used. More preferably, it is 50 to 60 ° C.
- the contact between the activated particulate cellulose-based substrate and the emulsion containing the ethylenically unsaturated monomer is preferably performed in an inert gas atmosphere such as nitrogen gas, neon gas, or argon gas. Thereby, reaction of a radical and oxygen can be prevented.
- an inert gas atmosphere such as nitrogen gas, neon gas, or argon gas.
- ⁇ Functional group binding step> a functional group capable of supporting cerium is bonded to the graft chain introduced in the graft chain introducing step.
- the functional group capable of supporting the cerium is introduced by reacting the graft chain with a compound in which the functional group is introduced by reacting with the graft chain. Therefore, when the graft chain has an epoxy group, a compound that can react with the epoxy group to introduce the functional group may be used as the compound.
- an iminodiacetic acid group disodium iminoacetate, hydroxyethyliminodiacetic acid, ethylenediaminediacetic acid, L-aspartic acid-N, Ndiacetic acid, etc. are preferably used.
- disodium iminoacetate, hydroxyethyliminodiacetic acid, ethylenediaminediacetic acid, L-aspartic acid-N, Ndiacetic acid, etc. are preferably used.
- sodium sulfite, 2-aminoethanesulfonic acid and the like can be preferably used.
- a phosphonic acid group phosphoric acid, phosphorous acid, etc. Can be suitably used.
- the carrier in the adsorbent according to the present invention is not limited as long as the graft chain has a functional group capable of supporting cerium, and the timing of introduction of the functional group is not particularly limited. Therefore, the carrier having the functional group may be obtained by introducing the functional group into the graft chain after introducing the graft chain into the base material, or the carrier having the particulate cellulose base. Further, it may be obtained by graft polymerization of an ethylenically unsaturated monomer having a functional group capable of supporting cerium.
- a reactive monomer such as an epoxy group-containing ethylene is graft-polymerized on a polymer substrate, and then an iminoacetic acid disodium etc.
- an iminodiacetic acid group can be suitably introduced into the graft polymerization chain.
- the ethylenically unsaturated monomer for example, when an iminodiacetic acid group is introduced, glycidyl methacrylate (GMA) or the like can be preferably used.
- mono (2-methacryloyloxyethyl) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, di (2- Acryloyloxyethyloyl) acid phosphate and the like can be preferably used.
- sodium styrene sulfonate, sodium methacryl sulfonate and the like can be suitably used.
- a phosphonic acid group vinyl phosphonic acid, vinyl phenylphosphonic acid can be used.
- An acid or the like can be preferably used.
- the introduction amount of the functional group capable of supporting cerium that is, the amount of the functional group capable of supporting cerium contained in 1 g of the carrier is preferably 1 mmol / g or more, and 1.3 mmol / g or more. More preferably, it is more preferably 1.5 mmol / g or more, and particularly preferably 2 mmol / g or more. Further, the amount of the functional group capable of supporting cerium contained in 1 g of the carrier is preferably 10 mmol / g or less, and more preferably 8 mmol / g or less.
- the amount of the functional group capable of supporting cerium contained in 1 g of the carrier refers to a value calculated by the method described in Examples described later.
- the amount of the functional group capable of supporting cerium contained in 1 g of the carrier is 1 mmol / g or more, cerium can be sufficiently supported in a short time.
- reaction conditions in this step may be appropriately selected according to the functional group capable of supporting cerium, and are not particularly limited.
- the particulate cellulose base material into which the graft chain is introduced may be introduced into a sodium iminodiacetate aqueous solution to cause a reaction.
- the molar concentration of the aqueous solution of sodium iminodiacetate that is, the number of moles of sodium iminodiacetate in 1 L of the aqueous solution of sodium iminodiacetate is not particularly limited, but is preferably 0.1 M or more and 0.8 M or less. Yes, more preferably from 0.3M to 0.6M.
- the reaction temperature is preferably 60 ° C. or higher and 90 ° C. or lower, more preferably 75 ° C. or higher and 85 ° C. or lower.
- the reaction can be performed at 80 ° C. for 12 hours.
- the carrier obtained as described above and having a functional group capable of supporting cerium bonded thereto can be easily purified by washing with water and drying, for example.
