CN103480345B - A kind of high speed selective caesium polymeric adsorbent material and its preparation method and application - Google Patents
A kind of high speed selective caesium polymeric adsorbent material and its preparation method and application Download PDFInfo
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- CN103480345B CN103480345B CN201310419324.4A CN201310419324A CN103480345B CN 103480345 B CN103480345 B CN 103480345B CN 201310419324 A CN201310419324 A CN 201310419324A CN 103480345 B CN103480345 B CN 103480345B
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Abstract
The present invention relates to a kind of caesium polymeric adsorbent material, by the organic-inorganic composite resin material of inorganic material by being formed after epoxide group ring-opening reaction of the macromolecular material containing epoxide group and phosphorous heteropolyacid salt, the superficial layer of described composite resin material is mainly inorganic constituents.Present invention achieves and import ion adsorbent on polymer base material surface, make caesium polymeric adsorbent material particle size can reach 400 microns, meet the need that in industry, adsorption column filling uses; This caesium polymeric adsorbent material has the feature of absorption at a high speed, and the Cs be adsorbed onto on resin is easy to it all be resolved with leacheate, and the polymeric adsorbent processed can adsorb Cs again, reaches Reusability, has good economic benefit.
Description
Technical field
The invention belongs to the technical field of caesium polymeric adsorbent material, particularly a kind of high speed selective caesium polymeric adsorbent material and its preparation method and application.
Background technology
Uranium base nuclear fuel can produce in fission process
134cs and
137the radionuclides such as Cs, these radioactivity Cs can release very strong gamma-rays in decay process, and the caesium in high activity liquid waste needs to give separation and recovery in nuclear fuel cycle process.In general these radioactivity Cs there will not be in the environment, and the recovery technology for the caesium of the low-activity occurred in environment is not all paid attention to all the time.But after in March, 2011 Fukushima, Japan Nuclear Power Accident, a large amount of radioactivity Cs has been leaked in environment, serious threat is constituted to raw body.In contaminated water body environment, the exploitation of radioactivity Cs separation and recovery technology receives the unprecedented attention of various countries researcher.The Cs be leaked in environment because of Nuclear Power Accident is different from the Cs in spentnuclear fuel, and concentration is minimum, and radiation activity is low, but required treating capacity is very big, needs fast processing.The adsorption treatment technology using adsorbent is one of effective way solved the problem, and therefore needs to develop a kind of high speed selective absorbent for Cs.
Ammonium phosphomolybdate (AMP) as inorganic ion exchanger, to the Cs in water
+ion has good adsorptivity and selective, can to Cs
+ion keeps higher ion exchange capacity, and does not almost have exchange interaction to Na, K, is all be separated from the post processing acidity that Na content is high fissions waste liquid and reclaim Cs all the time
+it is noticeable inorganic ion exchange material.But the shortcoming of ammonium phosphomolybdate is it is Powdered, and granularity is too little, filling cannot use in adsorption column.In order to address this problem, asbestos, silica gel and organic polymer are changed its granularity as support by Many researchers (can bibliography 1.IMPROVEDINORGANIC ION-EXCHANGERS II.AMMONIUM MOLYBDOPHOSPHATE--SILICAGEL SYSTEM.Journal of Radioanalytical.1.J.Dolezal, J.Steiskal, M.Tympl, and V.Kourin, Chemistry, 21,381 (1974).; Document 2.Cation exchange properties of the ammoniumheteropolyacid salts.J.Van R.Smit, J.J.Jacobs, and W.Robb, Journal of Inorganic and NuclearChemistry., 12,95 (1959).; Document 3.A.Preparations of PAN-based adsorbers for separation ofcesium and cobalt from radioactive wastes.Nilchi, H.Atashi, A.H.Javid, R.Saberi., AppliedRadiation and Isotopes.65,482 (2007) .).But in these materials, ammonium phosphomolybdate is distributed in material internal, affects adsorption rate.
As far as possible the key improving adsorption rate adsorption function group is concentrated on sorbing material surface, shortens the diffusion process of absorption object in sorbing material as far as possible.For above-mentioned requirements, in resin structure design, utilize Graft Method on the surface of specific base material, import the method for adsorbing functional group and be used to prepare among various adsorption and separation material.This method is conducive to importing highdensity adsorption group at material surface, and the material of synthesis carries out high speed absorption to rare element under being particularly suitable for low concentration environment.
