[go: up one dir, main page]

CN102481547A - Adsorbent, method for producing same, and use thereof - Google Patents

Adsorbent, method for producing same, and use thereof Download PDF

Info

Publication number
CN102481547A
CN102481547A CN2009801612534A CN200980161253A CN102481547A CN 102481547 A CN102481547 A CN 102481547A CN 2009801612534 A CN2009801612534 A CN 2009801612534A CN 200980161253 A CN200980161253 A CN 200980161253A CN 102481547 A CN102481547 A CN 102481547A
Authority
CN
China
Prior art keywords
cerium
sorbing material
carrier
mentioned
load
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2009801612534A
Other languages
Chinese (zh)
Inventor
赵龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NHV Corp
Original Assignee
NHV Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NHV Corp filed Critical NHV Corp
Publication of CN102481547A publication Critical patent/CN102481547A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Soil Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The method for producing an adsorbent of the present invention comprises the steps of: a cerium supporting step of supporting cerium having a valence-3 by a carrier having a functional group capable of supporting cerium; and a cerium oxidation step of oxidizing the supported cerium to have a valence of 4. Therefore, an adsorbent having a high adsorption capacity for 3-valent arsenic can be produced.

Description

Sorbing material, its manufacturing approach and utilization thereof
Technical field
The present invention relates to sorbing material, its manufacturing approach and utilization thereof.
Background technology
In recent years, because problems such as environmental pollutions, the removing of arsenic in the Environmental Water such as underground water, soil, thermal water, lakes and marhshes water, seawater, plant chimney stalk, mine wastewater, well water, rivers and creeks water becomes important problem.
Arsenic is present in various waste water, rivers and creeks water, the well water etc.Therefore in addition, arsenic also is present in the soil, has problems when the rivers and creeks water of a part or underground water being used as running water.Because therefore the strong toxicity of arsenic has set strict a reference value (environmental criteria 0.01ppm, waste water benchmark 0.1ppm), and the exploitation that the micro amount of arsenic in the water is removed treatment technology is attracted attention.
Remove technology as arsenic, proposed the precipitation method, absorption method etc., wherein, be widely used based on the arsenic processing method of the coagulative precipitation of using molysite, aluminium salt.But, utilize these methods to be difficult to remove 3 valency arsenic (form with arsenious acid exists).In addition, in the precipitation method, the isolated by filtration after the precipitation process and a large amount of offal treatments become problem, are difficult to remove the micro amount of arsenic of low concentration in anhydrating.
On the other hand, in absorption method, use activated alumina, strong-base anion-exchange resin etc.But, when using strong basic ion exchange resin, remove the significantly reduced problem of effect owing to there is arsenic in coexisting ion; When using activated alumina, though high for the compatibility of arsenic, exist in the acidic region dissolving on the contrary and problem such as can't use repeatedly.
In addition, these sorbing materials have the very big problem that can't directly adsorb 3 valency arsenic.Particularly, under phreatic situation,, therefore need to utilize the pretreatment procedure that adds oxidant that 3 valency arsenic are changed into than are adsorbed behind the 5 valency arsenic (arsenic acid ion) that are easier to adsorb because arsenic exists with the state of 3 valency arsenic basically.
Therefore, from establishing the aspect of the economic arsenic technology of removing, realize not carrying out pre-treatment and any one the sorbing material that can directly adsorb effectively in 3 valency arsenic, the 5 valency arsenic is very valuable.
In such trend, known in the past rare earth metal, particularly cerium have very high compatibility for arsenic, have studied the application of material in the processing of processed water that contains them.
Because 4 valency ceriums are 3 valency arsenic in the adsorbed water effectively; Therefore the composition as the sorbing material of the 3 valency arsenic that are used for removing underground water is known; For example, the water miscible rare earth metal salt of known interpolation with remove the object material and generate the method that insoluble salt is removed thus.
But, when using this method, can produce the identical problem of use with above-mentioned iron, aluminium salt.In addition, it is high a lot of that the cost of rare earth metal salt is compared with iron, aluminium salt, therefore need be for recycling and reuse through the insoluble salt after to processing of dissolving, Separation of Solid and Liquid etc. again, but the recovery process of rare earth metal salt is numerous and diverse, is difficult to utilize again.
On the other hand, water-insoluble rare earth metal exists with the form of the oxide of little coccoid usually, is therefore adsorbing, is having reluctant shortcoming aspect the wash-out regeneration plasma swap operation.
Therefore, in order to improve such shortcoming, proposed some rare earth metal has been carried on the method on the carrier.Here, water-soluble according to the rare earth metal reagent that uses in the load operation, the method that rare earth metal is carried on the carrier mainly is divided into two kinds.
Wherein a kind of method can be enumerated out: the microparticulate that makes the water-insoluble rare-earth oxide through suitable organic solvent is in the binding agent macromolecule resin material, and it is granular thereafter resin glue to be shaped to.
For example, proposed the manufacturing approach of following arsenic, fluorine sorbing material: it utilizes said method, and cerium oxide is particle loaded on ethylene-vinyl alcohol copolymer resins such as (EVOH), makes (for example, referring to patent documentation 1～4) thus.
But in these methods, the mechanical strength of the resin balls of moulding in order to keep needs the cerium oxide of load tens quality % above (many situation are issued to 85 quality %) usually.In addition, because the cost of resin glue is also than higher, so material cost is very high.In addition, the problem that in water flowing and regeneration, also exists carried metal to spill.In addition, because the difference of the size of raw material cerium oxide particle, adsorption capacity significantly changes.
Known another kind of method is: the aqueous solution of preparation water-solubility rare-earth slaine, porous inorganic carriers such as dipping bentonite, aluminium oxide, diatomite at high temperature burn till then, carry out load (for example, referring to patent documentation 5) thus.
In this method, need under the temperature of several Baidu, burn till usually, therefore have the numerous and diverse and inadequate problem of adsorption capacity resulting sorbing material of manufacturing approach.
In order to improve this shortcoming, proposed utilization and formed complex compound and make rare earth metal be carried on the method (for example, referring to patent documentation 6～7) on the carrier.For example, proposed to utilize water-solubility rare-earth aqueous metal salt and form the manufacturing approach that rare earth metal is carried on the sorbing material on the chelating resin through complex compound.
In addition; Also reported a kind of granular fiber prime system sorbing material that chelating forms group etc. of in granular fiber prime system base material, having introduced; This granular fiber prime system base material is at carried metal and be that cellulose more than 80% is as main component (for example, referring to patent documentation 8) with degree of crystallinity not on the carrier.
The prior art document
Patent documentation
Patent documentation 1: Japan's publication communique " TOHKEMY 2005-288363 number (on October 20th, 2005 is open) "
Patent documentation 2: Japan's publication communique " TOHKEMY 2005-28312 number (on February 3rd, 2005 is open) "
Patent documentation 3: Japan's publication communique " TOHKEMY 2009-72773 number (on April 9th, 2009 is open) "
Patent documentation 4: Japan's publication communique " TOHKEMY 2006-297382 number (on November 2nd, 2006 is open) "
Patent documentation 5: Japan's publication communique " TOHKEMY 2005-205368 number (on August 4th, 2005 is open) "
Patent documentation 6: Japan's publication communique " TOHKEMY 2004-188307 number (on July 8th, 2004 is open) "
Patent documentation 7: Japan's publication communique " TOHKEMY 2007-185604 number (on July 26th, 2007 is open) "
Patent documentation 8: Japan's publication communique " TOHKEMY 2009-13204 number (on January 22nd, 2009 is open) "
Summary of the invention
The problem that invention will solve
But, expect in a kind of and above-mentioned patent documentation 6～8 that the formation of record compares the higher sorbing material of adsorption capacity of arsenic.
For example, load the sorbing material of zirconium low for the adsorptivity of 3 valency arsenic, therefore be difficult to use in the phreatic processing that has a large amount of 3 valency arsenic etc.
The present invention carries out in view of the above problems, and its purpose is to realize for the adsorption capacity of 3 valency arsenic high sorbing material and manufacturing approach thereof.
The scheme that is used to deal with problems
In order to address the above problem, the inventor think if can be on carriers such as chelating resin load compare with zirconium for arsenic and have more 4 valency ceriums of high-affinity, then can make for the high sorbing material of the adsorption capacity of 3 valency arsenic.
But, the report of the example of successful load 4 valency ceriums on carrier not also up to now with the functional group that keeps through chelate structure.This be because, the oxidizing force of the aqueous solution of water-soluble 4 valency cerium salt is very strong, therefore the aqueous solution is highly acid, is difficult to load 4 valency ceriums on carrier.Particularly, in chelating resin,, thereby be very difficult to load 4 valency ceriums because resin self receives very big damage from cellulosic substrates.
Therefore, the inventor finds, if direct load 4 valency ceriums on chelating resin not, but initial load 3 valency ceriums, the cerium with institute's load is oxidized to 4 valencys then, then can be on chelating resin load 4 valency ceriums, accomplished the present invention thus.
That is, in order to address the above problem, the manufacturing approach of sorbing material of the present invention is characterised in that and comprises following operation: the cerium load operation that makes the carrier loaded 3 valency ceriums with functional group that can cerium-carrying; The above-mentioned cerium of oxidation institute load makes the valence mumber of this cerium become the oxidation operation of 4 valency ceriums.