- cerium supporting step may be performed under any conditions as long as trivalent cerium can be supported on a carrier having a functional group capable of supporting cerium.
- Examples of the water-soluble trivalent cerium salt include cerium trichloride. Cerium trichloride is preferable because it has a weak oxidizing ability and its aqueous solution is neutral, so that it hardly damages the carrier.
- the cerium supporting step using the aqueous solution of the water-soluble trivalent cerium salt can be performed at room temperature.
- the supporting rate and supporting rate of trivalent cerium are greatly improved. be able to.
- an adsorbent carrying a large amount of trivalent cerium can be produced in a short time.
- the cerium supporting step is preferably performed at 20 ° C. or higher, more preferably performed at 80 ° C. or higher, and further preferably performed at 100 ° C. or higher.
- the temperature of the said aqueous solution exceeds 100 degreeC, it can carry out using reaction containers, such as an autoclave, for example, and the temperature of the said aqueous solution can be measured with the temperature sensor etc. with which the reaction container was equipped.
- the supporting rate of cerium in the adsorbent is not particularly limited, but is usually 2 to 30% by mass, preferably 5 to 10% by mass, from the viewpoint of adsorption capacity, removal rate, physical stability, and the like.
- cerium Oxidation Process is performed by oxidizing the support carrying trivalent cerium obtained in the cerium carrying process from trivalent to tetravalent. And oxidizing.
- the surface color of the adsorbent is changed from white to dark brown as the cerium is changed from trivalent to tetravalent after the oxidation treatment.
- the method of oxidation treatment is not particularly limited.
- a method of contacting an aqueous solution of an oxidizing agent such as hydrogen peroxide or sodium hypochlorite with a carrier supporting cerium a method of contacting a carrier supporting cerium with ozone gas
- it can be carried out by a method of irradiating a carrier supporting cerium with UV or a method of irradiating a carrier supporting cerium with an electron beam (for example, a low energy electron beam).
- an oxidation treatment with an aqueous hydrogen peroxide solution or an aqueous sodium hypochlorite solution.
- the adsorbent according to the present invention includes a carrier having a functional group capable of carrying cerium and tetravalent cerium carried on the carrier, and the carrier is chelated with tetravalent cerium. Yes.
- the adsorbent can be manufactured by the manufacturing method described above.
- a graft chain is introduced by graft polymerization of an ethylenically unsaturated monomer on a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more.
- a graft chain is introduced, and the graft chain has a functional group capable of supporting cerium.
- a graft chain is introduced by graft polymerization of an ethylenically unsaturated monomer to a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more. It is preferable to have a functional group capable of supporting cerium.
- Examples of the functional group capable of supporting cerium include the above-described iminodiacetic acid group, phosphoric acid group, sulfonic acid group, and phosphonic acid group.
- the shape of the adsorbent is preferably particulate, and examples thereof include a spherical shape, an elliptical shape, and an indefinite diameter crushing shape. Among these, a spherical shape is more preferable from the viewpoint of mechanical strength.
- the average particle diameter of the adsorbent may be 100 to 1500 ⁇ m, more preferably 100 to 800 ⁇ m, and even more preferably 200 to 500 ⁇ m.
- conventional adsorption towers for ion exchange / chelating resin spheres, regeneration facilities, etc. can be used as they are.
- the adsorbent may be porous. Thereby, the adsorption target can flow in the pores. Therefore, more excellent adsorption performance can be obtained.
- the adsorbent can be suitably used as an arsenic adsorbent, but can also be suitably used as an adsorbent for anions such as fluorine ions and selenium ions.
- the adsorbent for example, by contacting with an object to be treated such as an aqueous solution containing arsenic, organic solvent solution, groundwater, soil, hot spring water, marsh lake water, seawater, factory wastewater, mine wastewater, well water, river water, etc. It can be used for removing fluorine and the like.
- an object to be treated such as an aqueous solution containing arsenic, organic solvent solution, groundwater, soil, hot spring water, marsh lake water, seawater, factory wastewater, mine wastewater, well water, river water, etc. It can be used for removing fluorine and the like.
- the supporting rate of cerium in the adsorbent is not particularly limited, but is usually 2 to 30% by mass, preferably 2 to 20% by mass from the viewpoint of adsorption capacity, removal rate, physical stability, and the like.