Due to ammonium phosphomolybdate slightly soluble in water, all the time, ammonium phosphomolybdate is all be held in porous material by cocrystallization load after use phosphomolybdic acid and ammonium nitrate impregnation carrier.As Japan Patent (Te Open 2000-84418 with Te Open 2000-93813) method mentioned, its shortcoming is that the ammonium phosphomolybdate generated does not have integrated distribution at material surface, and in cocrystallization, needing excessive use phosphomolybdic acid and ammonium nitrate, efficiency is low and cleaning up is cumbersome.If ammonium phosphomolybdate can be concentrated in material surface, the adsorption rate of Cs greatly can be improved.
At present, there is not yet pertinent literature report and ammonium phosphomolybdate can be fixed on sorbing material surface, prepare a kind of caesium polymeric adsorbent material with absorption feature at a high speed.
Summary of the invention
The object of the present invention is to provide a kind of high speed selective caesium polymeric adsorbent material and its preparation method and application.
Goal of the invention of the present invention is achieved through the following technical solutions:
The object of the present invention is to provide a kind of caesium polymeric adsorbent material, by the organic-inorganic composite resin material of inorganic material by being formed after epoxide group ring-opening reaction of the macromolecular material base material component containing epoxy group and phosphorous heteropolyacid salt, the superficial layer of described composite resin material is mainly inorganic constituents.
Another object of the present invention is to the preparation method that a kind of caesium polymeric adsorbent material is provided, comprise the steps:
1) carry out free radical activation process to polymer base material, grafting carries out polymerisation containing the unsaturated monomer of epoxy radicals, and percent grafting should ensure more than 50%, obtained sorbing material presoma;
2) above-mentioned presoma is imported phosphorous heteropolyacid salt by epoxy ring-opening reaction, control Drug delivery rate more than 10%, obtained caesium polymeric adsorbent material.
The shape of the polymer base material in described step 1) is average diameter is the rule of 30-800 micron or irregular spheroidal particle, or diameter 5-200 micron, the microfibrous material of length 100-10000 micron.
Wherein, the polymer base material one that can be selected from cellulose, polyethylene glycol, polypropylene, polyamide in extensive range; C-H is comprised, as long as the material that can produce free radical all can meet reaction requirement of the present invention in the molecular structure of the present invention's polymer base material used; Preferred degree of crystallinity is the polymer base material of more than 30%, and preferably degree of crystallinity is the polymer base material of more than 50% further.
Free radical activation process in described step 1) comprises and adopts Ionizing Radiation or add radical initiator and process.
Described Ionizing Radiation is by gamma gamma-rays, electron ray, and the ionizing ray that X-ray produces carries out irradiation, irradiation dose 10-250kGy scope.
Described radical initiator is selected from azodiisobutyronitrile, ABVN, one in the normal starters such as azo-bis-iso-dimethyl (AIBME), benzoyl peroxide, in suitable temperature and dicyandiamide solution, initiation contains the unsaturated monomer glycerol polymerization of epoxy radicals on polymer base material; In the chemical graft process using radical initiator, the use amount of radical initiator accounts for the 0.1-2% of overall reaction system (polymer base material+initator+containing the unsaturated monomer+emulsification system of epoxy radicals or organic solvent system) weight.
The unsaturated monomer containing epoxy radicals in described step 1) is selected from the one in GMA (GMA), acrylic acid hydroxyl butyl glycidyl ether (4-HBAGE).
Preferably, when described step 2) in percent grafting when reaching more than 100%, be more conducive to next step ring-opening reaction.
Graft polymerization reaction in described step 1) carries out in emulsification system or organic solvent system, controls reaction temperature 40-80 DEG C.
Described emulsification system is made up of unsaturated monomer, interfacial agent, water, and wherein, unsaturated monomer proportion is 10-80wt%, and interfacial agent proportion is 1-10wt%, and all the other are water; Described interfacial agent is fatty glyceride, the smooth or polysorbate of aliphatic acid sorb.
Described organic solvent system is made up of unsaturated monomer and organic solvent, and wherein, unsaturated monomer proportion is 10-80wt%.
Described step 2) in epoxy ring-opening reaction be carry out in the phosphorous heteropolyacid salt suspension of 1-10wt% in concentration, reaction temperature controls at 50-85 DEG C.
Described phosphorous heteropolyacid salt is selected from the one in ammonium phosphomolybdate, ammonium phosphotungstate.