According to said method, need not to use oxidizing force very strong and be the highly acid 4 valency cerium aqueous solution, and load 4 valency ceriums on carrier easily.Therefore, can not cause very big damage, can be able to make easily effect for the high sorbing material of the adsorption capacity of 3 valency arsenic to carrier.
Sorbing material of the present invention is characterised in that it obtains through said method of the present invention, and carrier and 4 valency cerium chelatings form.
In addition, sorbing material of the present invention is characterised in that, it comprises carrier with functional group that can cerium-carrying and is carried on 4 valency ceriums on this carrier, and carrier and 4 valency cerium chelatings form.
Through these formations, carrier and 4 valency ceriums have carried out chelating formation, therefore can be able to provide the effect for the high sorbing material of the adsorption capacity of 3 valency arsenic.
Adsorption treatment method of the present invention is characterised in that, it is the adsorption treatment method of the arsenic that exists in the water, and it uses above-mentioned sorbing material of the present invention.
According to said method,, therefore can be able to effectively 3 valency arsenic carried out the effect of adsorption treatment owing to used for the high of the present invention above-mentioned sorbing material of the adsorption capacity of 3 valency arsenic.
The effect of invention
As stated, sorbing material of the present invention is characterised in that, it obtains through the method that comprises following operation, and carrier and 4 valency ceriums have carried out chelating formation, and said operation is: the cerium load operation that makes the carrier loaded 3 valency ceriums with functional group that can cerium-carrying; The above-mentioned cerium of oxidation institute load makes the valence mumber of this cerium become the cerium oxidation operation of 4 valencys.
Therefore, can be able to provide effect for the high sorbing material of the adsorption capacity of 3 valency arsenic.
Description of drawings
Fig. 1 is result's the curve map that the adsorption experiment of 3 valency arsenic among the embodiment is shown.
Fig. 2 is result's the curve map that the adsorption experiment of 5 valency arsenic among the embodiment is shown.
The specific embodiment
Below, the present invention will be described in more detail, but the present invention does not receive any qualification of these explanations.In addition, short of special declaration, the various rerum naturas of then enumerating in this specification refer to through after the value measured of the method put down in writing among the embodiment that states.
Need to prove; In this specification; " main component " is meant in the composition that is contained in the maximum composition of mass conversion content, and " A～B " of expression scope is meant that A is above and below the B, and short of special declaration then " ppm " refers to the value of trying to achieve with mass conversion.
(I) manufacturing approach of sorbing material
Comprise following operation in the manufacturing approach of sorbing material of the present invention: the cerium load operation that makes carrier loaded 3 valency ceriums with functional group that can cerium-carrying; The above-mentioned cerium of oxidation institute load makes the valence mumber of this cerium become the cerium oxidation operation of 4 valencys.Therefore, need not to use 4 valency cerium salt of difficult treatment, and the sorbing material of 4 valency ceriums of can having made load.
Need to prove that above-mentioned " making carrier loaded " is meant " possessing on carrier with the carrier bonding ", this bonding can be covalent bond, also can be ionic bond, but preferred at 2 places the chelating bonding of above cerium-carrying.
As functional group that can cerium-carrying, for example, carry out the viewpoint that chelating forms from making carrier and cerium, can enumerate out iminodiacetic acid (salt) acidic group, phosphate, sulfonic group, phosphonate group etc.
Wherein, from the viewpoint of the easy property of the reaction of cerium-carrying, functional group that can cerium-carrying is the iminodiacetic acid (salt) acidic group more preferably.
Manufacturing approach of the present invention can also comprise the carrier production process that is used to make above-mentioned carrier.Below, each operation is described.
(I-I) carrier production process
As long as can make above-mentioned carrier, then the carrier production process is that which kind of method all can.
As above-mentioned carrier, for example, the carrier of functional group that can cerium-carrying that can use on the grafted chain of granular fiber prime system base material bonding; At oil such as polypropylene, polyethylene, ethylene-vinyl alcohol copolymers be on the grafted chain of plastic basis material bonding the carrier etc. of functional group that can cerium-carrying.
At bonding on the grafted chain of granular fiber prime system base material under the situation of carrier of functional group that can cerium-carrying; For example preferably include following operation in the carrier production process: activation procedure, making with degree of crystallinity is that cellulose more than 80% is as the granular fiber prime system base material activation of main component; Grafted chain is introduced operation, and the granular fiber prime system base material of activation is contacted with ethylenically unsaturated monomer, thus on above-mentioned granular fiber prime system base material this ethylenically unsaturated monomer of glycerol polymerization, the introducing grafted chain; Functional group's bond sequence, the functional group that bonding can cerium-carrying on the above-mentioned grafted chain of being introduced.
As above-mentioned base material, through use with degree of crystallinity be cellulose 80% or more as the granular fiber prime system base material of main component, thereby degree of crystallinity is high, so can obtain the sorbing material of mechanical strength excellence.In addition, cellulose is the maximum hydrophilic natural material of occurring in nature amount, thereby little to the burden of environment, can obtain cheap sorbing material, and be hydrophily.Therefore, can improve absorption property in water.In addition, owing to be granular, thereby can directly use adsorption tower that existing ion-exchange/the chelating resin ball is used, reclaim equiment etc.
As the carrier production process in this embodiment, for example, can enumerate out the method for putting down in writing in the TOHKEMY 2009-13204 communique.Below, as an example of this embodiment, introduce the carrier production process of operation and functional group's bond sequence and describe comprising activation procedure, grafted chain.
< activation procedure >
In this embodiment, at first, in activation procedure, to being that cellulose more than 80% carries out activation as the granular fiber prime system base material of main component with degree of crystallinity.
Activation is for example carried out through following mode: in advance the spherical particle of cellulose is disposed in the foil-type plastic bag; After utilizing non-active gas such as nitrogen that this bag is repeatedly purged and seals; Under nitrogen atmosphere; Utilizing irradiation ionizing radiation line under the cooling condition of dry ice, generate the free radical activity point.
Above-mentioned granular fiber prime system base material is so long as be that cellulose more than 80% does not limit as the granular fiber prime system base material of main component is then special with degree of crystallinity.That is, it is the cellulose more than 80% that above-mentioned granular fiber prime system base material preferably only comprises degree of crystallinity, but only otherwise absorption property is produced harmful effect, then also can contain other compositions.More specifically, " as main component " is meant that the degree of crystallinity that in above-mentioned granular fiber prime system base material, can contain more than 90%, more preferably more than 95%, further be preferably more than 99% is the cellulose more than 80%.
In addition, other compositions that can contain are not special to be limited, and for example, can enumerate out hemicellulose, lignin, starch etc.
As the cellulose of the main component of above-mentioned granular fiber prime system base material is that degree of crystallinity is that granular fiber more than 80% is plain.Here; Degree of crystallinity is that the granular fiber element more than 80% is meant in the plain particle of granular fiber as long as the mass fraction of crystallinity part is 80% or more, be included in common by crystallinity partly and in the cellulose grain that partly constitutes of amorphism degree of crystallinity be the cellulose grain more than 80%, the cellulose grain that constitutes by microcrystalline cellulose more than 80% etc.
In addition, microcrystalline cellulose is meant and removes common cellulosic amorphism part and refining material here, and its degree of crystallinity is near 100%.Need to prove that above-mentioned degree of crystallinity can be measured through X-ray diffraction method.
, more preferably more than 90%, further be preferably more than 95% as long as degree of crystallinity is more than 80% as the cellulose of the main component of above-mentioned granular fiber prime system base material, be preferably more than 99% especially.
As degree of crystallinity is the granular fiber prime system base material more than 99%, for example, can enumerate out the aggregate of microcrystalline cellulose 100%.As above-mentioned microcrystalline cellulose, particularly, for example can enumerate out as reagent with waiting and commercially available microcrystalline cellulose, as an example, for example can enumerate out the CEOLUS (registration mark), CELPHERE (registration mark) of Asahi Chemical Corp etc.
In addition, the shape of above-mentioned granular fiber prime system base material is so long as granular then not special the qualification can be sphere, ellipse, amorphous broken shape etc.Wherein, from the viewpoint of mechanical strength, the shape of above-mentioned granular fiber prime system base material is more preferably spherical.
In addition, the average grain diameter of above-mentioned granular fiber prime system base material is that 30～800 μ m get final product under drying regime, and more preferably 50～500 μ m further are preferably 100～300 μ m.
Need to prove that in this specification, except the situation of other special provisions, average grain diameter is meant the value of utilizing following method decision.At first, from some collection samples as the aggregate of the particle of sample.For each sample; Utilize electron microscope to observe; From whole samples of some collections, measure major axis footpath respectively, be the size of the maximum direction of the size of coating of particles as a particle of object for adding up to particle more than 100.In the measured value more than 100, remove up and down each 20%, the mean value of the measured value with resulting 60% is as the average grain diameter among the present invention.