- the content is preferably in the range of 5 to 10% by mass.
- the adsorption treatment method according to the present invention is an adsorption treatment method for arsenic existing in water, and uses the adsorbent according to the present invention described above.
- the adsorbent according to the present invention carries tetravalent cerium, it can efficiently adsorb trivalent arsenic, and can be suitably used for removing arsenic.
- the adsorbent is introduced into an aqueous solution containing these and stirred, shaken, or passed through the column or adsorption tower filled with the adsorbent.
- the arsenic and the adsorbent are brought into contact with each other.
- harmful ions such as arsenic are adsorbed on the adsorbent.
- the adsorbent can be reused by treating the adsorbed arsenic with an appropriate eluent and oxidizing agent (e.g., elution with sodium hydroxide and reoxidation with sodium hypochlorite). is there.
- an appropriate eluent and oxidizing agent e.g., elution with sodium hydroxide and reoxidation with sodium hypochlorite.
- the method for producing an adsorbent according to the present invention includes a cerium supporting step of supporting trivalent cerium on a carrier having a functional group capable of supporting cerium, oxidizing the supported cerium, and And a cerium oxidation step for converting the valence of cerium to tetravalence.
- tetravalent cerium can be easily supported on a carrier without using a tetravalent cerium aqueous solution having very strong oxidizing power and strong acidity. For this reason, there exists an effect that the adsorption material with high adsorption capability with respect to trivalent arsenic can be manufactured simply.
- the method for producing an adsorbent according to the present invention further includes a carrier preparation step of preparing the carrier having a functional group capable of supporting cerium, and the carrier preparation step includes cellulose having a crystallinity of 80% or more.
- An activation step of activating the particulate cellulose-based substrate as a main component, and bringing the activated particulate cellulose-based substrate into contact with the ethylenically unsaturated monomer allows the ethylenically unsaturated monomer to It is preferable to include a graft chain introducing step of introducing a graft chain by graft polymerization onto a particulate cellulose base material, and a functional group binding step of bonding a functional group capable of supporting cerium to the introduced graft chain.
- the carrier is prepared by performing graft polymerization on the particulate cellulose base material, the size of the carrier is arbitrarily controlled by appropriately adjusting the graft ratio and the size of the cellulose particles. can do. That is, according to the above method, it is possible to produce a spherical adsorbent that is easy to control the structure, has excellent stability, and has an arsenic adsorption ability superior to that of conventional arsenic adsorption resin balls.
- the graft chain introduction step includes bringing the activated particulate cellulose base material into contact with an emulsion containing an ethylenically unsaturated monomer, thereby producing the ethylenic material. It is preferable to introduce a graft chain by graft polymerization of an unsaturated monomer to the particulate cellulose base material.
- the radical utilization rate and the polymerization rate are higher than those of solution polymerization using an organic solvent.
- the irradiation dose required for generating radicals in the substrate can be lowered, and the reaction time can be greatly reduced.
- an adsorbent with high mechanical strength can be provided.
- the graft chain introduction step is preferably performed so that the graft ratio is 100% or more.
- the particulate cellulose-based substrate is activated by irradiating the particulate cellulose-based substrate with ionizing radiation, and the ionizing property.
- the radiation is ⁇ -rays, electron beams, or X-rays, and the dose is preferably 10 to 20 kGy.
- the cellulose base material has a crystallinity of 95% or more.
- an adsorbent excellent in mechanical strength and chemical stability can be produced.
- the functional group capable of supporting cerium is at least one selected from the group consisting of an iminoniacetic acid group, a phosphoric acid group, a sulfonic acid group, and a phosphonic acid group. It is preferable that
- the adsorbent can be more easily produced because it can be easily introduced into the graft chain.
- the content of the functional group capable of supporting cerium in the carrier is preferably 1 mmol / g or more.
- an adsorbent capable of sufficiently supporting cerium in a short time can be produced.
- the adsorbent can be manufactured more easily.
- the cerium supporting step is preferably performed at 20 ° C. or higher.
- the adsorbent can be manufactured more easily.
- the cerium supporting step is preferably performed at 80 ° C. or higher.