The third object of the present invention is to provide the application in the Cs separating technology of above-mentioned caesium polymeric adsorbent material in adsorbing separation water.
Compared with prior art, beneficial effect of the present invention is as follows:
1) the present invention adopts ionising radiation crosslinking technology to have can to select arbitrarily the kind of base material and monomer, substrate shapes is not limited, the not advantage such as residual catalyst in graft product, particularly electron beam irradiation pre-irradiation grafting method, the radiative process of base material and monomer-grafted course of reaction can be separated, be not easy in course of reaction to produce homopolymers, reaction efficiency high controllability is strong, is adapted at material surface high density and imports specific functional group.
2) the present invention selects microspheroidal or fibrous macromolecular material as base material, and existing commercial resin can be replaced more easily to use in adsorption column/tower.
3) the caesium sorbing material from traditional is different, present invention achieves and import ion adsorbent on polymer base material surface, make caesium polymeric adsorbent material particle size can reach 400 microns, meet in industry the demand adsorbing filling and use, there is very large industrial applications prospect.
4) the caesium polymeric adsorbent material that prepared by the present invention has the feature of absorption at a high speed, and the Cs be adsorbed onto on resin is easy to it all be resolved with leacheate, the polymeric adsorbent processed can adsorb Cs again, reaches Reusability, has good economic benefit.
Accompanying drawing explanation
Fig. 1 is outward appearance photo and electric wire microscope (the 100 times of multiplying powers) photo of Cs sorbing material prepared by the present invention.
Fig. 2 is Cs adsorption time curve.
Fig. 3 is the Dynamic Adsorption evaluation of Cs.
Fig. 4 is the desorption properties evaluation of Cs.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
1) with avicel cellulose microballoon (average diameter 200 microns, degree of crystallinity 76%) be polymer base material, 10 grams of above-mentioned materials are put into the PE bag containing nitrogen, uses electron accelerator to carry out electron beam irradiation, make it produce to can be used for the living radical of graft reaction.Illuminate condition: irradiation voltage 2MeV, exposure dose is 30kGy, close rate 10kGy/pass.
2) postradiation above-mentioned particulate, drops in the emulsion reaction system be made up of 30wt%GMA+3wt% polyoxyethylene 20 sorbitan monolaurate (Tween20)+67wt% water at once and carries out graft polymerization reaction.The emulsion reaction system of GMA monomer is blown into the nitrogen of 30 minutes before use continuously to discharge the oxygen in water.Graft polymerization reaction carries out at 50 DEG C, (percent grafting of base material reaches about 250%) cessation reaction after about 2 hours.
3) the monomer-grafted product of above-mentioned GMA, drop into after clean dry in the 3wt% ammonium phosphomolybdate suspension aqueous solution and carry out epoxy ring-opening reaction, in 80 DEG C of oscillating reactions 24 hours (Drug delivery rate of ammonium phosphomolybdate is about 18wt%), obtained caesium polymeric adsorbent material after taking out cleaning-drying.
The polymeric adsorbent material diameter obtained by said method is approximately 400 microns, and density is 450wet-g/L-Resin, moisture content ﹤ 30%, and the density of ammonium phosphomolybdate functional group is about 0.11mol/L-Resin.
Embodiment 2
1) with polypropylene micro-sphere material (average diameter 250 microns, degree of crystallinity 60%) be polymer base material, by 10 grams of above-mentioned materials and 1.5g azodiisobutyronitrile, drop in organic solvent (about 50g) reaction system be made up of 30wt%4-HBAGE+70wt% acetone and carry out graft polymerization reaction.Graft polymerization reaction carries out (percent grafting of base material reaches about 80%) cessation reaction after 8 hours at 60 DEG C.
2) the monomer-grafted product of above-mentioned 4-HBAGE, drop into after clean dry in the 5wt% ammonium phosphotungstate suspension aqueous solution and carry out epoxy ring-opening reaction, in 80 DEG C of oscillating reactions 24 hours (Drug delivery rate of ammonium phosphotungstate is about 15wt%), obtained caesium polymeric adsorbent material after taking out cleaning-drying.
The polymeric adsorbent material diameter obtained by said method is approximately 300 microns, and density is 480wet-g/L-Resin, moisture content ﹤ 30%, and the density of ammonium phosphotungstate functional group is about 0.13mol/L-Resin.