In addition, above-mentioned granular fiber prime system base material can be porous matter cellulose.Through using porous matter cellulose, the granular sorbing material of resulting cerium load in pore, also introduced can load 4 valency ceriums functional group and 4 valency ceriums, in addition, the absorption object can flow in pore.Therefore, can obtain the more excellent granular sorbing material of cerium load of absorption property.
About activation, as long as can generate free radical activity point so that in ensuing grafted chain introducing operation, can introduce grafted chain, then its method is not special limits.For example, can use following method: utilize radical polymerization initiator to carry out the method for chemical activation; Through shining the method that ionization radial line carries out activation; Carry out the method for activation through irradiation ultraviolet radiation; Carry out the method for activation through ultrasonic wave; Carry out the method for activation through plasma irradiating; Or the like.
Wherein, the method for irradiation ionization radial line have that manufacturing process is simple, the advantage of safety and low public hazards.In addition, the surface that can grafted chain be introduced into granular fiber prime system base material can obtain the more excellent sorbing material of adsorption capacity until inside.
When carrying out activation,, therefore to shine the ionization radial line that can not cause the dosage of damage to granular fiber prime system base material because the high cellulosic spherical particle of degree of crystallinity is representational radiation breakdown type macromolecule through the irradiation ionization radial line.As said dosage, be preferably 1～25kGy, more preferably 10～20kGy.
Through the dosage that makes ionization radial line is more than the 1kGy, and can generate with degree of crystallinity is that cellulose more than 80% is as the needed free radical activity point of the granular fiber prime system base material of main component.In addition, be below the 25kGy through the dosage that makes ionization radial line, can suppress with degree of crystallinity being the damage that the cellulose more than 80% causes as the granular fiber prime system base material of main component.The sorbing material of therefore, can manufacturing machine intensity do not reduce, chemical stability is excellent.In addition, through the ionization radial line of irradiation low dosage, can conserve energy, and can shorten irradiation time, therefore can reduce manufacturing cost.
As above-mentioned ionization radial line; Can enumerate out alpha ray, β ray, gamma-rays, electron ray, X ray etc.; Wherein from the viewpoint of industrial productivity, the electron ray that for example can more preferably use gamma-rays, produce by the electron ray accelerator, X ray etc. from cobalt-60.In addition; When using the electron ray that produces by the electron ray accelerator; As the electron ray accelerator, more preferably use the electron ray accelerator that can carry out thick thing irradiation, can be fit to use the electron ray accelerator of accelerating potential as the medium energy more than the 1MeV to high-energy.
In addition; When irradiation; If the stratum granulosum of above-mentioned granular fiber prime system base material is also sealed in for example polybag middle plateformization,, therefore can be fit to the above-mentioned granular fiber prime system of activation base material even then utilize the middle low energy electrons ray accelerator below the 1MeV also can see through electron ray.
In addition, the irradiation of ionization radial line is more preferably carried out under non-active gas atmosphere such as nitrogen, neon, argon gas.Thus, can carry out the introducing of grafted chain effectively, so preferred.
In addition, the irradiation of ionization radial line is more preferably carried out under-20～0 ℃ cooling condition.Thus, can carry out the introducing of grafted chain effectively, so preferred.
< grafted chain introducing operation >
Granular fiber prime system base material through above-mentioned activation procedure activation contacts this ethylenically unsaturated monomer of glycerol polymerization on above-mentioned granular fiber prime system base material with ethylenically unsaturated monomer in grafted chain introducing operation.Thus, on above-mentioned granular fiber prime system base material, introduce grafted chain.
Here, ethylenically unsaturated monomer be meant have ethylenically unsaturated group, be the monomer of carbon-to-carbon double bond.As said ethylenically unsaturated monomer, not special the qualification for example can be fit to use the ethylenically unsaturated monomer that contains epoxy radicals or styrene derivatives such as the styrene that contains epoxy radicals, chlorostyrene etc.Wherein, can be more suitable for using the ethylenically unsaturated monomer that contains epoxy radicals.
As the ethylenically unsaturated monomer that contains epoxy radicals, not special the qualification for example can be fit to use the monomer of the structure with formula (1) expression.
Here, in the above-mentioned general formula, R 1, R 2, R 3, R 4, R 5And R 6Expression independently of one another replaces or non-substituted saturated hydrocarbyl or hydrogen atom.In addition, the carbon atom of a part can be used O, N, P, S or Si displacement in this saturated hydrocarbyl.As can be on above-mentioned saturated hydrocarbyl substituted substituting group, not special the qualification, for example can enumerate out aryl, alkyl, alkanoyl, oxo base (oxo group ,=O) etc.
Wherein, R 1, R 2, R 3, R 4, R 5And R 6The more preferably alkyl of carbon number 1～6 or hydrogen atom independently of one another.
In addition, in the above-mentioned general formula, A representes to replace or non-substituted saturated hydrocarbon chain, promptly replace or non-substituted divalent saturated hydrocarbyl.In addition, the carbon atom of a part can be used O, N, P, S or Si displacement in this saturated hydrocarbon chain.As can be on above-mentioned saturated hydrocarbon chain substituted substituting group, not special the qualification for example can not enumerated out aryl, alkyl, alkanoyl, oxo base etc.In addition, in the above-mentioned general formula, n is 0 or 1.
Wherein, A more preferably comprises at least 1 oxygen base (oxy group ,-O-) saturated hydrocarbon chain in saturated hydrocarbon chain or this saturated hydrocarbon chain of carbon number 1～2.In addition, as substituting group, more preferably has oxygen base etc.
More specifically; As above-mentioned ethylenically unsaturated monomer; For example, can enumerate out (methyl) glycidyl acrylate, allyl glycidyl ether, glycidyl vinyl ethers, 2-vinyl oxirane, (methyl) acrylic acid 2-methyl epoxy ethyl methyl esters, itaconic acid 2-glycidyl ester, penetenoic acid ethylene oxidic ester, hexenoic acid ethylene oxidic ester, heptenoic acid ethylene oxidic ester etc.
Above-mentioned ethylenically unsaturated monomer can use separately, also can combination more than 2 kinds be used.
In addition, in this embodiment, preferably glycerol polymerization has the ethylenically unsaturated monomer of 1 above-mentioned ethylenically unsaturated group on the plain base material of above-mentioned granular fiber, in addition can other monomers of glycerol polymerization.
For example, have the multi-functional monomer of 2 above ethylenically unsaturated groups through coexistence, grafted chain can form crosslinked structure.Thus, can adjust the swellbility on the surface of sorbing material.
As the above-mentioned multi-functional monomer with 2 above ethylenically unsaturated groups, for example can be fit to use number-average molecular weight is diacrylate (polyethylene glycol #400～1000 diacrylates), ethoxylated bisphenol a diacrylate, divinylbenzene of 400～1000 polyethylene glycol etc.
When use had the above-mentioned multi-functional monomer of 2 above ethylenically unsaturated groups, with respect to the ethylenically unsaturated monomer with 1 above-mentioned ethylenically unsaturated group, its consumption was preferably 1～20 mole of %, more preferably 3～10 moles of %.
In the sorbing material of this embodiment, the percent grafting of the grafted chain of introducing through glycerol polymerization ethylenically unsaturated monomer on above-mentioned granular fiber prime system base material is preferably more than 100%.Through making percent grafting is more than 100%, can improve the load factor of the cerium in the resulting sorbing material.Therefore, can obtain the high sorbing material of adsorption capacity.
Need to prove that percent grafting is meant the ethylenically unsaturated monomer introduced through the glycerol polymerization amount (mass percent) with respect to above-mentioned granular fiber prime system base material here, for through after state the value that the method put down in writing among the embodiment is calculated.
Above-mentioned percent grafting more preferably more than 150%, is preferably more than 200% especially.
In addition; In this embodiment, above-mentioned grafted chain is introduced operation preferably, and the granular fiber prime system base material of activation is contacted with the emulsion that comprises ethylenically unsaturated monomer; Thereby this ethylenically unsaturated monomer of glycerol polymerization on above-mentioned granular fiber prime system base material is introduced grafted chain.
In the emulsion polymerisation of water solvent, monomer is scattered in the micella, and monomer improves for the compatibility of base material, therefore compares with the polymerisation in solution that utilizes organic solvent, and the utilization rate of free radical and polymerization speed improve.Thus, can be reduced in and produce the needed exposure dose of free radical in the base material, can also significantly reduce the reaction time.Its result can provide mechanical strength high sorbing material.
In addition, in the emulsion polymerisation of water solvent since in the glycerol polymerization operation not with an organic solvent, therefore can reduce the cost of technology, environmental protection in addition, the security that can improve technology.
The amount of contained above-mentioned ethylenically unsaturated monomer is preferably more than the 30 quality % with respect to the emulsion total amount and below the 80 quality % in the above-mentioned emulsion; More preferably more than the 40 quality % and below the 60 quality %, further be preferably more than the 45 quality % and below the 55 quality %.
Thus, can with high percent grafting with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer.Can shorten the granular fiber prime system base material and the time of contact that comprises the emulsion of ethylenically unsaturated monomer of activation in addition.
In addition, be below the 80 quality % through the amount that makes above-mentioned ethylenically unsaturated monomer with respect to the emulsion total amount, can prepare emulsion well, can make its dispersion equably, stability is high, so preferred.
Above-mentioned emulsion is water serial emulsion more preferably, promptly comprises the emulsion of above-mentioned ethylenically unsaturated monomer and water.Need to prove,, can use ion exchange water, pure water, ultra-pure water etc. as water as used herein.
Thus; Above-mentioned ethylenically unsaturated monomer is scattered in the little micella; The utilization rate of free radical and polymerization speed improve, therefore can with high percent grafting with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer.In addition because grafted chain introduces in the operation not with an organic solvent, therefore from the cost that reduces technology, to reduce for the burden of environment and the aspect that improves the security of technology be preferred.
In addition, more preferably also to comprise with respect to ethylenically unsaturated monomer be 3～10 quality %, the surfactant of 3～8 quality % more preferably to above-mentioned emulsion.Thus, can with high percent grafting with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer.Can shorten the granular fiber prime system base material and the time of contact that comprises the emulsion of ethylenically unsaturated monomer of activation in addition.
Need to prove; As especially preferably forming of the emulsion of this embodiment, surfactant is in the scope of 3～8 quality %, and monomer is in the scope of 30～80 quality %; For example, can make surfactant is that 5 quality %, monomer are that 50 quality %, water are 45 quality %.
Above-mentioned surfactant is not special to be limited, and can be fit to use the surfactant that in emulsion polymerisation, uses usually.
As such surfactant, particularly, for example can enumerate out alkyl polyoxyethylene ether, S-alkyl polyoxyethylene ether, alkyl phenyl APEO, N, non-ionic surface active agents such as N '-two (alkanol) alkylamide, amine oxide; Soap, alkylbenzenesulfonate, alkyl diphenyl ether sulfonate, alkylsulfonate, alpha-alkene sulfonate, alpha-sulfo fatty acid methyl ester, alkyl sodium sulfate salt, alkyl sodium sulfate (polyoxyethylene) salt, alkyl acid phosphate salt, N-acyl amino hydrochlorate, dialkyl dimethyl ammonium chloride, monoalkyl trimethyl ammonium chloride isoiony surfactant; Amphoteric surfactant such as DMPT, betaine.
In addition, the granular fiber prime system base material of activation does not limit with the contact method of the emulsion that comprises ethylenically unsaturated monomer is special, and for example, the granular fiber prime system base material that can enumerate the activation of sening as an envoy to impregnated in the method in the above-mentioned emulsion etc.
During as contact method, the granular fiber prime system base material of activation is 5 minutes～8 hours with the time of contact that comprises the emulsion of ethylenically unsaturated monomer, more preferably 30 minutes～60 minutes in the method for using dipping.That is, can reach high percent grafting with short time of contact.
In addition, in the method for using dipping during as contact method, even the temperature that the granular fiber prime system base material of reaction temperature activation contacts with the emulsion that comprises ethylenically unsaturated monomer is 40～80 ℃, more preferably 50～60 ℃.
In addition, the granular fiber prime system base material of activation carries out under non-active gas atmosphere such as nitrogen, neon, argon gas with contacting preferably of the emulsion that comprises ethylenically unsaturated monomer.Thus, can prevent the reaction of free radical and oxygen.
< functional group's bond sequence >
In functional group's bond sequence, introduce the functional group that bonding on the above-mentioned grafted chain of being introduced in the operation can cerium-carrying at above-mentioned grafted chain.
Above-mentioned functional group that can cerium-carrying introduces as follows: introduce the such compound of above-mentioned functional group with above-mentioned grafted chain reaction and the reaction of above-mentioned grafted chain is introduced through making.Therefore, have at above-mentioned grafted chain under the situation of epoxy radicals, as above-claimed cpd, the compound that use can be introduced above-mentioned functional group with epoxy reaction gets final product.
As such compound, for example when introducing the iminodiacetic acid (salt) acidic group, can be fit to use acetimidic acid disodium, hydroxyethyliminodiacetic acid, EDDA, L-aspartic acid-N, N oxalic acid etc.
In addition, for example when introducing sulfonic group, sodium sulfite, 2-tarine etc. can be fit to use, for example when introducing phosphonate group, phosphoric acid, phosphorous acid etc. can be fit to use.
In addition, the carrier in the sorbing material of the present invention need only above-mentioned grafted chain have can cerium-carrying functional group, introducing not special qualification the in period of this functional group.Therefore; Carrier with above-mentioned functional group can obtain through after introducing above-mentioned grafted chain on the base material, on this grafted chain, introducing above-mentioned functional group, also can obtain through the ethylenically unsaturated monomer that glycerol polymerization on above-mentioned granular fiber prime system base material has a functional group that can cerium-carrying.
Because it is few to have the reactive monomer of iminodiacetic acid (salt) acidic group; Therefore when introducing the iminodiacetic acid (salt) acidic group; Contain the ethene isoreactivity monomer of epoxy radicals in glycerol polymerization on the polymer base material after; Utilize reagent such as acetimidic acid disodium to carry out conversion reaction, thereby can on the glycerol polymerization chain, introduce the iminodiacetic acid (salt) acidic group suitably.As above-mentioned ethylenically unsaturated monomer, for example when introducing the iminodiacetic acid (salt) acidic group, can be fit to use GMA (GMA) etc.
In addition; For example when introducing phosphate, can be fit to use single (2-methacryloxyethyl) phosphate ester acid, two (2-methacryloxyethyl) phosphate ester acid, list (2-acryloxy ethyl) phosphate ester acid, two (2-acryloxy acetyl group) phosphate ester acid etc.
In addition, for example when introducing sulfonic group, SSS, novalgin (sodium methacryl sulfonate) etc. can be fit to use, for example when introducing phosphonate group, vinyl phosphonate, ethenylphenyl phosphonic acids etc. can be fit to use.
The introducing amount of above-mentioned functional group that can cerium-carrying, be contained in the 1g carrier can cerium-carrying the amount of above-mentioned functional group be preferably more than the 1mmol/g; More preferably more than the 1.3mmol/g; Further be preferably more than the 1.5mmol/g, be preferably more than the 2mmol/g especially.In addition, contained in the 1g carrier can cerium-carrying the amount of above-mentioned functional group be preferably below the 10mmol/g, further be preferably below the 8mmol/g.
Need to prove, here, contained in the 1g carrier can cerium-carrying the amount of above-mentioned functional group be meant through after state the value that the method put down in writing among the embodiment is calculated.
Through make contained in the 1g carrier can cerium-carrying the amount of above-mentioned functional group be more than the 1mmol/g, can be at short notice cerium-carrying fully.
Reaction condition in this operation suitably selects get final product not special qualification according to functional group that can cerium-carrying.For example, when introducing iminodiacetic acid sodium, the granular fiber prime system base material of having introduced above-mentioned grafted chain put into its reaction is got final product.
Here, the molar concentration of the iminodiacetic acid sodium aqueous solution, be not special qualification of molal quantity of the iminodiacetic acid sodium in the 1L iminodiacetic acid sodium aqueous solution, it is above and below the 0.8M to be preferably 0.1M, and more preferably 0.3M is above and below the 0.6M.
In addition, reaction temperature is preferably more than 60 ℃ and below 90 ℃, more preferably more than 75 ℃ and below 85 ℃, for example can carries out with 80 ℃, 12 hours condition.
The bonding that obtains as stated can cerium-carrying the carrier of functional group for example can clean and dry and easily refining through water.
(I-II) cerium load operation
As long as cerium load operation can be on carrier with functional group that can cerium-carrying load 3 valency ceriums, then can under any condition, carry out.For example, in the cerium load operation, preferably use aqueous solution load 3 valency ceriums on above-mentioned carrier of water miscible 3 valency cerium salt.
As above-mentioned water-soluble 3 valency cerium salt, for example can enumerate out cerous chloride etc.A little less than the oxidability of cerous chloride, its aqueous solution is neutral, therefore can not cause damage to carrier basically, so preferred.
Used the cerium load operation of the aqueous solution of above-mentioned water-soluble 3 valency cerium salt at room temperature to carry out, but, can significantly improve the loading speed and the load factor of 3 valency ceriums through at high temperature carrying out this operation.Its result, the sorbing material of a large amount of 3 valency ceriums of can having made load at short notice.
Particularly, above-mentioned cerium load operation is preferably being carried out more than 20 ℃, is more preferably carrying out more than 80 ℃, is further preferably carrying out more than 100 ℃.Need to prove, when the temperature of the above-mentioned aqueous solution surpasses 100 ℃, for example can use reaction vessel such as autoclave to carry out, the temperature of this aqueous solution can be measured through the temperature sensor that possesses in the reaction vessel etc.
The load factor of the cerium of sorbing material is not special to be limited, and according to adsorption capacity, remove speed and physical stability etc., is generally 2～30 quality %, is preferably 5～10 quality %.
(I-III) cerium oxidation operation
The cerium oxidation operation is following operation: to the load that obtains through above-mentioned cerium load operation the carrier of 3 valency ceriums carry out oxidation processes, the cerium with load on the carrier is oxidized to 4 valencys from 3 valencys thus.For example, in load on the above-mentioned cellulosic substrates under the situation of sorbing material of cerium, after the oxidation processes, cerium becomes 4 valencys by 3 valencys, thus the color on sorbing material surface becomes dark brown by white.
The method of oxidation processes is not special to be limited, and for example can carry out through following method: the method that contacts with the aqueous solution of oxidants such as hydrogen peroxide, clorox of the carrier of cerium that made load; The method that contacts with ozone gas of the carrier of cerium that made load; To load the method for carrier irradiation ultraviolet radiation (UV) of cerium; Or to load the method for the carrier irradiating electron beam of cerium (for example low energy electrons bundle).
Consider from aspects such as the easy property of security, processing, costs, preferably utilize aqueous hydrogen peroxide solution, aqueous sodium hypochlorite solution to carry out oxidation processes.
Need to prove that those skilled in the art can suitably determine various conditions such as treatment temperature, time and oxidant concentration, so that the damage of carrier is not influenced practicability less, basically.
(II) sorbing material
Sorbing material of the present invention comprises carrier with functional group that can cerium-carrying and is carried on 4 valency ceriums on this carrier, and carrier and 4 valency cerium chelatings form.This sorbing material can be through above-mentioned manufacturing approach manufacturing.
