CN103508509A - Method for removing silver, cobalt, and strontium nuclide ions in radioactive waste water - Google Patents
Method for removing silver, cobalt, and strontium nuclide ions in radioactive waste water Download PDFInfo
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- CN103508509A CN103508509A CN201310352951.0A CN201310352951A CN103508509A CN 103508509 A CN103508509 A CN 103508509A CN 201310352951 A CN201310352951 A CN 201310352951A CN 103508509 A CN103508509 A CN 103508509A
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- calcium phosphate
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Abstract
The invention relates to the field of treatment of waste water, waste solid and waste gas in the nuclear industry, and discloses a method for removing the silver, cobalt, and strontium ions in radioactive waste water. The method comprises the following steps: mechanically mixing an insoluble solid absorbent with a mass percentage of 1 to 5% with a water body containing silver, cobalt and strontium ions to carry out reactions, and separating the water body and the solid deposit after the reactions are over so as to obtain a water body whose residual nuclide ion concentration is less than 12% of the original concentration. The method has the advantages that the technology process of the method for processing radioactive waste water is simple, the method only comprises two main steps, namely a step of mechanical mixing and a step of solid-liquid separation, besides, the method has low requirements on the equipment and no need for other addictives, is easy and convenient to operate, is convenient for radioactive protection, and helps to further reduce the cost and risk of processing the radioactive waste water.
Description
Technical field
The present invention relates to nuclear industry disposal of three wastes field, relate in particular to a kind of method of removing silver-colored cobalt strontium ion in radioactive wastewater.
Background technology
The core disposal of three wastes is very important as the important component part ，Qi status of China's nuclear industry, is subject to public's common concern.The processing of radioactive wastewater, disposal are one of important contents of the core disposal of three wastes.In radioactive wastewater, conventionally contain the nucleic ions such as silver, cobalt, strontium, remove nucleic ion for reducing waste water radioactive level, significant.
Absorption method is the main method of Spent Radioactive water treatment, and the exploitation of sorbent material and selection are one of research emphasis of absorption method removal radioactive wastewater Radionuclide pollution.Because inorganic adsorbent has, raw materials cost is low, manufacture craft simple, the advantage of by product Shao Deng aspect, is highly suitable for the improvement of metal ion pollution water body.The method of utilizing inorganic adsorbent to remove metal ion in water body open or report mainly contains at present:
(1) Gao Zihan, Gao Zihui propose in patent " a kind of preparation method of the material for Adsorption of Heavy Metals " (CN 102641725 A), take Nanoscale Iron, magnesium salts, aluminium salt, caustic soda is inorganic reaction thing, take Thiocarb as functionalizers, after Thiocarb is mixed with Nanoscale Iron, join in the mixing solutions of caustic soda and aluminium salt, mix, more slowly add magnesium salt solution, obtain the material of Adsorption of Heavy Metals.By this material feed liquid body by volume per-cent 1～10% join in heavy metal wastewater thereby, counterweight metal has good absorption property and magnetic separation performance.Yet sorbent material cost of the present invention is higher, complex manufacturing technology, and the removal technological process of metal ion is more complicated also.
(2) disclosed " a kind of preparation method of adsorbent for heavy metal " (CN 102962028 A) such as Shen Jianxing: with P25 nano-TiO
2for body material, adopt hydrothermal method to prepare netted K
3ti
8o
17presoma, it is placed in retort furnace and calcines, and obtaining adsorbent for heavy metal is K
3ti
8o
17sorbent material.This sorbent material cost is higher, needs high temperature and preparation time longer during reaction, and this sorbent material only has adsorption effect to heavy metal cadmium ion.
(3) Wang Yinye discloses a kind of modification float stone for purification of heavy metal sewage and its production and use in patent " for modification float stone of purification of heavy metal sewage and its production and use " (CN 102580666 A), taking float stone is raw material, by fragmentation, and screening, ball milling is processed into irregular granular, be processed into the particle of particle diameter 16-100 order sizes, put into oven for drying, retort furnace calcining, tap water cancellation, drain, oven for drying, granule shape float stone is finished product.After adopting modification, float stone is by absorption-ion exchange, by the heavy metal ion Cu in water body
2+, Pb
2+, Zn
2+, Cd
2+, Cr
2+, Hg
2+, As
5+remove.This raw materials cost is cheap, and complete processing is simple, uses modification float stone removal monomer heavy metal and mixture-metal effective, instant effect, non-secondary pollution.But the method is failed to prove and can be removed silver, cobalt and the strontium ion in water.