- the adsorbent can be manufactured more easily.
- the cerium carrying step it is preferable to carry the cerium carrying step so that the cerium carrying ratio of the carrier is in the range of 2 to 20% by mass.
- an adsorbent excellent in adsorption capacity, removal rate and physical stability can be produced.
- the cerium oxidation step is performed by contacting a carrier supporting cerium with an aqueous oxidant solution, contacting a carrier supporting cerium with ozone gas, and a carrier supporting cerium. It is preferable to carry out by a method of irradiating UV or a method of irradiating an electron beam onto a carrier supporting cerium.
- the adsorbent according to the present invention is obtained by the above method according to the present invention, and is characterized in that the carrier is chelated with tetravalent cerium.
- the adsorbent according to the present invention includes a carrier having a functional group capable of carrying cerium and tetravalent cerium carried on the carrier, and the carrier is chelated with tetravalent cerium. It is a feature.
- the carrier is chelated with tetravalent cerium, an adsorbent having a high adsorption ability for trivalent arsenic can be provided.
- the carrier has graft chains introduced by graft polymerization of an ethylenically unsaturated monomer to a particulate cellulose base material mainly composed of cellulose having a crystallinity of 80% or more. It is preferable that the graft chain has a functional group capable of supporting cerium.
- the average particle diameter is preferably in the range of 100 to 1500 ⁇ m.
- the adsorbent according to the present invention is preferably an adsorbent for adsorbing at least one anion selected from the group consisting of arsenic ions, fluorine ions, and selenium ions.
- the adsorbent according to the present invention is preferably an adsorbent for adsorbing arsenic dissolved in soil, groundwater, tap water, seawater, industrial wastewater, hot spring water, or mine wastewater.
- the adsorption treatment method according to the present invention is a method for adsorption treatment of arsenic existing in water, and is characterized by using the adsorbent according to the present invention.
- the adsorbent according to the present invention which has a high adsorption ability for trivalent arsenic, is used, there is an effect that trivalent arsenic can be efficiently adsorbed.
- adsorption treatment method it is preferable to use a column or an adsorption tower packed with the adsorbent.
- trivalent arsenic can be adsorbed more efficiently.
- the graft ratio that is, the amount (mass percentage) of the ethylenically unsaturated monomer introduced by graft polymerization with respect to the particulate cellulose base material was determined by the following method.
- the graft polymer of the particulate cellulose base material into which the ethylenically unsaturated monomer has been introduced is immersed in an organic solvent such as methanol or acetone for 48 hours to remove unreacted ethylenically unsaturated monomer and homopolymer Removed. Thereafter, the graft polymer of the particulate cellulose base material was further immersed in water for 24 hours, washed with water, and dried at 50 ° C. for 24 hours.
- an organic solvent such as methanol or acetone
- the graft ratio is calculated from the weight (Wg) of the graft polymer of the particulate cellulose base material after drying and the dry weight (W0) of the particulate cellulose base material before introducing the ethylenically unsaturated monomer.
- Graft ratio (%) ((Wg ⁇ W0) / W0) ⁇ 100 ⁇ Amount of functional group capable of supporting cerium contained in 1 g of carrier>
- the amount of the functional group capable of supporting cerium contained in 1 g of the carrier is the mass (Wg, unit: g) of the graft polymer of the particulate cellulose base material obtained by the above method, and the functional group capable of supporting cerium. It was calculated by the following equation from the weight (Wp, unit: g) of the support obtained by binding an equivalent (M) and a functional group capable of supporting cerium, washing and drying.
- the amount of cerium supported that is, the amount of cerium supported (mass percentage) relative to the mass of the adsorbent is calculated from the mass of the carrier used (Wp) and the mass of the adsorbent obtained (Wq) by the following equation. did.
- Cerium loading (mass%) ((Wq ⁇ Wp) / Wq) ⁇ 100
- Cellulose fine particles composed of only microcrystalline cellulose (diameter: 200 to 300 ⁇ m, product name: SELFIA (registered trademark), manufactured by Asahi Kasei Chemicals Corporation, crystallinity: 99% or more) are placed in a thin plastic bag. The bag was purged several times with nitrogen and sealed.