As above-mentioned carrier; For example can enumerate out following carrier: through with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer introduce grafted chain, thereby this grafted chain has the carrier of functional group that can cerium-carrying; Perhaps, introduce grafted chain through going up the glycerol polymerization ethylenically unsaturated monomer at the base material except that cellulose (polypropylene, polyethylene, ethylene-vinyl alcohol copolymer etc.), this grafted chain has the carrier of functional group that can cerium-carrying.
Wherein, preferred following carrier: through with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer introduce grafted chain, this grafted chain has the carrier of functional group that can cerium-carrying.
As functional group that can cerium-carrying, for example can enumerate out above-mentioned iminodiacetic acid (salt) acidic group, phosphate, sulfonic group, phosphonate group etc.
The shape of above-mentioned sorbing material is preferably granular, for example, can enumerate out sphere, ellipse, amorphous broken shape etc.Wherein, from the viewpoint of mechanical strength, more preferably spherical.
When above-mentioned sorbing material was granular, the average grain diameter of above-mentioned sorbing material was that 100～1500 μ m get final product, and more preferably 100～800 μ m further are preferably 200～500 μ m.Through making average grain diameter is above-mentioned scope, can directly use adsorption tower that existing ion-exchange/the chelating resin ball is used, reclaim equiment etc.
In addition, above-mentioned sorbing material can be porous matter.Thus, the absorption object can flow in pore.Thereby, can obtain more excellent absorption property.
Above-mentioned sorbing material can be suitable as arsenic adsorbent material, also can be suitable as anionic sorbing materials such as fluorine ion and plasma selenium.
Above-mentioned sorbing material is through contacting with process object such as the aqueous solution that for example contains arsenic etc., organic solvent solution, underground water, soil, thermal water, lakes and marhshes water, seawater, plant chimney stalk, mine wastewater, well water, rivers and creeks water, thereby can be used in removing of fluorine etc.
The load factor of the cerium of above-mentioned sorbing material is not special to be limited, and according to adsorption capacity, remove speed and physical stability etc., is generally 2～30 quality %, preferably in the scope of 2～20 quality %, more preferably in the scope of 5～10 quality %.
(III) adsorption treatment method
Adsorption treatment method of the present invention is the adsorption treatment method of the arsenic that exists in the water, and it uses the sorbing material of the invention described above.
As stated, sorbing material load of the present invention 4 valency ceriums, therefore can adsorb 3 valency arsenic effectively, can be suitable for removing of arsenic.
In order to use above-mentioned sorbing material to come arsenic-adsorbing, for example,, perhaps make post or the adsorption tower of this aqueous solution, thereby arsenic is contacted with sorbing material through being filled with sorbing material through in the aqueous solution that contains them, dropping into sorbing material and stirring or vibration.Through these processing, harmful ions such as arsenic are adsorbed on the sorbing material.
In addition, through utilizing suitable eluant, eluent and oxidant adsorbed arsenic etc. is handled (for example, with the NaOH wash-out, reoxidize with clorox), thereby can utilize above-mentioned sorbing material again.
As stated, the manufacturing approach of sorbing material of the present invention is characterised in that and comprises following operation: the cerium load operation that makes the carrier loaded 3 valency ceriums with functional group that can cerium-carrying; The above-mentioned cerium of oxidation institute load, the valence mumber that makes this cerium are the cerium oxidation operation of 4 valencys.
According to said method, need not to use oxidizing force very strong and be the highly acid 4 valency cerium aqueous solution, and load 4 valency ceriums on carrier easily.Therefore, can be able to make easily effect for the high sorbing material of the adsorption capacity of 3 valency arsenic.
In addition, owing to do not use the aqueous solution of 4 valency ceriums, therefore can suppress the suffered damage of carrier, its result can manufacturing machine intensity and the sorbing material of excellent in stability.
In addition; In the manufacturing approach of sorbing material of the present invention preferably; Also comprise the carrier production process of making above-mentioned carrier with functional group that can cerium-carrying; Above-mentioned carrier production process comprises following operation: activation procedure, and making with degree of crystallinity is that cellulose more than 80% is as the granular fiber prime system base material activation of main component; Grafted chain is introduced operation, and the granular fiber prime system base material of activation is contacted with ethylenically unsaturated monomer, thus on above-mentioned granular fiber prime system base material this ethylenically unsaturated monomer of glycerol polymerization, the introducing grafted chain; Functional group's bond sequence, the functional group that bonding can cerium-carrying on the above-mentioned grafted chain of being introduced.
According to said method, make carrier through granular fiber prime system base material is carried out glycerol polymerization, thereby, can at random control the size of carrier through suitably adjusting the size of percent grafting and cellulose grain.That is, according to said method, control that can manufacturing structure easily, excellent in stability and having than the existing arsenic polymeric adsorbent ball spherical sorbing material of excellent arsenic adsorption capacity more.
In addition; In the manufacturing approach of sorbing material of the present invention preferably; Above-mentioned grafted chain is introduced operation makes the granular fiber prime system base material of activation contact with the emulsion that comprises ethylenically unsaturated monomer; Thereby this ethylenically unsaturated monomer of glycerol polymerization on above-mentioned granular fiber prime system base material is introduced grafted chain.
According to said method, owing to carry out the emulsion polymerisation of water solvent, therefore to compare with the polymerisation in solution that utilizes organic solvent, the utilization rate of free radical and polymerization speed improve.Thus, can be reduced in and produce the needed exposure dose of free radical in the base material, can also significantly reduce the reaction time.Its result can provide mechanical strength high sorbing material.
In addition, in the manufacturing approach of sorbing material of the present invention, it is that mode more than 100% is carried out with percent grafting preferably that above-mentioned grafted chain is introduced operation.
According to said method, can improve the load factor of the cerium in the resulting sorbing material, therefore can obtain the high sorbing material of adsorption capacity.
In addition; In the manufacturing approach of sorbing material of the present invention preferably; In above-mentioned activation procedure,, thereby make the activation of granular fiber prime system base material to granular fiber prime system base material irradiation ionizing radiation line; Above-mentioned ionizing radiation line is gamma-rays, electron ray or X ray, and its dosage is 10～20kGy.
According to said method, can suppress to degree of crystallinity being the damage that the cellulose more than 80% causes as the granular fiber prime system base material of main component sorbing material that therefore can manufacturing machine intensity does not reduce, chemical stability is excellent.
In addition, in the manufacturing approach of sorbing material of the present invention, the degree of crystallinity of above-mentioned cellulose-based base material is preferably more than 95%.
According to said method, can manufacturing machine intensity and the more excellent sorbing material of chemical stability.
In addition, in the manufacturing approach of sorbing material of the present invention, above-mentioned functional group that can cerium-carrying is preferably at least a kind that is selected from the group of being made up of iminodiacetic acid (salt) acidic group, phosphate, sulfonic group and phosphonate group.
According to said method, can easily be incorporated on the grafted chain, therefore can make sorbing material more easily.
In addition, in the manufacturing approach of sorbing material of the present invention, in the above-mentioned carrier can cerium-carrying the content of above-mentioned functional group be preferably more than the 1mmol/g.
According to said method, can make the sorbing material of abundant cerium-carrying at short notice.
Preferably, in cerium load operation, utilize the water-soluble cerium salt of 3 valencys that 3 valency ceriums are carried on the carrier in the manufacturing approach of sorbing material of the present invention.
According to said method, can easily 3 valency ceriums be carried on the carrier, therefore can make sorbing material more easily.
In the manufacturing approach of sorbing material of the present invention, preferably carrying out cerium load operation more than 20 ℃.
According to said method, can easily 3 valency ceriums be carried on the carrier, therefore can make sorbing material more easily.
In the manufacturing approach of sorbing material of the present invention, preferably carrying out cerium load operation more than 80 ℃.
According to said method, can more easily 3 valency ceriums be carried on the carrier, therefore can make sorbing material more easily.
Preferably, in above-mentioned cerium load operation, be that the mode in the scope of 2～20 quality % is carried out load with the cerium load factor of carrier in the manufacturing approach of sorbing material of the present invention.
According to said method, can make adsorption capacity, remove speed and the excellent sorbing material of physical stability.
In the manufacturing approach of sorbing material of the present invention, preferably carry out above-mentioned cerium oxidation operation: the method that contacts with aqueous oxidizing agent solution of the carrier of cerium that made load through following method; The method that contacts with ozone gas of the carrier of cerium that made load; To load the method for carrier irradiation UV of cerium; Or to load the method for carrier irradiating electron beam of cerium.
According to said method, therefore the 3 valency ceriums of oxidation easily can make sorbing material more easily.
Sorbing material of the present invention is characterised in that it obtains through said method of the present invention, and carrier and 4 valency cerium chelatings form.
In addition, sorbing material of the present invention is characterised in that, it comprises carrier with functional group that can cerium-carrying and is carried on 4 valency ceriums on this carrier, and carrier and 4 valency cerium chelatings form.
