CN113373681A - Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber - Google Patents

Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber Download PDF

Info

Publication number
CN113373681A
CN113373681A CN202110510071.6A CN202110510071A CN113373681A CN 113373681 A CN113373681 A CN 113373681A CN 202110510071 A CN202110510071 A CN 202110510071A CN 113373681 A CN113373681 A CN 113373681A
Authority
CN
China
Prior art keywords
uranium
xkxw
nuclear fuel
amino
fluorine
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
CN202110510071.6A
Other languages
Chinese (zh)
Inventor
聂小琴
张玉靖
董发勤
李书居
刘畅
万强
何平
潘宁
王君玲
丁聪聪
程文财
夏雪
蒋亚廷
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.)
Southwest University of Science and Technology
Original Assignee
Southwest University of Science and Technology
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 Southwest University of Science and Technology filed Critical Southwest University of Science and Technology
Priority to CN202110510071.6A priority Critical patent/CN113373681A/en
Publication of CN113373681A publication Critical patent/CN113373681A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/007—Recovery of isotopes from radioactive waste, e.g. fission products
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/20—Disposal of liquid waste
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile

Abstract

The invention discloses a method for treating uranium fluoride wastewater in a nuclear fuel element process, belonging to the technical field of radioactive waste liquid treatment. The method takes a self-made novel poly-amino functionalized fiber (with the number of XKXW-V) as an adsorption material (wherein the grafting rate of the poly-amino is more than or equal to 45 percent) to adsorb and extract uranium in the uranium fluoride wastewater. The preparation method of the material adopted by the invention is simple and rapid, the XKXW-V has stable physical and chemical properties, good hydrophilicity and high uranium selectivity, and the adsorption capacity of uranium is up to 459.27 mg/g. Aiming at the acidic uranium fluoride wastewater prepared by the high-concentration F-coexisting real pressurized water reactor fuel element preparation process, the XKXW-V prepared by the invention has good selectivity (Kd is more than or equal to 559.9L/g) on uranium, and the uranium removal rate can reach 99.8%. Therefore, the XKXW-V developed by the invention has better application prospect in deep purification of the uranium fluoride wastewater generated at the front end of the nuclear fuel cycle.