- the bag was cooled with dry ice and irradiated with ionizing radiation having a dose of 20 kGy using an industrial high-performance electron accelerator (product name: EPS-800, manufactured by NHV Corporation) to generate radical active sites.
- EPS-800 industrial high-performance electron accelerator
- the sample after irradiation was immediately immersed in an emulsion solution of glycidyl methacrylate substituted with nitrogen prepared in advance.
- composition of the emulsion used was 3% by mass of a surfactant (trade name: Tween 20, manufactured by Wako Reagent Co., Ltd.), 30% by mass of glycidyl methacrylate, and 67% by mass of water.
- a surfactant trade name: Tween 20, manufactured by Wako Reagent Co., Ltd.
- the glycidyl methacrylate-grafted cellulose particles obtained under the above conditions were charged into a 0.5 M aqueous solution of sodium iminoniacetate and reacted at 80 ° C. for 12 hours.
- the obtained sample was washed with water and dried to obtain a carrier (diameter: 400 to 500 ⁇ m).
- the functional group density of iminodiacetic acid groups in this carrier was about 2.2 mol / g.
- the carrier was immersed in a 0.1 M cerium chloride (CeCL 3 ) solution at about 80 ° C. for 8 hours to obtain an adsorbent carrying trivalent cerium.
- the loading of trivalent cerium in the adsorbent was 9% by mass.
- the adsorbent carrying trivalent cerium is brought into contact with a 20% by mass aqueous solution of H 2 O 2 at room temperature for 24 hours, and then washed with pure water and dried to obtain tetravalent cerium having a dark brown color.
- a supported adsorbent (hereinafter referred to as “CCM-As”) was obtained.
- the adsorption rate of cerium in the adsorbent was 9% by mass.
- Trivalent arsenic> A commercially available trivalent arsenic standard solution was diluted with pure water to prepare a 5 ppm trivalent arsenic solution (initial pH: around 6.5).
- Adsorbent CCM-As (0.1 g) was put in 100 mL of 5 ppm arsenic aqueous solution and stirred at room temperature for 24 hours. Thereafter, arsenic in the supernatant was measured with an ICP emission spectrometer, and the amount of arsenic adsorbed was determined from the initial concentration in the solution and the residual concentration after treatment.
- Figure 1 shows the results.
- the adsorbent CCM-As has an adsorption capacity for trivalent arsenic that is equal to or higher than that of a commercially available arsenic adsorption resin sphere. That is, the adsorbent CCM-As can remove almost all of the arsenic in water after the treatment with the adsorbent, and can achieve a water supply standard of 0.01 ppm.
- the adsorbent CCM-As (0.1 g) was placed in 100 mL of a 5 ppm arsenic aqueous solution and stirred at room temperature for 24 hours. Thereafter, arsenic in the supernatant was measured with an ICP emission spectrometer, and the amount of arsenic adsorbed was determined from the initial concentration in the solution and the residual concentration after treatment.
- Figure 2 shows the results.
- the adsorbent CCM-As showed an adsorption capacity equal to or higher than that of pentavalent arsenic compared to the commercially available arsenic adsorbent resin sphere and the commercially available alumina adsorbent. That is, the adsorbent CCM-As can remove almost all of the arsenic in water after the treatment with the adsorbent, and can achieve a water supply standard of 0.01 ppm.
- the adsorbent according to the present invention has a high adsorption capacity for both trivalent arsenic and pentavalent arsenic.
- the adsorbent of the present invention has an excellent adsorption capacity for arsenic and the like, and purifies groundwater, factory wastewater, hot spring water, mine wastewater, etc. contaminated with these harmful substances. It was confirmed that this was very advantageous.
- the adsorbent produced in the present example is manufactured by ionizing radiation, in particular, electron beam irradiation using an electron accelerator, so that it is industrially easily mass-produced and practical.
- the adsorbent of the present invention can replace the conventional arsenic adsorbent.
- the adsorbent of the present invention can be suitably used as an adsorbent for various harmful substances such as arsenic.
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Abstract
Description
本発明に係る吸着材の製造方法では、セリウムを担持可能な官能基を有する担体に、3価のセリウムを担持させるセリウム担持工程と、担持した上記セリウムを酸化して、当該セリウムの価数を4価にするセリウム酸化工程とを含む。このため、取り扱いが困難である4価のセリウム塩を用いることなく、4価のセリウムを担持した吸着材を製造することができる。
担体作製工程は、上記担体を製造することができればどのような方法であってもよい。
本実施の形態では、まず、活性化工程において、結晶化度が80%以上のセルロースを主成分とする粒子状セルロース系基材を活性化する。
上記活性化工程で活性化された粒子状セルロース系基材は、グラフト鎖導入工程で、エチレン性不飽和モノマーと接触させて、当該エチレン性不飽和モノマーを上記粒子状セルロース系基材にグラフト重合させる。これにより、上記粒子状セルロース系基材にグラフト鎖が導入される。
官能基結合工程では上記グラフト鎖導入工程で導入された上記グラフト鎖に、セリウムを担持可能な官能基を結合させる。
セリウム担持工程は、セリウムを担持可能な官能基を有する担体に3価のセリウムを担持させることができれば、どのような条件下で行ってもよい。例えば、セリウム担持工程では、水溶性である3価のセリウム塩の水溶液を用いて上記担体に3価のセリウムを担持させることが好ましい。
セリウム酸化工程は、上記セリウム担持工程によって得られた、3価のセリウムを担持した担体を酸化処理することによって、担体において担持されたセリウムを3価から4価へと酸化させる工程である。例えば、上述したセルロース基材にセリウムを担持した吸着材の場合では、酸化処理後、セリウムは3価から4価になることによって吸着材の表面の色が白色から濃い茶色となる。
本発明に係る吸着材は、セリウムを担持可能な官能基を有する担体と、当該担体に担持された4価のセリウムとを含み、担体が4価のセリウムとキレート形成している。当該吸着材は、上述した製造方法によって製造することができる。
本発明に係る吸着処理方法は、水中に存在するヒ素の吸着処理方法であって、上述した本発明に係る吸着材を用いる。
グラフト率、即ち、粒子状セルロース系基材に対する、グラフト重合により導入されているエチレン性不飽和モノマーの量(質量百分率)は、以下の方法で求めた。
グラフト率(%)=((Wg-W0)/W0)×100
<担体1g中に含まれるセリウムを担持可能な官能基の量>
担体1g中に含まれるセリウムを担持可能な官能基の量は、上記方法で求めた粒子状セルロース系基材のグラフト重合物の質量(Wg、単位:g)、セリウムを担持可能な官能基の当量(M)、セリウムを担持可能な官能基を結合し洗浄乾燥して得られた担体の質量(Wp、単位:g)から次式により算出した。
<セリウムの担持率>
セリウムの担持率、即ち、吸着材の質量に対する、担持されたセリウムの量(質量百分率)は、用いた担体の質量(Wp)と、得られた吸着材の質量(Wq)から次式により算出した。
セリウムの担持率(質量%)=((Wq-Wp)/Wq)×100
〔実施例1〕
微結晶セルロースのみから構成されるセルロース微粒子(直径:200~300μm、製品名:セルフィア(登録商標)、旭化成ケミカルズ社製、結晶化度:99%以上)を、薄いプラスチックバッグの中に配置して、当該バッグを窒素で数回パージし、密封した。
実施例1で得た吸着材CCM-Asを用いて、以下のようなヒ素のバッチ吸着実験を行った。
市販の3価のヒ素標準液を純水で希釈して、5ppmの3価のヒ素溶液を調製した(初期pH:6.5前後)。
市販の5価のヒ素標準液を純水で希釈して、5ppmの5価のヒ素溶液を調製した(初期pH:6.5前後)。
Claims (21)
- セリウムを担持可能な官能基を有する担体に、3価のセリウムを担持させるセリウム担持工程と、
担持した上記セリウムを酸化して、当該セリウムの価数を4価にするセリウム酸化工程と、
を含むことを特徴とする吸着材の製造方法。 - セリウムを担持可能な官能基を有する上記担体を作製する担体作製工程を更に含み、
上記担体作製工程は、
結晶化度が80%以上のセルロースを主成分とする粒子状セルロース系基材を活性化する活性化工程と、