According to these formations, carrier and 4 valency cerium chelatings form, and therefore can be able to provide the effect for the high sorbing material of the adsorption capacity of 3 valency arsenic.
In the sorbing material of the present invention preferably; Above-mentioned carrier through with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer; Thereby introducing grafted chain, this grafted chain have can cerium-carrying functional group.
According to above-mentioned formation, the control that structure can be provided easily, excellent in stability and having than the existing arsenic polymeric adsorbent ball spherical sorbing material of excellent arsenic adsorption capacity more.
In addition, in the sorbing material of the present invention, average grain diameter is preferably in the scope of 100～1500 μ m.
According to above-mentioned formation, can directly use adsorption tower that existing ion-exchange or chelating resin ball use, reclaim equiment etc.
In addition, in the sorbing material of the present invention, be preferably and be used for adsorbing at least a kind of anionic sorbing material that is selected from the group of forming by arsenic ion, fluorine ion and plasma selenium.
In addition, in the sorbing material of the present invention, be preferably the sorbing material that is used for being adsorbed on the arsenic that soil, underground water, running water, seawater, industrial wastewater, thermal water or mine wastewater dissolve.
Adsorption treatment method of the present invention is characterised in that, it is the adsorption treatment method of the arsenic that exists in the water, and it uses above-mentioned sorbing material of the present invention.
According to said method,, therefore can be able to effectively 3 valency arsenic carried out the effect of adsorption treatment owing to used for the high of the present invention above-mentioned sorbing material of the adsorption capacity of 3 valency arsenic.
In the adsorption treatment method of the present invention, the preferred post or the adsorption tower of having filled above-mentioned sorbing material that use.
According to said method, can carry out adsorption treatment to 3 valency arsenic effectively.
Embodiment
Below, come more specifically to explain the present invention through embodiment, but the present invention is not limited thereto.Definite method of " percent grafting " among the embodiment, " contained in the 1g carrier can cerium-carrying the amount of functional group " and " load factor of cerium " at first, below is shown.
< percent grafting >
Percent grafting, the ethylenically unsaturated monomer of promptly introducing through glycerol polymerization are tried to achieve through following method with respect to the amount (mass percent) of granular fiber prime system base material.
After the glycerol polymerization, the graft polymers of the granular fiber prime system base material of having introduced ethylenically unsaturated monomer was flooded 48 hours in methyl alcohol, acetone and other organic solvent, remove unreacted ethylenically unsaturated monomer and homopolymers.Afterwards, the graft polymers with granular fiber prime system base material flooded in water 24 hours again, and water cleans then, 50 ℃ of dryings 24 hours.Calculate percent grafting according to following formula by the quality (Wg) of the graft polymers of this dried granular fiber prime system base material and the dry mass (W0) of the granular fiber prime system base material before the introducing ethylenically unsaturated monomer.
Percent grafting (%)=((Wg-W0)/W0) * 100
< contained in the 1g carrier can cerium-carrying the amount of functional group >
About contained in the 1g carrier can cerium-carrying the amount of functional group, according to following formula by the quality of the graft polymers of the granular fiber prime system base material of trying to achieve through said method (Wg, unit: g), the equivalent (M) of functional group that can cerium-carrying, bonding can cerium-carrying functional group and quality (Wp, the unit: g) calculate of the carrier that cleaning-drying obtains.
Contained in the 1g carrier can cerium-carrying amount (mmol/g)={ ((Wp-Wg)/M)/Wp} * 1000 of functional group
< load factor of cerium >
About the load factor of cerium, promptly with respect to the amount (mass percent) of the cerium of institute's load of the quality of sorbing material, calculate by the quality (Wp) of employed carrier and the quality (Wq) of resulting sorbing material according to following formula.
The load factor of cerium (quality %)=((Wq-Wp)/Wq) * 100
(embodiment 1)
The cellulose fine particle that only is made up of microcrystalline cellulose (diameter: 200～300 μ m, goods name: CELPHERE (registration mark), Asahi Chemical Corp make, degree of crystallinity: more than 99%) is disposed in the foil-type plastic bag, utilizes nitrogen that this bag is repeatedly purged and seals.
With this bag cooling, utilizing industrial high-performance electronic accelerator (goods name: EPS-800, NHV Corporation system) exposure dose is the ionizing radiation line of 20kGy, generates the free radical activity point through dry ice.
In the emulsion solution of GMA of nitrogen displacement that postradiation sample has been impregnated in advance immediately the carrying out of making.
Consisting of of employed emulsion: surfactant (trade name: Tween20 and light reagent Co., Ltd. make) 3 quality %, GMA 30 quality %, water 67 quality %.
Need to prove that their percent grafting is 250%.
The glycidyl methacrylate graft cellulose grain that obtains is under these conditions dropped in the iminodiacetic acid sodium aqueous solution of 0.5M, reacted 12 hours down at 80 ℃.After resulting sample water cleaning, carry out drying, obtain carrier (diameter: 400～500 μ m).The functional group densities of the iminodiacetic acid (salt) acidic group in this carrier is about 2.2mol/g.
Afterwards, above-mentioned carrier impregnation is arrived about 80 ℃ 0.1M cerium chloride (CeCL 3) in the solution 8 hours, the sorbing material of 3 valency ceriums that obtained load thus.The load factor of 3 valency ceriums in this sorbing material is 9 quality %.
With load 3 valency ceriums sorbing material at room temperature with 20 quality %H 2O 2Aqueous solution contact 24 hours is cleaned with pure water afterwards and is made its drying, obtain having auburn load thus the sorbing material of 4 valency ceriums (below be designated as " CCM-As ".)。The load factor of the cerium of this sorbing material is 9 quality %.
(adsorption experiment in batches of arsenic)
Use the sorbing material CCM-As that obtains among the embodiment 1, carry out the adsorption experiment in batches of following arsenic.
< 3 valency arsenic >
3 commercially available valency arsenic titers are diluted the 3 valency arsenic solutions of preparation 5ppm (about initial pH:6.5) with pure water.
0.1g sorbing material CCM-As is joined among the 5ppm arsenic aqueous solution 100mL, at room temperature stirred 24 hours.Afterwards, measure the arsenic in the supernatant, obtain the adsorbance of arsenic by the residual concentration after initial concentration in the solution and the processing through ICP emission spectrographic analysis device.
As relatively, for commercially available arsenic polymeric adsorbent ball (trade name: Read-As, Japanese seawater society make), the applicant unexposed international patent application of application (application number: PCT/JP2009/52796) as the zirconium loaded resin ball (load factor of Zr: be designated as " CCM-F " 15%, of embodiment 1 record in the past.) also under identical condition, carried out adsorption experiment.
Its result is shown in Fig. 1.As shown in Figure 1, compare with commercially available arsenic polymeric adsorbent ball, sorbing material CCM-As is identical with it or on it for the adsorption capacity of 3 valency arsenic.That is, when using sorbing material CCM-As, after utilizing sorbing material to handle, can reach the last water base standard of 0.01ppm basically all except that the arsenic in anhydrating.
In addition, compare, can know that sorbing material CCM-As demonstrates very high adsorption capacity with CCM-F.
Need to prove, except above-mentioned experiment, utilize the preceding sorbing material of oxidation processes among the embodiment 1 (to be designated as " before the CMM-As oxidation processes ".) under identical condition, carried out adsorption experiment, but do not adsorb 3 valency arsenic basically.Think that by this result the adsorption mechanism of sorbing material CCM-As is earlier the 3 valency arsenic that exist in the water to be oxidized to 5 valency arsenic, then absorption.
< 5 valency arsenic >
5 commercially available valency arsenic titers are diluted the 5 valency arsenic solutions of preparation 5ppm (about initial pH:6.5) with pure water.
0.1g sorbing material CCM-As is joined among the 5ppm arsenic aqueous solution 100mL, at room temperature stirred 24 hours.Afterwards, measure the arsenic in the supernatant, obtain the adsorbance of arsenic by the residual concentration after initial concentration in the solution and the processing through ICP emission spectrographic analysis device.
As relatively, also under identical condition, carried out adsorption experiment for commercially available arsenic polymeric adsorbent ball (trade name: Read-As, Japanese seawater society make), CCM-F, commercially available alumina adsorption material (making) with the pure medicine of light society.
Its result is shown in Fig. 2.As shown in Figure 2, sorbing material CCM-As compares with commercially available alumina adsorption material with commercially available arsenic polymeric adsorbent ball, demonstrates the adsorption capacity for 5 valency arsenic identical or on it.That is, when using sorbing material CCM-As, after utilizing sorbing material to handle, can reach the last water base standard of 0.01ppm basically all except that the arsenic in anhydrating.
Can know that by these results sorbing material of the present invention all has high absorption capacity for 3 valency arsenic and 5 valency arsenic.
As stated, can confirm: sorbing material of the present invention has excellent adsorption capacity for arsenic etc., and is highly beneficial when the underground water that pollutes because of these harmful substances, plant chimney stalk, thermal water, mine wastewater etc. are purified.
In addition, the sorbing material of making in the present embodiment uses ionization radial line, particularly electron accelerator to make through the electron ray irradiation, and therefore a large amount of easily production in industry has practicality.
In addition, if consider factors such as manufacturing process, adsorption capacity, reproduction speed, environment aspect, sorbing material of the present invention can replace existing arsenic adsorbent material.
The present invention is not limited to above-mentioned each embodiment, can in the scope shown in claims, carry out various changes, and the embodiment that disclosed respectively technological means appropriate combination in the different embodiment is obtained is also contained in the technical scope of the present invention.
Utilizability on the industry
Sorbing material of the present invention can be suitable as the sorbing material of various harmful substances such as arsenic.

Claims (21)

1. the manufacturing approach of a sorbing material is characterized in that, it comprises following operation:
Make the cerium load operation of carrier loaded 3 valency ceriums with functional group that can cerium-carrying; With
The said cerium of oxidation institute load makes the valence mumber of this cerium become the cerium oxidation operation of 4 valencys.
2. the manufacturing approach of sorbing material according to claim 1 is characterized in that, it also comprises makes said carrier production process with carrier of functional group that can cerium-carrying,
Said carrier production process comprises following operation:
Activation procedure: making with degree of crystallinity is that cellulose more than 80% is as the granular fiber prime system base material activation of main component;
Grafted chain is introduced operation: the granular fiber prime system base material of activation is contacted with ethylenically unsaturated monomer, thereby on above-mentioned granular fiber prime system base material this ethylenically unsaturated monomer of glycerol polymerization, the introducing grafted chain;
Functional group's bond sequence: the functional group that bonding can cerium-carrying on the above-mentioned grafted chain of being introduced.
3. the manufacturing approach of sorbing material according to claim 2; It is characterized in that; Introduce in the operation at said grafted chain; The granular fiber prime system base material of activation is contacted with the emulsion that comprises ethylenically unsaturated monomer, thus on said granular fiber prime system base material this ethylenically unsaturated monomer of glycerol polymerization, introduce grafted chain.
4. according to the manufacturing approach of claim 2 or 3 described sorbing materials, it is characterized in that it is that mode more than 100% is carried out with percent grafting that above-mentioned grafted chain is introduced operation.
5. according to the manufacturing approach of each described sorbing material of claim 2～4, it is characterized in that,
In said activation procedure, to granular fiber prime system base material irradiation ionizing radiation line, thereby make the activation of granular fiber prime system base material,
Above-mentioned ionizing radiation line is gamma-rays, electron ray or X ray, and its dosage is 10～20kGy.
6. according to the manufacturing approach of each described sorbing material of claim 2～5, it is characterized in that the degree of crystallinity of above-mentioned cellulose-based base material is more than 95%.
7. according to the manufacturing approach of each described sorbing material of claim 1～6, it is characterized in that said functional group that can cerium-carrying is at least a kind that is selected from the group of being made up of iminodiacetic acid (salt) acidic group, phosphate, sulfonic group and phosphonate group.
8. according to the manufacturing approach of each described sorbing material of claim 1～7, it is characterized in that, in the said carrier can cerium-carrying the content of said functional group be more than the 1mmol/g.
9. according to the manufacturing approach of each described sorbing material of claim 1～8, it is characterized in that, in cerium load operation, utilize the water-soluble cerium salt of 3 valencys that 3 valency ceriums are carried on the carrier.
10. according to the manufacturing approach of each described sorbing material of claim 1～9, it is characterized in that, carrying out cerium load operation more than 20 ℃.
11. the manufacturing approach according to each described sorbing material of claim 1～10 is characterized in that, is carrying out cerium load operation more than 80 ℃.
12. the manufacturing approach according to each described sorbing material of claim 1～11 is characterized in that, in said cerium load operation, is that the mode in the scope of 2～20 quality % is carried out load with the cerium load factor of carrier.
13. the manufacturing approach according to each described sorbing material of claim 1～12 is characterized in that, carries out said cerium oxidation operation through following method: the method that contacts with aqueous oxidizing agent solution of the carrier of cerium that made load; The method that contacts with ozone gas of the carrier of cerium that made load; To load the method for carrier irradiation ultraviolet radiation of cerium; Or to load the method for carrier irradiating electron beam of cerium.
14. a sorbing material is characterized in that, its each described method through claim 1～13 obtains, and carrier and 4 valency cerium chelatings form.
15. a sorbing material is characterized in that, it comprises carrier with functional group that can cerium-carrying and is carried on 4 valency ceriums on this carrier, and carrier and 4 valency cerium chelatings form.
16. sorbing material according to claim 15; It is characterized in that; Said carrier through with degree of crystallinity be cellulose more than 80% as the granular fiber prime system base material of main component on the glycerol polymerization ethylenically unsaturated monomer; Thereby introducing grafted chain, this grafted chain have can cerium-carrying functional group.
17. each the described sorbing material according to claim 14～16 is characterized in that average grain diameter is in the scope of 100～1500 μ m.
18. each the described sorbing material according to claim 14～17 is characterized in that, it is to be used for adsorbing at least a kind of anionic sorbing material that is selected from the group of being made up of arsenic ion, fluorine ion and plasma selenium.
19. each the described sorbing material according to claim 14～18 is characterized in that it is the sorbing material that is used for adsorbing the arsenic that is dissolved in soil, underground water, running water, seawater, industrial wastewater, thermal water or mine wastewater.
20. an adsorption treatment method is characterized in that, it is the adsorption treatment method of the arsenic that exists in the water,
It uses each described sorbing material of claim 14～19.
21. adsorption treatment method according to claim 20 is characterized in that, the post or the adsorption tower of said sorbing material filled in its use.
CN2009801612534A 2009-10-29 2009-10-29 Adsorbent, method for producing same, and use thereof Pending CN102481547A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2009/005727 WO2011052008A1 (en) 2009-10-29 2009-10-29 Adsorbent, method for producing same, and use of same

Publications (1)

Publication Number Publication Date
CN102481547A true CN102481547A (en) 2012-05-30

Family

ID=43921453

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009801612534A Pending CN102481547A (en) 2009-10-29 2009-10-29 Adsorbent, method for producing same, and use thereof

Country Status (3)

Country Link
JP (1) JP5316645B2 (en)
CN (1) CN102481547A (en)
WO (1) WO2011052008A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108289991A (en) * 2015-11-30 2018-07-17 东丽株式会社 Phosphorus adsorbent, Porous fiber and phosphorus adsorption column

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2527128A (en) * 2014-06-13 2015-12-16 Imp Innovations Ltd Method for reducing arsenic concentration in aqueous solutions
CN104592397B (en) * 2015-01-24 2018-01-23 浙江工商大学 Thioglycolic acid modified cellulose, its preparation method and application
JP7319619B2 (en) * 2018-03-07 2023-08-02 島根県 Arsenic-adsorbing cellulose material
CN111995053B (en) * 2020-08-24 2022-01-28 哈尔滨工业大学 A/A/O system based on synchronous reinforced biochemical phosphorus removal of powdered lanthanum-based adsorbent

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61187931A (en) * 1985-02-18 1986-08-21 Asahi Chem Ind Co Ltd Adsorbent of arsenic in aqueous solution
JP2003225559A (en) * 2001-06-21 2003-08-12 Japan Science & Technology Corp Adsorbent made from plant biomass
CN1470477A (en) * 2002-07-26 2004-01-28 中国科学院大连化学物理研究所 A kind of metal zirconium phosphate and its preparation method and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04317738A (en) * 1991-04-16 1992-11-09 Agency Of Ind Science & Technol Production of fluoride ion adsorbing material
JP3924381B2 (en) * 1998-07-08 2007-06-06 千代田化工建設株式会社 Method for adsorbing and removing arsenic dissolved in water
JP4840907B2 (en) * 2005-11-11 2011-12-21 独立行政法人産業技術総合研究所 Method for producing organic sulfur compound adsorbent
JP5045269B2 (en) * 2007-06-29 2012-10-10 株式会社Ｎｈｖコーポレーション Particulate cellulose-based adsorbent and method for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61187931A (en) * 1985-02-18 1986-08-21 Asahi Chem Ind Co Ltd Adsorbent of arsenic in aqueous solution
JP2003225559A (en) * 2001-06-21 2003-08-12 Japan Science & Technology Corp Adsorbent made from plant biomass
CN1470477A (en) * 2002-07-26 2004-01-28 中国科学院大连化学物理研究所 A kind of metal zirconium phosphate and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈腾飞等: "Ce-10La合金在氢气中的表面气相反应特征研究", 《矿冶工程》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108289991A (en) * 2015-11-30 2018-07-17 东丽株式会社 Phosphorus adsorbent, Porous fiber and phosphorus adsorption column

Also Published As

Publication number Publication date
WO2011052008A1 (en) 2011-05-05
JP5316645B2 (en) 2013-10-16
JPWO2011052008A1 (en) 2013-03-14

Similar Documents

Publication Publication Date Title
Ibrahim et al. Crown ether modification of starch for adsorption of heavy metals from synthetic wastewater
JP5045269B2 (en) Particulate cellulose-based adsorbent and method for producing the same
Nasef et al. Radiation-grafted copolymers for separation and purification purposes: Status, challenges and future directions
KR100861452B1 (en) Method for preparing polyacrylate microspheres in surface-engraved core-shell form for selective separation of heavy metal ions
Chai et al. Facile fabrication of pH-sensitive nanoparticles based on nanocellulose for fast and efficient As (V) removal
JP2010253359A (en) Metal adsorbent containing chelating polymer compound
CN102481547A (en) Adsorbent, method for producing same, and use thereof
Guibal et al. Immobilization of extractants in biopolymer capsules for the synthesis of new resins: a focus on the encapsulation of tetraalkyl phosphonium ionic liquids
Grisdanurak et al. The study of copper adsorption from aqueous solution using crosslinked chitosan immobilized on bentonite
Yang et al. Biopolymer‐based membrane adsorber for removing contaminants from aqueous solution: Progress and prospects
KR100732227B1 (en) Organic polymer material, its manufacturing method and heavy metal ion remover
Li et al. Development of chitosan-based granular adsorbents for enhanced and selective adsorption performance in heavy metal removal
Zheng et al. Thiol-rich and ion-imprinted alginate hydrogel as a highly adsorptive and recyclable filtration membrane for rapid and selective Sr (II) removal
JP2007530717A (en) Polymer beads incorporating iron oxide particles
Jiang et al. Polyethylenimine‐modified sugarcane bagasse cellulose as an effective adsorbent for removing Cu (II) from aqueous solution
Su et al. Surface ion-imprinted brewer’s spent grain with low template loading for selective uranyl ions adsorption from simulated wastewater
US7001963B2 (en) Cobalt imprinted polymer composition for selective removal of cobalt, process for preparation thereof, and process for removal of cobalt
KR100742769B1 (en) Separation Functional Material
WO2010095222A1 (en) Zirconium-loaded particulate adsorbent and method for producing the same
KR101621954B1 (en) Chelating compound, and method of use of, poly(2-octadecyl-butanedioate) and the corresponding acid, poly(2-octadecyl-butanedioate)
CN106807340B (en) A kind of crosslinked resin-hydroximic acid composite adsorbing material and the preparation method and application thereof
CA3188018A1 (en) Lithium ion adsorbents
JP5711510B2 (en) Acrylic resin for adsorbent, water treatment column, and water treatment method
Chakraborty et al. Radiation-induced graft copolymerization–A facile technology for polymer surface modification and applications
Alcazar et al. Sulfonation of microcapsules containing selective extractant agents

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120530