Description

Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber
Technical Field
The invention belongs to the field of radioactive wastewater treatment, and particularly relates to deep purification of high-fluorine uranium-containing wastewater generated in a pressurized water reactor nuclear fuel element production process and efficient extraction of uranium by novel poly-amino functionalized fiber.
Background
With the rapid development of the nuclear power industry in China, the demand for uranium is increasing day by day. At the front end of the nuclear fuel cycle, especially during the manufacture of nuclear fuel elements, UF is mainly used because of its current use6As a raw material for preparing UO2 core, a large amount of high-fluorine uranium-containing wastewater is generated, wherein the fluorine content can reach 1-20 g/L, and the wastewater has extremely strong acidity and certain corrosivity. At present, silica gel is mainly used for removing uranium in high-fluorine uranium-containing wastewater in a nuclear industrial system, but the practical problems that the number of silica gel recycling is small, secondary wastes are difficult to degrade, effluent is difficult to continuously meet the national emission standard and the like still exist. Therefore, it is important to develop an adsorbing material which can replace and is superior to silica gel. With the research on the adsorption separation technologyIn addition, a novel filamentous adsorbent, namely ion exchange fiber is developed on the basis of ion exchange resin, and compared with materials such as resin, silica gel and the like, the ion exchange fiber has larger specific surface area, faster adsorption/desorption rate and better cyclic regeneration performance, and has wide application prospect in the aspects of deep purification of uranium-containing wastewater and extraction and recovery of uranium.
High fluorine is one of the difficulties in effective and economic treatment of the wastewater, and because the fluorine and uranium complex forms are different under different pH values, the pH value of the wastewater needs to be adjusted to be suitable firstly, so that the normal operation of processes such as subsequent treatment and the like and the effluent quality can be ensured, and the maximum effect of the processes can be exerted.
The XKXW-V is an adsorption material with the grafting rate of polyamine groups being more than or equal to 45 percent, has good selectivity and higher uranium adsorption capacity, and has no report in the field of high-fluorine uranium-containing wastewater generated in the production process of nuclear fuel elements by applying the fiber. Therefore, the XKXW-V has potential application value to the sustainable development of the nuclear resources.
Disclosure of Invention
The invention aims to provide a method for efficiently removing uranium in high-fluorine uranium-containing wastewater generated in the production process of nuclear fuel elements by using polyamine-group modified ion exchange fibers.
In order to achieve the purpose, the invention adopts the technical scheme that.
Polyacrylonitrile fiber is used as a base material, grafting temperature and time are controlled under the condition that a swelling agent exists, a polyamine group is grafted to the base material in one step through hydrothermal reaction, and XKXW-V is synthesized. Soaking XKXW-V as adsorbing material in distilled water, and packing in chromatographic column with height of 100mm and diameter of 17mm and packing density of 0.19g/cm3The multistage series connection or parallel connection can be carried out, the pH of the uranium fluoride waste water containing hydrofluoric acid is adjusted to alkalinity by using an alkaline solution, waste water is subjected to chromatography column by a mode of feeding in and feeding out through a water pump, and finally waste liquid with the standard outlet uranium concentration is obtained.
The invention provides a method for preparing polyamine group modified polyacrylonitrile fiber and treating high-fluorine uranium-containing wastewater, which has the following advantages compared with the prior art.
(1) The uranium removal rate of XKXW-V is still high (> 85%) under the condition of F-concentration of 1-6 g/L.
(2) The XKXW-V and uranium have short action time, and the adsorption balance can be achieved within 1-2 h.
(3) The XKXW-V has various application forms, and can be made into various forms of fiber cloth, gauze and the like so as to adapt to various devices and environments.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the prior art will be briefly described below.
FIG. 1, a shows the effect of XKXW-V on the adsorption capacity of uranium at different temperatures and initial concentrations. b and c are respectively simulated Langmuir, Freundlich and other adsorption isothermal models, and the adsorption of the fiber conforms to the Langmuir adsorption isothermal model, which shows that the adsorption of the XKXW-V on uranium belongs to single-layer adsorption on the surface of the fiber.
FIG. 2 is F at 2g/L-In the coexistence system, the initial uranium concentration was 50mg/L, and the optimum pH =7, which indicates that the adsorption amount was 99.45 mg/g, depending on the influence of pH on the adsorption amount of uranium.
FIG. 3 shows the adsorption of uranium by XKXW-V in the presence of different concentrations of F-, and it can be seen from the figure that the adsorption amount of uranium is slightly reduced and less influenced with the increase of the concentration of F-.
FIG. 4, in order to verify the practical application effect of XKXW-V, 50mL of real waste liquid obtained from nuclear fuel element manufacturing plant was added with 0.02g of XKXW-V material, and ICP-OES was used to measure the concentration of the remaining elements in the waste liquid containing conventional metal elements and radioactive elements, including: u, Cr, Fe, Mn, K, Zn, As, P, Pb, Sr. The results in the figure show that the uranium removal rate reaches 99.8%, and the distribution coefficient can reach 559.9L g-1。
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments.
Example 1.
0.02g of XKXW-V is respectively taken, 50mL of uranium solution with initial concentration of 10, 20, 50, 80, 100, 120, 150, 200, 250, 300 and 350mg/L is added, the optimal pH is adjusted under the conditions of 20, 30 and 40 ℃, and the reaction is carried out for 2h, and the result is shown in figure 1 a. Simulations using the Langmuir model and the Freundlich model gave FIG. 1b and FIG. 1c, respectively. The result shows that the adsorption of the fiber conforms to the Langmuir adsorption isotherm, and the maximum adsorption quantity of the XKXW-V to uranium is 459.27 mg/g.
Example 2.
Adding 0.02g of XKXW-V into 50ml of uranium solution with initial uranium concentration of 50mg/L and fluorine concentration of 2g/L, respectively setting the pH values to be 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11, reacting for 2 hours at the reaction temperature of 25 ℃, and taking supernatant to analyze uranium concentration and F-The results are shown in FIG. 2. The result shows that the optimum pH =7 for adsorption, the adsorption capacity reaches 99.45 mg/g under the condition, the uranium adsorption capacity is greatly improved compared with the original polyacrylonitrile fiber, and the high-concentration F is not influenced-The influence of (c).
Example 3.
Adding 0.02g XKXW-V into 50ml, adjusting the initial uranium concentration to 50mg/L and the F-concentration to 1, 2, 3, 4, 5, 6g/L respectively, adjusting the pH to 7, reacting at 25 ℃ for 2h, and measuring the uranium concentration and the F concentration of the adsorbed solution-The results are shown in FIGS. 3a and 3b, indicating F-The increase of the concentration can reduce the adsorption amount of uranium by XKXW-V to some extent.
Example 4.
In order to verify the practical application effect of XKXW-V, XKXW-V is used for processing real uranium-containing process waste liquid of nuclear fuel element manufacturing plants, wherein the waste liquid comprises elements such As U, Cr, Fe, Mn, K, Zn, As, P, Pb, Sr and the like, the pH is =2, and the initial F is-The concentration was 3.4 g/L. 0.02g of XKXW-V is taken, 50mL of uranium-containing process waste liquid is added, and the reaction is carried out for 2h at the temperature of 25 ℃, and the result is shown in figure 4. The removal rate and the distribution coefficient Kd of the XKXW-V to uranium are respectively 99.8 percent and 559.9L g-1The composite material shows better selective adsorption and has better application prospect.