(4) fourth refined (CN 101898926 A) etc. has found a kind of heavy metal ion adsorption carrier heavy metal ion to be had to good adsorption effect.Described heavy metal ion adsorption carrier, by inorganic nano poriferous titanium dioxide fiber, formed, the concrete steps of its preparation method are: hydrophobic polymer is dissolved in solvent, adds titania nanoparticles or solubility titanium salt, stir and form uniform solution; This solution is at room temperature carried out to electrostatic spinning, by the prepared fiber Direct precipitation of electrostatic spinning to accepting to obtain tunica fibrosa on material; By tunica fibrosa, at 1-10MPa pressure, 90-120 ℃, the time is 20-60 minute hot-pressing processing, carries out subsequently 400-500 ℃ of calcining, and the organic composition of removing in fiber obtains inorganic nano poriferous titanium dioxide fiber film, as heavy metal ion adsorption carrier.The making work of this sorbent material is complicated, process is loaded down with trivial details, and the cost needing is higher.
(5) Jia Y. J., at its paper, (Ind. Eng. Chem. Res. 2012,51, has reported a kind of mesoporous zirconium phosphonate mixing material NTAZP in 12266-12273) to the people such as Zhang Y. J., and heavy metal ion is had to good adsorption.This material is prepared from by eight water zirconium oxychlorides and Amino Trimethylene Phosphonic Acid (ATMP), is rendered as the globosity with lobule thin slice, therefore shows the vermicular mesoporous and higher surface-area of class.It has good adsorption for heavy metal ion as Pb2+, Cu2+, Cd2+.
(6) Guangdong Prov. Inst. of Ecological Environment & Soil Science's disclosure of the invention the surfactant-modified inorganic mineral of a kind of process be the heavy metal absorbent (CN 102389776 A) that carrier, load organic complexing agent are prepared from.Described inorganic mineral is wilkinite, kaolin, diatomite, zeolite, aluminum oxide or ferriferous oxide; Described tensio-active agent is cationic surfactant or nonionic surface active agent; Described organic complexing agent is the compound that contains sulfydryl or contain amido.Heavy metal absorbent of the present invention has stable performance, environmental friendliness, loading capacity is high, selectivity is strong, reclaim the advantages such as convenient post-treatment, to the loading capacity of the heavy metals such as cadmium, mercury, lead, all over 100mg/g, in administering the water surrounding of heavy metal contamination and edatope, can reach good regulation effect.
(7) patent " a kind of preparation method of porous calcium titanate heavy metal adsorbent " that is applying in east of Shenyang Univ. of Science and Engineering, it is the solid waste of utilizing alditol industry---alditol slag is template, the porous flake calcium titanate heavy metal absorbent that adopts sol-gel method to prepare.By the broken calcium titanate colloidal sol that adds of dry alditol ground-slag, stir, dry, obtain alditol slag---calcium titanate gel composite, high-temperature calcination, the organism in oxygenolysis alditol slag and calcium titanate gel, obtains porous calcium titanate sorbent material.Absorption in the time of for various heavy such as water lead, cadmium, nickel, copper, zinc and silver.It is low that the method synthetic adsorbent has cost, and technique is simple, and the loading capacity of sorbent material is large, and use range is wide, hydrothermally stable, and resistance to acids and bases is strong, regenerates and reclaims the advantages such as convenient.
In above-mentioned prior art, the inorganic adsorbent of use all will, through more complicated synthetic, preparation process or surface treatment process, be unfavorable for the reduction of cost and the popularization of technology.And the method that above-mentioned technology does not have or only part relates to removal silver, cobalt, strontium ion, not yet there is report can remove the method for these three kinds of ions simultaneously.
In disclosed patent and document, to utilizing report that sorbent material removes strontium ion in water body seldom.A patent of China Atomic Energy Science Research Institute's application relates to " preparation method of inorganic strontium selective adsorbent " (CN 102247796 A), by adding MnCl
2solution and NaOH solution are optionally to remove Preparation of Metallic Strontium ion, and still, this method is only applicable to the processing of various low levels strontium waste liquids, and does not belong to the treatment process of using inorganic adsorbent.
Summary of the invention
In order to solve the problems of the prior art, the invention provides a kind of method of removing silver-colored cobalt strontium ion in radioactive wastewater, solve the problem that can not simultaneously remove silver-colored cobalt strontium ion in nuclear waste water in prior art.
The invention provides a kind of method of removing silver-colored cobalt strontium ion in radioactive wastewater, comprise the steps: with insoluble solid adsorbent, 1 ~ 5% react with the water body mechanically mixing of argentiferous, cobalt and strontium ion by mass percentage, reaction finishes rear separated water body and solid precipitation, obtains remaining nucleic ionic concn not higher than the water body of former content 12%.