Embodiment 3
The Static Adsorption test of 1.Cs polymeric adsorbent material
Take sorbing material 0.1g prepared by embodiment 1, at room temperature drop into 100ml and contain stable isotope 133Cs modulation and form in the aqueous solution and carry out static Batch adsorption test.The Cs solution of adsorption test is modulated by the nitrate of 133Cs and is formed, and initial concentration is 5mg/L, pH5.8.Above-mentioned adsorption test is at room temperature stirred, and adsorption time is the different time of 5min to 60min respectively, reclaims its supernatant, analyzes its residual Cs concentration thus calculate its adsorbance with atom extinction spectrum.
From Fig. 2, we can find out that the present invention obtains Cs polymeric adsorbent adsorption rate quickly, within 20 minutes, substantially all reach adsorption equilibrium, have the feature of absorption Cs at a high speed.
The post pressure test of 2.Cs polymeric adsorbent material in adsorption column
In actual process, in the adsorption column that polymeric adsorbent must be filled to certain volume or adsorption tower, object water solution carries out adsorbing separation with certain flow velocity by pillar.This requires that polymeric adsorbent is when high speed processing, must ensure enough low post pressure, otherwise cannot apply in actual process.The shortcoming of ammonium phosphomolybdate is exactly it is Powdered, and granularity is too little, and when high speed processing, post presses through greatly, and liquid is difficult to smooth flow, finally filling cannot use in adsorption column.
Sorbing material embodiment 1 prepared in adsorption column at moisture state retrofilling, passes into pure water thing adjustment flow velocity, tests its post pressure.Post pressure appreciation condition: adsorption column size
amount of resin 15ml, test post pressure during following flow: 2.5ml/min (SV10), 5ml/min (SV20), 10ml/min (SV40), 25ml/min (SV100) (SV*:Space Velocity, space velocity, the liquid volume multiple flowing through adsorption column per hour, multiplex SV5-50 in water treatment technology).In order to compare, we also to have selected in actual process conventional a kind of be that the cationic ion-exchange resin (DIAION SK1B, Mitsubishi Chemical) of base material carries out the test of post pressure under similarity condition with polystyrene.Result in table 1 shows under several flow velocitys of space velocity SV from 10 to 100, polymeric adsorbent prepared by the present invention solves and uses ammonium phosphomolybdate institute unvanquishable post pressure problem itself, its post pressure is all equal to or is slightly less than commercial resin, all post pressures are all lower than 0.1MPa, reach the post pressure request of practical application, filling use can be carried out in adsorbent equipment.
Table 1
The Dynamic Adsorption test of 3.Cs polymeric adsorbent material
Sorbing material embodiment 1 prepared in adsorption column at moisture state retrofilling, passes into modulating with stable isotope 133Cs of modulating in advance and forms the Dynamic Adsorption that the aqueous solution evaluates it.
Dynamic Adsorption appreciation condition: adsorption column size
amount of resin 15ml, containing caesium concentration of aqueous solution 5mg/L, pH5.8, flow 2.5ml/min (SV10).
Carried out Dynamic Adsorption evaluation experimental according to above-mentioned condition, by fixed time interval to outlet liquid sampling analysis, the absorption behavior curve of above-mentioned sorbing material can be obtained, as shown in Figure 3.
The polymeric adsorbent that the present invention obtains can process the Cs solution of about 150 times of its volume and can not spill, and the adsorption capacity during breakthrough point of its Cs is 0.8g/L-Resin.Consider that the concentration of the water that radioactivity Cs in environment pollutes is more much lower than the setting concentration of 5ppm, can think that adsorbent of the present invention can the molten Cs ion deposited in adsorbed water well.
The dynamic desorption test of 4.Cs polymeric adsorbent material
In general its regeneration and being separated of absorbing elements must be considered after polymeric adsorbent absorption.After implementing dynamic saturated adsorption according to the experiment condition in embodiment 3, after being gone out by Cs residual in adsorption column with pure water, carry out desorption absorption to the Cs on resin with 1MNH4Cl solution.
Dynamic desorption condition: adsorption column size
amount of resin 15ml, 1MNH4Cl, flow 1.25ml/min (SV5).
Carried out Dynamic Adsorption evaluation experimental according to above-mentioned condition, the result of Fig. 4 shows that the Cs be adsorbed onto on resin is easy to it all be resolved with little leacheate.Concentrated Cs leacheate can be processed by the precipitation method etc., decreases volume of waste.On the other hand, the polymeric adsorbent processed can adsorb Cs again, Reusability, has very large actual application prospect.