Claims (6)

1. A novel poly-amino functionalized fiber (number is XKXW-V) is characterized in that polyacrylonitrile fiber is used as a matrix, grafting time and temperature are controlled, poly-amino is grafted onto the matrix in one step through hydrothermal reaction, and the grafting rate of poly-amino is more than or equal to 45%.
2. The multi-amino-grafted multi-amino-functionalized fiber according to claim 1, characterized in that it is used in a variety of forms. The fiber has better flexibility and certain elasticity, and can be made into various forms such as fiber cloth, gauze and the like so as to adapt to various devices and environments.
3. The multi-amino functionalized fiber according to claim 1, which can be used as a high-efficiency adsorption material for uranium in fluorine-containing uranium-containing wastewater.
4. The fluorine-uranium wastewater generated in the production process of the nuclear fuel element is characterized by having pH =0-3 and extremely strong acidity.
5. The fluorine-uranium wastewater generated in the production process of the nuclear fuel element is characterized by containing a large amount of hydrofluoric acid, having extremely strong corrosivity and fluorine concentration of 1-20 g/L.
6. The waste water containing fluorine and uranium produced in the production process of nuclear fuel elements is characterized in that the concentration of uranium is 0.05-100 mg/L.
CN202110510071.6A 2021-05-11 2021-05-11 Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber Pending CN113373681A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110510071.6A CN113373681A (en) 2021-05-11 2021-05-11 Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110510071.6A CN113373681A (en) 2021-05-11 2021-05-11 Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber

Publications (1)

Publication Number Publication Date
CN113373681A true CN113373681A (en) 2021-09-10

Family

ID=77572440

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110510071.6A Pending CN113373681A (en) 2021-05-11 2021-05-11 Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber

Country Status (1)

Country Link
CN (1) CN113373681A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070049A (en) * 2021-04-13 2021-07-06 哈尔滨工程大学 Preparation method of amino-enhanced amidoxime-based swelling layer polyacrylonitrile fiber adsorbent

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1478950A (en) * 2002-08-30 2004-03-03 中国船舶重工集团公司第七研究院第七 Chelating function fiber and synthesis method
CN102491555A (en) * 2011-12-01 2012-06-13 核工业北京化工冶金研究院 Method for removing fluorine in acid uranium process wastewater
CN109289803A (en) * 2018-09-29 2019-02-01 西南科技大学 Polyamines base/amidoxime group modification polyfunctional group ion-exchange fibre method of preparation and use
CN110732160A (en) * 2019-11-26 2020-01-31 中国科学院过程工程研究所 method for dynamically adsorbing heavy metals in solution and application thereof
CN110963598A (en) * 2018-09-30 2020-04-07 中核四0四有限公司 Treatment method for uranium conversion alkaline fluorine-containing wastewater
CN112452305A (en) * 2020-11-05 2021-03-09 中国工程物理研究院核物理与化学研究所 Antibacterial adhesion type fiber uranium extraction material and preparation method thereof
CN112759110A (en) * 2020-11-26 2021-05-07 中核二七二铀业有限责任公司 Circulation method of uranium-containing fluorine-containing wastewater