As a further improvement on the present invention: described insoluble fixed adsorbent is crystalline state or amorphous calcium phosphate salt; The ratio of calcium and phosphorus of described crystalline state or amorphous calcium phosphate salt is 0.5～2.5.
As a further improvement on the present invention: described in reaction times of reacting be not less than 5 minutes.
As a further improvement on the present invention: described crystalline state or amorphous calcium phosphate salt are the combination of single pure phase calcium phosphate salt or multiple phase calcium phosphate calcium salt.
The invention has the beneficial effects as follows: the crystalline state of ratio of calcium and phosphorus between 0.5～2.5 or amorphous calcium phosphate salt are easy is easy to get, at nature ubiquity, synthetic is also comparatively easy, belong to the industrial chemicals that can directly buy, its material cost is lower, add that usage quantity is only 1～5% of Water quality, be of value to the cost that reduces Spent Radioactive water treatment method, reduce the quantity of second-order activity residue.The technological process that the method the present invention relates to is processed radioactive wastewater is simple, key step is only mechanically mixing and separated solid liquid phase, not high and without using other additive to equipment requirements, therefore simple and easy to do, be convenient to radio-protective, be conducive to further reduce the cost and risk of Spent Radioactive water treatment.
[embodiment]
Below in conjunction with embodiment, the present invention is further described.
A kind of method of removing silver-colored cobalt strontium ion in radioactive wastewater, comprise the steps: with insoluble solid adsorbent, 1 ~ 5% react with the water body mechanically mixing of argentiferous, cobalt and strontium ion by mass percentage, reaction finishes rear separated water body and solid precipitation, obtains remaining nucleic ionic concn not higher than the water body of former content 12%.
Described insoluble fixed adsorbent is crystalline state or amorphous calcium phosphate salt; The ratio of calcium and phosphorus of described crystalline state or amorphous calcium phosphate salt is 0.5～2.5.
The described reaction times reacting is not less than 5 minutes.
Described crystalline state or amorphous calcium phosphate salt are the combination of single pure phase calcium phosphate salt or multiple phase calcium phosphate calcium salt.
Calcium phosphate salt can be attached to other solid material surface as sorbent material.
Silver, cobalt, strontium ion for removing in radioactive wastewater, utilize inorganic adsorbent to obtain method few at present.Contriver is through comparative studies discovery, and insoluble calcium phosphate salt solid (powder or block) has very strong adsorption to above-mentioned three kinds of ions, can be used for processing radioactive wastewater.Contriver's research shows, no matter crystalline state or amorphous calcium phosphate salt, all can interact by silver, cobalt, the strontium ion in ion-exchange or phase transformation reaction and water, reaches the effect of quick adsorption; This reaction process is very fast, and under suitable sorbent material consumption and mixing condition, the reaction of 5 minutes can reach the effect of removing 80% ion; And the precipitated solid of reacting after finishing is comparatively stable, has no the nucleic ion phenomenon of stripping again.After reaction finishes, can use precipitation, the separation means such as centrifugal that solid, liquid is separated, the remaining nucleic ion content in gained liquid, not higher than 12% of former content, is realized good removal effect.The method can Reusability to improve nucleic ion remaval effect.
Exemplify embodiment below and comparative example is further described the present invention.
Embodiment 1
Using insoluble, ratio of calcium and phosphorus at 1.6～1.7 crystalline state hydroxy apatite powder as solid adsorbent, 5% is the water mixing of 100 μ g/ml with silver, cobalt, strontium ion content respectively by mass percentage, stirring reacts 1 hour, and reaction finishes rear centrifugation water body and solid precipitation.By separated soln using plasma mass spectrograph and spectrometer measurement residual metals content.Adopt the result that calibration curve method obtains to show, concentration of silver ions is 6.9 μ g/ml, and concentration of cobalt ions is 6.1 μ g/ml, and strontium ion concentration is 11.3 μ g/ml, and metal ion clearance is respectively 93.1%, 93.9% and 88.7%.
Embodiment 2
Using insoluble, ratio of calcium and phosphorus at 0.5 non-crystalline state calcium phosphate powder as solid adsorbent, other condition is as embodiment 1.In solution after separation, concentration of silver ions is 7.8 μ g/ml, and concentration of cobalt ions is 9.0 μ g/ml, and strontium ion concentration is 10.8 μ g/ml, and metal ion clearance is respectively 92.2%, 91.0% and 89.2%.
Embodiment 3
Using insoluble, total ratio of calcium and phosphorus at 2.4 crystalline state hydroxyapatite and calcium phosphate salt mixed powder as solid adsorbent, other condition is as embodiment 1.In solution after separation, concentration of silver ions is 9.3 μ g/ml, and concentration of cobalt ions is 10.2 μ g/ml, and strontium ion concentration is 10.0 μ g/ml, and metal ion clearance is respectively 90.7%, 89.8% and 90.0%.
The method can Reusability to improve nucleic ion remaval effect.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (4)
1. a method of removing silver-colored cobalt strontium ion in radioactive wastewater, it is characterized in that: comprise the steps: with insoluble solid adsorbent, 1 ~ 5% react with the water body mechanically mixing of argentiferous, cobalt and strontium ion by mass percentage, reaction finishes rear separated water body and solid precipitation, obtains remaining nucleic ionic concn not higher than the water body of former content 12%.
2. remove according to claim 1 the method for silver-colored cobalt strontium ion in radioactive wastewater, it is characterized in that: described insoluble fixed adsorbent is crystalline state or amorphous calcium phosphate salt; The ratio of calcium and phosphorus of described crystalline state or amorphous calcium phosphate salt is 0.5～2.5.
3. remove according to claim 1 the method for silver-colored cobalt strontium ion in radioactive wastewater, it is characterized in that: described in reaction times of reacting be not less than 5 minutes.
4. remove according to claim 1 the method for silver-colored cobalt strontium ion in radioactive wastewater, it is characterized in that: described crystalline state or amorphous calcium phosphate salt are the combination of single pure phase calcium phosphate salt or multiple phase calcium phosphate calcium salt.
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| CN201310352951.0A CN103508509A (en) | 2013-08-14 | 2013-08-14 | Method for removing silver, cobalt, and strontium nuclide ions in radioactive waste water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170474A (en) * | 2020-01-21 | 2020-05-19 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under aerobic condition |
| CN112439396A (en) * | 2019-08-28 | 2021-03-05 | 南京理工大学 | Hydroxyethylidene diphosphonic acid/hydroxyapatite organic-inorganic hybrid composite material and preparation method thereof |
| CN113247998A (en) * | 2021-05-25 | 2021-08-13 | 中国人民解放军陆军勤务学院 | Application of titanium trichloride and treatment method of rhenium-containing wastewater |
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| CN101796592A (en) * | 2007-12-05 | 2010-08-04 | 日挥株式会社 | Method for treating radioactive waste solution and treatment apparatus |
| CN101891271A (en) * | 2010-06-04 | 2010-11-24 | 清华大学 | Method of using diatomite to pretreat radioactive waste water |
| JP2012507000A (en) * | 2008-10-27 | 2012-03-22 | コミッサリア ア ロンネルジー アトミック エ オ ゾンネルジー ザルテルナティーフ | Method for decontamination of liquid effluent containing one or more radioactive chemical elements by treatment in a fluidized bed |
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2013
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Patent Citations (3)
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| CN101796592A (en) * | 2007-12-05 | 2010-08-04 | 日挥株式会社 | Method for treating radioactive waste solution and treatment apparatus |
| JP2012507000A (en) * | 2008-10-27 | 2012-03-22 | コミッサリア ア ロンネルジー アトミック エ オ ゾンネルジー ザルテルナティーフ | Method for decontamination of liquid effluent containing one or more radioactive chemical elements by treatment in a fluidized bed |
| CN101891271A (en) * | 2010-06-04 | 2010-11-24 | 清华大学 | Method of using diatomite to pretreat radioactive waste water |
Non-Patent Citations (2)
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|---|
| 吴梧桐 等: "《生物制药工艺学》", 30 April 2013 * |
| *** 等: "《生物产品分离纯化技术》", 31 August 2009 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112439396A (en) * | 2019-08-28 | 2021-03-05 | 南京理工大学 | Hydroxyethylidene diphosphonic acid/hydroxyapatite organic-inorganic hybrid composite material and preparation method thereof |
| CN112439396B (en) * | 2019-08-28 | 2023-10-13 | 南京理工大学 | Organic-inorganic hybrid composite material of hydroxy ethylidene diphosphonic acid/hydroxy apatite and preparation method thereof |
| CN111170474A (en) * | 2020-01-21 | 2020-05-19 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under aerobic condition |
| CN113247998A (en) * | 2021-05-25 | 2021-08-13 | 中国人民解放军陆军勤务学院 | Application of titanium trichloride and treatment method of rhenium-containing wastewater |
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Application publication date: 20140115 |