活性化された粒子状セルロース系基材を、エチレン性不飽和モノマーと接触させることにより、当該エチレン性不飽和モノマーを上記粒子状セルロース系基材にグラフト重合させてグラフト鎖を導入するグラフト鎖導入工程と、
導入された上記グラフト鎖にセリウムを担持可能な官能基を結合させる官能基結合工程とを含むことを特徴とする請求項1に記載の吸着材の製造方法。 - 上記グラフト鎖導入工程では、活性化された粒子状セルロース系基材を、エチレン性不飽和モノマーを含むエマルションと接触させることにより、当該エチレン性不飽和モノマーを上記粒子状セルロース系基材にグラフト重合させてグラフト鎖を導入することを特徴とする請求項2に記載の吸着材の製造方法。
- 上記グラフト鎖導入工程は、グラフト率が100%以上となるように行うことを特徴とする請求項2又は3に記載の吸着材の製造方法。
- 上記活性化工程では、粒子状セルロース系基材に対して電離性放射線を照射することによって粒子状セルロース系基材を活性化し、
上記電離性放射線が、γ線、電子線、又はX線であり、その線量が10~20kGyであることを特徴とする請求項2~4の何れか1項に記載の吸着材の製造方法。 - 上記セルロース系基材の結晶化度が95%以上であることを特徴とする請求項2~5の何れか1項に記載の吸着材の製造方法。
- セリウムを担持可能な上記官能基が、イミノニ酢酸基、リン酸基、スルホン酸基、及びホスホン酸基からなる群から選択される少なくとも1種であることを特徴とする請求項1~6の何れか1項に記載の吸着材の製造方法。
- 上記担体における、セリウムを担持可能な上記官能基の含有率が1mmol/g以上であることを特徴とする請求項1~7の何れか1項に記載の吸着材の製造方法。
- セリウム担持工程では、3価の水溶性セリウム塩を用いて、3価のセリウムを担体に担持させることを特徴とする請求項1~8の何れか1項に記載の吸着材の製造方法。
- セリウム担持工程を20℃以上で行うことを特徴とする請求項1~9の何れか1項に記載の吸着材の製造方法。
- セリウム担持工程を80℃以上で行うことを特徴とする請求項1~10の何れか1項に記載の吸着材の製造方法。
- 上記セリウム担持工程では、担体のセリウム担持率が2~20質量%の範囲内となるように担持させることを特徴とする請求項1~11の何れか1項に記載の吸着材の製造方法。
- 上記セリウム酸化工程を、セリウムを担持した担体を酸化剤水溶液と接触させる方法、セリウムを担持した担体をオゾンガスと接触させる方法、セリウムを担持した担体に対してUVを照射する方法、又はセリウムを担持した担体に対して電子ビームを照射する方法によって行うことを特徴とする請求項1~12の何れか1項に記載の吸着材の製造方法。
- 請求項1~13の何れか1項に記載の方法によって得られ、担体が4価のセリウムとキレート形成していることを特徴とする吸着材。
- セリウムを担持可能な官能基を有する担体と、当該担体に担持された4価のセリウムとを含み、担体が4価のセリウムとキレート形成していることを特徴とする吸着材。
- 上記担体は、結晶化度が80%以上のセルロースを主成分とする粒子状セルロース系基材に、エチレン性不飽和モノマーをグラフト重合することによってグラフト鎖が導入されており、当該グラフト鎖がセリウムを担持可能な官能基を有していることを特徴とする請求項15に記載の吸着材。
- 平均粒子径が100~1500μmの範囲内であることを特徴とする請求項14~16の何れか1項に記載の吸着材。
- ヒ素イオン、フッ素イオン、及びセレンイオンからなる群から選択される少なくとも1種の陰イオンを吸着するための吸着材であることを特徴とする請求項14~17の何れか1項に記載の吸着材。
- 土壌、地下水、水道水、海水、工業排水、温泉水、又は鉱山廃水に溶解しているヒ素を吸着するための吸着材であることを特徴とする請求項14~18の何れか1項に記載の吸着材。
- 水中に存在するヒ素の吸着処理方法であって、
請求項14~19の何れか1項に記載の吸着材を用いることを特徴とする吸着処理方法。 - 上記吸着材を充填した、カラム又は吸着塔を用いることを特徴とする請求項20に記載の吸着処理方法。
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