Although preferred embodiment discloses as above by the present invention; so itself and be not used to limit content of the present invention; anyly be familiar with this those skilled in the art; not departing from main spirits of the present invention and context; when doing various change and retouching, the protection domain therefore invented should be as the criterion with the basic right claimed range applied for a patent.
Claims (8)
1. a preparation method for caesium polymeric adsorbent material, comprises the steps:
1) carry out free radical activation process to polymer base material, grafting carries out polymerisation containing the unsaturated monomer of epoxy radicals, and percent grafting should ensure more than 50%, obtained sorbing material presoma;
2) above-mentioned presoma is imported phosphorous heteropolyacid salt by epoxy ring-opening reaction and control Drug delivery rate more than 10%, obtained caesium polymeric adsorbent material.
2. the preparation method of a kind of caesium polymeric adsorbent material according to claim 1, it is characterized in that: described step 1) in the shape of polymer base material be average diameter be the rule of 30-800 micron or irregular spheroidal particle, or diameter 5-200 micron, length 100-10000 micron microfibrous material.
3. the preparation method of a kind of caesium polymeric adsorbent material according to claim 1, is characterized in that: described step 1) in free radical activation process comprise and adopt Ionizing Radiation or add radical initiator and process.
4. the preparation method of a kind of caesium polymeric adsorbent material according to claim 3, is characterized in that: described Ionizing Radiation is that the ionizing ray produced by gamma/gamma-rays, electron ray, X-ray carries out irradiation, dose of radiation 10-250kGy scope.
5. the preparation method of a kind of caesium polymeric adsorbent material according to claim 1, is characterized in that: described step 1) in the one be selected from containing the unsaturated monomer of epoxy radicals in GMA, acrylic acid hydroxyl butyl glycidyl ether.
6. the preparation method of a kind of caesium polymeric adsorbent material according to claim 1, is characterized in that: described step 1) in percent grafting reach more than 100%.
7. the preparation method of a kind of caesium polymeric adsorbent material according to claim 1, it is characterized in that: described step 2) in epoxy ring-opening reaction be carry out in the phosphorous heteropolyacid salt suspension of 1-10wt% in concentration, reaction temperature controls at 50-85 DEG C; Described phosphorous heteropolyacid salt is selected from the one in ammonium phosphomolybdate, ammonium phosphotungstate.
8. according to the application in the caesium separating technology of the arbitrary described caesium polymeric adsorbent material of claim 1-7 in adsorbing separation water.
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| CN104689802B (en) * | 2015-02-11 | 2017-06-13 | 上海交通大学 | A kind of high selectivity gold polymeric adsorbent material, preparation method and applications |
| CN105632575B (en) * | 2016-01-29 | 2017-07-21 | 北京师范大学 | Magnetic material with Adsorption of Radioactive nucleic function and preparation method based on hydroxyl modification |
| CN106975470B (en) * | 2017-05-12 | 2020-02-11 | 滨州学院 | Preparation method and application of porous AMP/CNC-PUF adsorbing material |
| CN110923480B (en) * | 2019-12-20 | 2020-10-02 | 华中科技大学 | Application of aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium |
| CN114259997B (en) * | 2021-12-15 | 2023-06-30 | 淮阴工学院 | High-strength rubidium/cesium specific adsorbent and preparation method and application thereof |
| CN114452950B (en) * | 2021-12-15 | 2023-10-20 | 淮阴工学院 | Preparation method and application of high-strength double-crosslinked network rubidium/cesium specific adsorbent |
| CN117116520B (en) * | 2023-08-16 | 2024-02-06 | 西南科技大学 | Method for deeply purifying strongly alkaline high-fluorine uranium wastewater and recycling uranium resources |
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| US6616860B1 (en) * | 1999-02-16 | 2003-09-09 | Agency Of Industrial Science And Technology | Biopolymer composite ion-exchanger with high cesium selectivity and its manufacturing method |
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Non-Patent Citations (2)
| Title |
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| "Removal of cobalt, strontium and cesium from radioactive laundry wastewater by ammonium molybdophosphate-polyacrylonitrile (AMP-PAN)";Younjin Park, et al;《Chemical Engineering Journal》;20101231;第162卷;2.2 Adsorbent preparation * |
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