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1478950A (en) * 2002-08-30 2004-03-03 中国船舶重工集团公司第七研究院第七 Chelating function fiber and synthesis method
CN102491555A (en) * 2011-12-01 2012-06-13 核工业北京化工冶金研究院 Method for removing fluorine in acid uranium process wastewater
CN109289803A (en) * 2018-09-29 2019-02-01 西南科技大学 Polyamines base/amidoxime group modification polyfunctional group ion-exchange fibre method of preparation and use
CN110963598A (en) * 2018-09-30 2020-04-07 中核四0四有限公司 Treatment method for uranium conversion alkaline fluorine-containing wastewater
CN110732160A (en) * 2019-11-26 2020-01-31 中国科学院过程工程研究所 method for dynamically adsorbing heavy metals in solution and application thereof
CN112452305A (en) * 2020-11-05 2021-03-09 中国工程物理研究院核物理与化学研究所 Antibacterial adhesion type fiber uranium extraction material and preparation method thereof
CN112759110A (en) * 2020-11-26 2021-05-07 中核二七二铀业有限责任公司 Circulation method of uranium-containing fluorine-containing wastewater

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张玉靖: "核燃料元件制造过程产生的复杂含铀废水处理新方法研究", 中国优秀硕士学位论文全文数据库工程科技I辑 *
王凤菊;丁海云;宿延涛;陈树森;: "壳聚糖基吸附剂的制备及其对铀的吸附性能研究", 湿法冶金 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070049A (en) * 2021-04-13 2021-07-06 哈尔滨工程大学 Preparation method of amino-enhanced amidoxime-based swelling layer polyacrylonitrile fiber adsorbent

Similar Documents

Publication Publication Date Title
Lee et al. Removal of heavy metals from aqueous solution by apple residues
CN110129561B (en) Method for removing fluorine in lepidolite neutral leaching solution by using modified bentonite adsorbent
CN113373681A (en) Method for treating nuclear fuel element process wastewater by using polyamine functionalized fiber
CN114797795B (en) Using GMA/H 3 PO 4 Method for treating uranium-containing wastewater by modified natural fibers
CN107216415B (en) Preparation method of anion resin for adsorbing heat-stable salt in amine liquid
CN108620022B (en) Iodide ion adsorbent, preparation method and application thereof
CN103272566A (en) Method for preparing ammonia nitrogen adsorbent by using banana peel and application of ammonia nitrogen adsorbent
CN115254051A (en) Modified polypropylene hollow fiber membrane and preparation method and application thereof
CN111036182A (en) Preparation of uranium adsorption gel balls based on aluminum sludge and method for treating uranium-containing wastewater
CN107473332B (en) Method for treating high-hardness high-arsenic underground water through ion exchange of Fe-based resin
CN105688828A (en) Method for preparing plant-inorganic composite adsorbents from phosphoric-acid-modified folium cycas for extracting uranium from seawater
CN113578267A (en) Polycrystalline nano-magnesia charcoal adsorbent for enriching uranium in nuclear wastewater
CN106710659B (en) A kind of method using silicon dioxide composite material absorption Uranium in Waste Water acyl
CN101912767A (en) Method for preparing modified furfural residue heavy metal adsorbent
CN102965312A (en) Modification method for improving bacteria heavy metal adsorption capacity, adsorbent and application thereof
CN113842892A (en) Method for treating uranium-containing wastewater by using amide/phosphate group modified natural fibers
CN103626129B (en) With industrial liquid chlorine for the method for electronic grade high-purity chlorine prepared by raw material
CN108854944B (en) Adsorbent for treating uranium-containing wastewater and application thereof
Lu et al. Preliminary research on Cr (VI) removal by bacterial cellulose
Klimiuk et al. The effect of poly (vinyl alcohol) on cadmium adsorption and desorption from alginate adsorbents
CN113000034B (en) Preparation method of uranium ion affinity membrane based on natural plant polyphenol composite coating
CN114522744A (en) Method for washing, desorbing and regenerating D363 resin
CN109384872B (en) Chelate resin and preparation method and application thereof
CN113499753A (en) Preparation and regeneration method of renewable demercuration adsorbent
CN107930598B (en) By using load Ce4+Method for removing fluoride ions from urea-formaldehyde resin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination