WO2016179935A1 - Method for enriching uranium from aqueous solution containing uranyl ions - Google Patents

Method for enriching uranium from aqueous solution containing uranyl ions Download PDF

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WO2016179935A1
WO2016179935A1 PCT/CN2015/089919 CN2015089919W WO2016179935A1 WO 2016179935 A1 WO2016179935 A1 WO 2016179935A1 CN 2015089919 W CN2015089919 W CN 2015089919W WO 2016179935 A1 WO2016179935 A1 WO 2016179935A1
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aqueous solution
uranyl
solution containing
adsorption
acid
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PCT/CN2015/089919
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French (fr)
Chinese (zh)
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李景烨
张伯武
马红娟
刘西艳
凌长见
杨晓娟
虞鸣
张阔
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中国科学院上海应用物理研究所
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Publication of WO2016179935A1 publication Critical patent/WO2016179935A1/en

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    • 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
    • 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

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  • the invention particularly relates to a process for enriching uranium from an aqueous solution containing uranyl ions.
  • China's energy strategy has taken nuclear energy as an important component, and the demand for uranium will increase year by year.
  • China's medium and long-term development plan for nuclear power by 2020, China's total installed nuclear power capacity will reach 86 million kilowatts, and the demand for natural uranium will be about 8,500 tons.
  • China's terrestrial uranium resources are not abundant, and most of them are poor ore.
  • the annual output of natural uranium is only about 700 tons. Therefore, by 2020, China's uranium fuel gap will reach more than 90%, relying heavily on imports, which poses a serious threat to China's nuclear energy development.
  • AO adsorbent fibrous material.
  • the AO-containing adsorbent fiber is irradiated with polyacrylonitrile (AN) on a stronger base material such as polyethylene (PE), polypropylene (PP) fiber or nonwoven fabric, and then subjected to amidoximation reaction.
  • the nitrile group is converted to an AO group that can adsorb uranium.
  • Further studies have shown that the fibers are graft copolymerized with acrylic acid (AA) and AN, followed by amide amination to obtain an adsorbent material.
  • an AO-based adsorbent was prepared by fluorination of a high specific surface area polyethylene polymer material by radiation grafting of polyacrylonitrile and re-amined to pump seawater (the concentration of uranyl ions in seawater was 3.5 ppb) to 0.8 L.
  • the adsorption capacity of the AO-containing adsorbent material has a high adsorption capacity and good selectivity because the coordination ability of the AO group and the uranyl ion is strong, especially alkali and alkaline earth metals such as calcium, which are relatively concentrated in seawater. Magnesium ions, etc.
  • the cost and cost of increasing the adsorption capacity by increasing the grafting rate of acrylonitrile or designing a more efficient adsorption function group is enormous.
  • the preparation method of AO-based adsorbent material has several fatal problems: First, the chemical stability of AO is poor.
  • the adsorption capacity loss of the material is serious, and the material reuse efficiency is low.
  • the adsorption capacity of AO for vanadium, one of uranium and competing ions is comparable to that of uranium, and vanadium elements are difficult to elute from the adsorbent material.
  • the material "vanadium poisoning" will directly reduce the adsorption capacity of the material.
  • the technical problem to be solved by the present invention provides a method for overcoming defects such as low adsorption rate, poor selectivity, low recycling rate, short service life, high production cost, and unsuitability for industrial production in the prior art.
  • the uranyl ion adsorbing material of the invention has low production cost, high adsorption rate, high selectivity, long service life, high recycling rate and is suitable for industrial production.
  • the present invention provides a method for enriching uranium from an aqueous solution containing uranyl ions, comprising the steps of: adsorbing an aqueous solution containing uranyl ions with a uranyl ion adsorbing material; said uranyl ion Adsorbent material or s material.
  • the concentration of the uranyl ion in the aqueous solution containing uranyl ions is generally greater than or equal to 1 ppb, preferably from 1 ppb to 1000 ppb.
  • the uranyl ion-containing aqueous solution containing uranyl ions having a concentration of 1 ppb to 1000 ppb may be expressed in natural water, salt lake water, seawater desalination project concentrated wastewater or uranium mining wastewater.
  • the "containing group" or Material” for various types of groups or Inorganic materials or organic polymer materials may be an inorganic material conventionally used in the art, preferably activated carbon or magnetic iron oxide.
  • the organic polymer material may be a conventional organic polymer material in the art, preferably polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), nylon, polyacrylic acid, polymethacrylic acid, acrylic acid. Copolymer, methacrylic acid copolymer or weak acid type cation exchange resin.
  • the weak acid type cation exchange resin means a carboxylic acid group
  • the resin may be a resin containing an aliphatic carboxylic acid or a resin containing an aromatic carboxylic acid; the resin containing an aliphatic carboxylic acid is preferably an aliphatic carboxylic acid resin having an alkyl group or a cycloalkyl group bonded to a carboxyl group;
  • the aromatic carboxylic acid-containing resin is preferably an aromatic carboxylic acid resin in which a benzene ring is bonded to a carboxyl group.
  • the aromatic carboxylic acid resin in which a benzene ring is bonded to a carboxyl group is, for example, a carboxylated polystyrene resin.
  • the cycloalkyl group-bonded aliphatic carboxylic acid resin such as a cyclopentylic acid resin.
  • the alkyl group-bonded aliphatic carboxylic acid resin is, for example, a carboxylated polystyrene resin.
  • the group containing group The organic polymer material is preferably polyethylene grafted polyacrylic acid, polyethylene grafted polymethacrylic acid, polypropylene grafted polymaleic acid, polyvinylidene fluoride grafted polyacrylic acid, polyvinylidene fluoride grafted polymethacrylic acid.
  • the organic polymer material is preferably a polyglycidyl methacrylate resin material.
  • Said The inorganic material is preferably benzoic acid modified magnetic iron oxide or maleic acid modified activated carbon.
  • the uranyl ion adsorbing material has a granular form, a fiber filament shape, a felt shape, a film shape or a gel form.
  • the uranyl ion adsorbing material in the adsorption, may be in contact with the aqueous solution containing uranyl ions in an immersion or flow-through manner.
  • the flow rate of the uranyl ion-containing aqueous solution is preferably from 5 mL to 2000 mL/min and/or the linear velocity through the cross section of the line is preferably from 0.1 to 350 cm/s, more preferably 20 mL/min and/or 0.86 cm/s.
  • an immersion type it is preferably accompanied by an oscillating process.
  • the contact time of the uranyl ion adsorbing material with the aqueous solution containing the uranyl ion is preferably close to the adsorption capacity of the material, and generally can be selected according to the demand in actual use. , can be 1 hour to 90 days, or 2 hours to 50 days, or 24 hours ⁇ 42 days, or 20 to 30 days.
  • the adsorption temperature may be a conventional temperature for such operation in the art, and may be 0 to 80 ° C, for example, 0 to 40 ° C, and further, for example, 10 to 30 ° C, preferably 25 ° C.
  • the step of taking out the uranyl ion adsorbing material is further included.
  • the uranyl ion adsorbing material may be desorbed after the uranyl ion adsorbing material is taken out.
  • the steps and conditions of the desorption can be selected as conventional in the art.
  • the desorption preferably comprises the steps of: immersing the adsorbed uranyl ion adsorbing material in an aqueous hydrochloric acid solution for 0 to 3 hours, and then taking it out and washing it with deionized water.
  • the aqueous hydrochloric acid solution is preferably an aqueous solution of hydrochloric acid of 0.01 to 0.5 mol/L.
  • the washing is preferably carried out 3 times.
  • the uranyl ion adsorbing material may be a group containing a group prepared by a physical or chemical method conventional in the art. or s material.
  • the physical method may be blending, and the chemical method may be copolymerization, graft polymerization or crosslinking.
  • the reagents and starting materials used in the present invention are commercially available.
  • the room temperature refers to an ambient temperature of 0 to 40 °C.
  • the positive progress of the present invention is that the conventionally recognized low concentration uranyl ion-enriched material is an amidoxime-based chelating material.
  • amidoxime-based materials have the above drawbacks.
  • the present invention corrects a technical bias in which it has traditionally been believed that the adsorption of uranium should select a group that can chelate with uranium, and research practice has been conducted in this direction, and the present invention has re-recognized the group-containing group. or The application prospects of materials enriched in uranium from low concentrations of uranyl ion aqueous solution.
  • the invention uses a uranyl ion adsorption material with low production cost, can enrich uranium element from a low concentration uranyl ion aqueous solution, avoids the use of the toxic compound acrylonitrile, and has little environmental pollution during the production process.
  • the uranyl ion adsorbing material of the invention has low adsorption capacity for vanadium, does not reduce the adsorption capacity and re-use efficiency of the material due to vanadium poisoning of the material, and has high adsorption rate (the adsorption capacity for uranium can reach up to 7.57 mg/g) Good material stability and high reusability (the average adsorption capacity of uranium is still very high after only 10 times of 10 times of adsorption capacity loss.
  • each ion concentration (in terms of elements) is: UO 2 2+ 330ppb, VO 3 - 152ppb, Fe 3+ 141ppb, Co 2+ 5.3ppb, Ni 2+ 101ppb, Cu 2+ 65ppb , Zn 2+ 408 ppb, Pb 2+ 34.6 ppb, Mg 2+ 1.2 ⁇ 10 5 ppb, Ca 2+ 0.6 ⁇ 10 5 ppb.
  • the PE grafted polymethacrylic acid film material was placed in seawater at 25 ° C for 50 days, and the concentration of each ion in seawater was the same as in Example 2.
  • the PE grafted polymethacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms.
  • the adsorption capacity of each ion on the PE grafted polymethacrylic acid film material was as shown in Table 4:
  • the PE grafted polyacrylic film material was placed in salt lake water at 25 ° C for 50 days. Among them, the ion concentration of salt lake water is shown in Table 5:
  • the PE grafted polyacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms.
  • the adsorption capacity of each ion on the PE grafted polyacrylic acid film material was as shown in Table 6:
  • the PE grafted polyacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms.
  • the adsorption capacity of each ion on the PE grafted polyacrylic acid film material was as shown in Table 8:
  • Example 6 adsorption of uranyl ion in seawater by PP grafted polymaleic acid fiber material
  • the seawater was grafted with PVDF at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) at 30 ° C for 30 days.
  • concentration of each ion in the uranium mining wastewater (in terms of elements) is: UO 2 2+ 87ppb, VO 3 - 92ppb, Fe 3+ 500ppb, Co 2+ 7.8ppb, Ni 2+ 200ppb, Cu 2+ 80ppb, Zn 2 + 398 ppb, Pb 2+ 50 ppb, Mg 2+ 2.5 ⁇ 10 3 ppb, Ca 2+ 5.3 ⁇ 10 4 ppb.
  • Example 8 Adsorption of uranyl ions in seawater by PE blended polyacrylic felt material
  • the seawater of 25 ° C was blended with PE at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) through PE, and adsorbed for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the seawater at 20 ° C was passed through a cross-linked polymethacrylic acid gel material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the seawater at 15 ° C was passed through a carboxylated polystyrene resin material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the seawater at 10 ° C was passed through a cyclopentylcarboxylic acid resin material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the seawater of 25 ° C was passed through a polyacrylate hydrolyzate polyacrylic acid material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • polyacrylic acid hydrolyzate polyacrylic acid material is taken out, and the adsorption capacity of each ion on the polyacrylic acid hydrolyzate polyacrylic acid material is tested as shown in Table 15:
  • the seawater was modified with benzoic acid at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) at 25 ° C for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the seawater was modified with maleic acid at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) at 30 ° C for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the seawater at 25 ° C was passed through a polyglycidyl methacrylate material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for 30 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • Example 18 PE grafted polyacrylic acid film material for adsorption of uranyl ions in seawater
  • each ion concentration (in terms of elements) is: UO 2 2+ 1.2ppb, VO 3 - 0.8ppb, Fe 3+ 1ppb, Co 2+ 0.05ppb, Ni 2+ 0.5ppb, Cu 2+ 0.07 ppb, Zn 2+ 1.7 ppb, Pb 2+ 0.06 ppb, Mg 2+ 1.2 ⁇ 10 5 ppb, Ca 2+ 0.6 ⁇ 10 5 ppb.
  • the PE grafted polyacrylic acid film material is taken out to test the PE grafted polyacrylic acid film material.
  • the adsorption capacity of each ion is shown in Table 21:
  • Example 19 adsorption grafting desorption cycle of uranyl ion in concentrated seawater by PE grafted polyacrylic acid film material
  • each ion concentration (in terms of elements) is: UO 2 2+ 330ppb, VO 3 - 152ppb, Fe 3+ 141ppb, Co 2+ 5.3ppb, Ni 2+ 101ppb, Cu 2+ 65ppb , Zn 2+ 408 ppb, Pb 2+ 34.6 ppb, Mg 2+ 1.2 ⁇ 10 5 ppb, Ca 2+ 0.6 ⁇ 10 5 ppb.
  • the PE grafted polyacrylic acid film material was taken out, and the concentration of uranyl ions in the concentrated seawater after adsorption was tested to calculate the adsorption capacity of the PE grafted polyacrylic acid film material.
  • the PE grafted polyacrylic film material was immersed in 0.5 M HCl for 3 hours.
  • the PE grafted polyacrylic acid film material was taken out and washed 3 times with deionized water.
  • the experimental results show that the material of the present invention has an average loss of about 5% of U adsorption per 10 cycles, and the amidoxime based material is tested by the method of this embodiment, and each cycle has about 5%. loss.
  • Example 20 adsorption of uranyl ions in seawater by PE grafted polymethacrylic acid film material
  • the PE grafted polymethacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms.
  • the adsorption capacity of each ion on the PE grafted polymethacrylic acid film material was as shown in Table 23:
  • Example 21 adsorption of uranyl ions in seawater by PE grafted polymethacrylic acid film material
  • the seawater flow rate is 320 cm/s, and the polyglycolic acid film material is grafted by PE, and adsorbed at 25 ° C for 50 days.
  • the concentration of each ion in seawater was the same as in Example 2.
  • the PE grafted polymethacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms.
  • the adsorption capacity of each ion on the PE grafted polymethacrylic acid film material was as shown in Table 23:

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A method for enriching uranium from an aqueous solution containing uranyl ions, comprising the following steps: adsorbing an aqueous solution containing uranyl ions with a uranyl ion adsorbing material; and the uranyl ion absorbing material is a material containing a group. A low-production-cost uranyl ion adsorbing material is used for enriching the uranium element from a low concentration uranyl ion aqueous solution, avoiding the use of the toxic compound acrylonitrile, with low pollution to the environment in the production process and a low adsorption capacity for vanadium; the adsorption capacity and the re-use efficiency of the material cannot be reduced because of the vanadium poisoning of the material; the adsorption rate is high; the maximum adsorption capacity for uranium can be as high as 7.57 mg/g; the stability is good and the re-use efficiency is high; and the average adsorption capacity loss is only 5% after 10 times of recycling use, and the adsorption capacity for uranium is still very high after 100 times.

Description

一种从含铀酰离子的水溶液中富集铀的方法Method for enriching uranium from aqueous solution containing uranyl ion
本申请要求申请日为2015年5月11日的中国专利申请CN201510237626.9的优先权。本申请引用上述中国专利申请的全文。The present application claims priority from Chinese Patent Application No. CN201510237626.9, filed on May 11, 2015. This application cites the entire text of the above-mentioned Chinese patent application.
技术领域Technical field
本发明具体涉及一种从含铀酰离子的水溶液中富集铀的方法。The invention particularly relates to a process for enriching uranium from an aqueous solution containing uranyl ions.
背景技术Background technique
近年来我国的能源战略将核能作为重要组成部分，对铀的需求量将逐年增加。根据我国核电中长期发展规划，到2020年我国核电总装机容量将达到8600万千瓦，对天然铀的需求量约8500吨。而我国陆地铀矿资源不丰富，且大多是贫矿，天然铀年产量只有700吨左右。因此，到2020年，我国铀燃料缺口将达90％以上，严重依赖于进口，这对我国的核能发展形成严重的威胁。In recent years, China's energy strategy has taken nuclear energy as an important component, and the demand for uranium will increase year by year. According to China's medium and long-term development plan for nuclear power, by 2020, China's total installed nuclear power capacity will reach 86 million kilowatts, and the demand for natural uranium will be about 8,500 tons. China's terrestrial uranium resources are not abundant, and most of them are poor ore. The annual output of natural uranium is only about 700 tons. Therefore, by 2020, China's uranium fuel gap will reach more than 90%, relying heavily on imports, which poses a serious threat to China's nuclear energy development.
除陆地铀矿之外，自然水体系中蕴藏着大量的铀资源。以海水和盐湖水为例：在海水中存在着很低浓度的铀，总量却达到40亿吨，约为陆地铀矿储量的一千倍。盐湖作为古老海洋经过地球运动的结果，经过数百万年的天然浓缩蒸发，铀含量为海洋水的几十到几百倍。柴达木盆地湖泊众多，其中盐湖达二十五个之多。盐湖类型齐全，成分复杂，其卤水中赋存有极其丰富的U、Th、Rb、Cs、Br和I等稀有分散元素资源，其含量之高和储量之大，在世界同类型现代盐湖中均属罕见。水体系中的这类资源如果能够富集利用，可以提供可谓取之不尽的铀资源。自然水体系中虽然铀储量丰富，然而其浓度很低，海水中铀浓度约为3.0～3.5ppb，盐湖水中铀浓度稍高但也在1000ppb以下，并与大量其他金属离子共存。如何经济、有效得从海水和盐湖水中提取铀是一个极具挑战的研究方向。 In addition to terrestrial uranium deposits, natural water systems contain large amounts of uranium resources. Take seawater and salt lake water as an example: there is a very low concentration of uranium in seawater, the total amount is 4 billion tons, about a thousand times the reserves of terrestrial uranium. As a result of the movement of the ancient ocean through the earth, the salt lake has been tens of millions of years of natural concentrated evaporation, and the uranium content is tens to hundreds of times of ocean water. There are many lakes in the Qaidam Basin, of which there are twenty-five of the salt lakes. The salt lake is complete in type and complex in composition. Its brine contains extremely abundant resources of rare dispersing elements such as U, Th, Rb, Cs, Br and I. Its high content and large reserves are in the same type of modern salt lakes in the world. It is rare. Such resources in the water system can provide inexhaustible uranium resources if they can be enriched and utilized. Although the natural water system is rich in uranium reserves, its concentration is very low. The concentration of uranium in seawater is about 3.0-3.5 ppb. The concentration of uranium in salt lake water is slightly higher but below 1000 ppb, and it coexists with a large number of other metal ions. How to extract uranium from seawater and salt lake water economically and effectively is a very challenging research direction.
目前人们普遍认同的最有希望实现商业化的低浓度铀酰离子吸附材料是日本在1980年前后发明了一种含偕胺肟基(
Figure PCTCN2015089919-appb-000001
AO)的纤维状材料。这种含AO基的吸附纤维是在强度较好的基底材料如聚乙烯(PE)、聚丙烯(PP)纤维或无纺布上辐射接枝聚丙烯腈(AN)，再通过肟胺化反应将腈基转化为可以吸附铀的AO基。进一步的研究表明，使用丙烯酸(AA)与AN接枝共聚改性纤维，然后进行肟胺化，得到吸附材料。2003年，日本高崎研究所采用辐射接枝法制备了350公斤的高分子纤维吸附剂并在真实海水中进行吸铀试验，240天内提取了超过1公斤铀。具体参考文献如下：1、Seko,N.；Katakai,A.；Hasegawa,S.；Tamada,M.；Kasai,N.；Takeda,H.；Sugo,T.；Saito,K.Nucl Technol 2003,144,274。2、Tamada,M.Japan Atomic Energy Agency 2009。3、Takeda,T.；Saito,K.；Uezu,K.；Furusaki,S.；Sugo,T.；Okamoto,J.Industrial&Engineering Chemistry Research 1991,30,185。4、Sekiguchi,K.；Saito,K.；Konishi,S.；Furusaki,S.；Sugo,T.；Nobukawa,H.Industrial&Engineering Chemistry Research 1994,33,662。5、Kitamura,A.；Hamamoto,S.；Taniike,A.；Ohtani,Y.；Kubota,N.；Furuyama,Y.Radiation Physics and Chemistry 2004,69,171。6、Seko,N.；Tamada,M.；Yoshii,F.Nuclear Instruments&Methods in Physics Research Section B-Beam Interactions with Materials and Atoms 2005,236,21。At present, the most promising low-concentration uranyl ion adsorbent material that is widely expected to be commercialized is that Japan invented an amidoxime-containing group around 1980.
Figure PCTCN2015089919-appb-000001
AO) fibrous material. The AO-containing adsorbent fiber is irradiated with polyacrylonitrile (AN) on a stronger base material such as polyethylene (PE), polypropylene (PP) fiber or nonwoven fabric, and then subjected to amidoximation reaction. The nitrile group is converted to an AO group that can adsorb uranium. Further studies have shown that the fibers are graft copolymerized with acrylic acid (AA) and AN, followed by amide amination to obtain an adsorbent material. In 2003, the Takasaki Research Institute of Japan used the radiation grafting method to prepare 350 kg of polymer fiber adsorbent and carried out the uranium test in real seawater, and extracted more than 1 kg of uranium in 240 days. Specific references are as follows: 1. Seko, N.; Katakai, A.; Hasegawa, S.; Tamada, M.; Kasai, N.; Takeda, H.; Sugo, T.; Saito, K. Nucl Technol 2003, 144,274.2, Tamada, M. Japan Atomic Energy Agency 2009. 3. Takeda, T.; Saito, K.; Uezu, K.; Furusaki, S.; Sugo, T.; Okamoto, J. Industrial & Engineering Chemistry Research 1991, 30,185.4, Sekiguchi, K.; Saito, K.; Konishi, S.; Furusaki, S.; Sugo, T.; Nobukawa, H. Industrial & Engineering Chemistry Research 1994, 33, 662. 5. Kitamura, A.; Hamamoto, S ;Taniike, A.; Ohtani, Y.; Kubota, N.; Furuyama, Y. Radiation Physics and Chemistry 2004, 69, 171. 6. Seko, N.; Tamada, M.; Yoshii, F. Nuclear Instruments & Methods in Physics Research Section B-Beam Interactions with Materials and Atoms 2005, 236, 21.
近年来海水提铀研究受到世界各国的重新重视。研究者在日本吸附材料的基础上，开始对偕胺肟基吸附材料进行优化。美国在一种高比表面积的聚乙烯高分子材料上利用辐射接枝聚丙烯腈再胺肟化制备一种AO基吸附材料，泵送海水(海水中铀酰离子浓度为3.5ppb)以0.8L/min流速通过该材料，6周后最高可以达到3.3mg/g(参考文献：Kim J,Tsouris C,Mayes RT,Oyola Y,Saito T,Janke CJ,Dai S,Schneider E,Sachde D.Separation Science and Technology,2012,48:367-387)。日本的样品在同样条件下吸附容量约为0.5mg/g。(参考文献：Kim,J.；Oyola,Y.；Tsouris,C.；Hexel,C.R.；Mayes,R.T.； Janke,C.J.；Dai,S.Industrial&Engineering Chemistry Research 2013,52,9433.)中国科学院上海应用物理研究所基于超高分子量聚乙烯纤维通过辐射接枝聚丙烯腈再胺肟化制备的含AO基吸附纤维，委托美国能源部对海水(海水中铀酰离子浓度为3.5ppb)进行测试，发现最佳吸附容量为2.3mg/g，达到了世界一流水平。(参考文献：Xing,Z.；Hu,J.；Wang,M.；Zhang,W.；Li,S.；Gao,Q.；Wu,G.Science China Chemistry 2013,56,1504.)尽管如此，基于目前日本和美国最好的吸附材料估算出来的海水提铀的成本仍然比陆地铀矿开采的成本高。日本的海水提铀成本预算报告中显示，从海水提取1公斤铀的成本约为3万2千日元，其中的83％用于高分子吸附材料的制备。无机吸附剂例如水合TiO2等吸附容量低(一般低于1‰)、选择性差；有机吸附剂化学稳定性差、使用寿命短等都是海水提铀成本高的根源。降低成本的关键在于提高吸附材料的吸附容量和使用寿命。In recent years, research on seawater uranium has been re-emphasized by countries all over the world. Based on the Japanese adsorption materials, the researchers began to optimize the amidoxime-based adsorbent materials. In the United States, an AO-based adsorbent was prepared by fluorination of a high specific surface area polyethylene polymer material by radiation grafting of polyacrylonitrile and re-amined to pump seawater (the concentration of uranyl ions in seawater was 3.5 ppb) to 0.8 L. /min flow rate through the material, up to 3.3mg / g after 6 weeks (Reference: Kim J, Tsouris C, Mayes RT, Oyola Y, Saito T, Janke CJ, Dai S, Schneider E, Sachde D. Separation Science And Technology, 2012, 48: 367-387). The Japanese sample had an adsorption capacity of about 0.5 mg/g under the same conditions. (References: Kim, J.; Oyola, Y.; Tsouris, C.; Hexel, CR; Mayes, RT; Janke, CJ; Dai, S. Industrial & Engineering Chemistry Research 2013, 52, 9433.) Shanghai Applied Physics, Chinese Academy of Sciences The Institute based on ultra-high molecular weight polyethylene fibers prepared by radiation-grafted polyacrylonitrile re-amine deuteration containing AO-based adsorption fibers, commissioned the US Department of Energy to test the seawater (the concentration of uranyl ions in seawater is 3.5ppb), found the most The good adsorption capacity is 2.3mg/g, which has reached the world-class level. (Reference: Xing, Z.; Hu, J.; Wang, M.; Zhang, W.; Li, S.; Gao, Q.; Wu, G. Science China Chemistry 2013, 56, 1504.) The cost of seawater uranium estimated based on the current best adsorbent materials in Japan and the United States is still higher than the cost of land uranium mining. Japan's seawater uranium cost budget report shows that the cost of extracting 1 kilogram of uranium from seawater is about 32,000 yen, of which 83% is used for the preparation of polymer adsorbent materials. Inorganic adsorbents such as hydrated TiO 2 have low adsorption capacity (generally less than 1 ‰) and poor selectivity; poor chemical stability of organic adsorbents and short service life are the root causes of high cost of seawater uranium extraction. The key to reducing costs is to increase the adsorption capacity and service life of the adsorbent material.
含AO基的吸附材料具有较高的吸附容量和很好的选择性是由于AO基与铀酰离子配位能力很强，特别是相对于海水中浓度高的碱金属和碱土金属，例如钙、镁离子等。然而从目前的研究水平看，用提高丙烯腈的接枝率提高吸附容量，或者设计更高效的吸附功能团提高吸附容量所产生的代价和成本巨大。此外，含AO基吸附材料的制备方法具有几大致命问题：一、AO的化学稳定性差，当材料上的铀酰离子被酸洗脱之后，材料的吸附容量损失严重，材料重复使用效率低。二、AO基对铀和竞争离子之一的钒的吸附容量与铀相当，且钒元素很难从吸附材料上洗脱下来。材料“钒中毒”会直接降低材料的吸附容量。(参考文献：1、P.K.Tewari,Recovery of Uranium from Sea Water,Chemical Sciences&Engineering,BARC HIGHLIGHTS(2006-2007)53。2、P.A.Kavakli,N.Seko,M.Tamada and O.Guven,Adsorption efficiency of a new adsorbent towards uranium and vanadium ions at low concentrations,Sep.Sci.Technol.,39(2004)1631-1643.)三、AO基材料制备的关键步骤所需要的丙烯腈单体是一种有毒危险化合物。 The adsorption capacity of the AO-containing adsorbent material has a high adsorption capacity and good selectivity because the coordination ability of the AO group and the uranyl ion is strong, especially alkali and alkaline earth metals such as calcium, which are relatively concentrated in seawater. Magnesium ions, etc. However, from the current research level, the cost and cost of increasing the adsorption capacity by increasing the grafting rate of acrylonitrile or designing a more efficient adsorption function group is enormous. In addition, the preparation method of AO-based adsorbent material has several fatal problems: First, the chemical stability of AO is poor. When the uranyl ion on the material is eluted by acid, the adsorption capacity loss of the material is serious, and the material reuse efficiency is low. Second, the adsorption capacity of AO for vanadium, one of uranium and competing ions, is comparable to that of uranium, and vanadium elements are difficult to elute from the adsorbent material. The material "vanadium poisoning" will directly reduce the adsorption capacity of the material. (References: 1, PKTewari, Recovery of Uranium from Sea Water, Chemical Sciences & Engineering, BARC HIGHLIGHTS (2006-2007) 53. 2, PAKavakli, N. Seko, M. Tamada and O. Guven, Adsorption efficiency of a new Adsorbent towards uranium and vanadium ions at low concentrations, Sep. Sci. Technol., 39 (2004) 1631-1643.) III. The acrylonitrile monomer required for the critical step in the preparation of AO-based materials is a toxic hazardous compound.
因此，制备生产成本低、吸附速率高、选择性高、使用寿命长、重复利用率高、适合于工业化生产且环境友好型的铀酰离子吸附材料是目前急需解决的技术问题。Therefore, the preparation of uranyl ion adsorption materials with low production cost, high adsorption rate, high selectivity, long service life, high recycling rate, and suitable for industrial production and environmentally friendly is an urgent technical problem to be solved.
发明内容Summary of the invention
本发明所要解决的技术问题为了克服现有技术中铀酰离子吸附材料吸附速率低、选择性差、重复利用率低、使用寿命短、生产成本高、不适合于工业化生产等缺陷而提供了一种从含铀酰离子的水溶液中富集铀的方法。本发明的铀酰离子吸附材料生产成本低、吸附速率高、选择性高、使用寿命长、重复利用率高、适合于工业化生产。The technical problem to be solved by the present invention provides a method for overcoming defects such as low adsorption rate, poor selectivity, low recycling rate, short service life, high production cost, and unsuitability for industrial production in the prior art. A method of enriching uranium from an aqueous solution containing uranyl ions. The uranyl ion adsorbing material of the invention has low production cost, high adsorption rate, high selectivity, long service life, high recycling rate and is suitable for industrial production.
本发明提供了一种从含铀酰离子的水溶液中富集铀的方法，其包括下述步骤：用铀酰离子吸附材料对含铀酰离子的水溶液进行吸附即可；所述的铀酰离子吸附材料为含基团
Figure PCTCN2015089919-appb-000002
或
Figure PCTCN2015089919-appb-000003
的材料。The present invention provides a method for enriching uranium from an aqueous solution containing uranyl ions, comprising the steps of: adsorbing an aqueous solution containing uranyl ions with a uranyl ion adsorbing material; said uranyl ion Adsorbent material
Figure PCTCN2015089919-appb-000002
or
Figure PCTCN2015089919-appb-000003
s material.
本发明中，所述的含铀酰离子的水溶液中铀酰离子的浓度一般为大于或等于1ppb，优选1ppb～1000ppb。所述的铀酰离子的浓度为1ppb～1000ppb的含铀酰离子的水溶液具体表现形式可以为自然界中的海水、盐湖水、海水淡化工程浓缩废水或铀矿开采废水等。In the present invention, the concentration of the uranyl ion in the aqueous solution containing uranyl ions is generally greater than or equal to 1 ppb, preferably from 1 ppb to 1000 ppb. The uranyl ion-containing aqueous solution containing uranyl ions having a concentration of 1 ppb to 1000 ppb may be expressed in natural water, salt lake water, seawater desalination project concentrated wastewater or uranium mining wastewater.
本发明中，所述的“含基团
Figure PCTCN2015089919-appb-000004
或
Figure PCTCN2015089919-appb-000005
的材料”为各类含基团
Figure PCTCN2015089919-appb-000006
或
Figure PCTCN2015089919-appb-000007
的无机材料或有机高分子材料。所述的无机材料可以为本领域中常规的无机材料优选活性炭或磁性氧化铁。所述的有机高分子材料可以为本领域中常规的有机高分子材料优选聚乙烯(PE)、聚丙烯(PP)、聚偏氟乙烯(PVDF)、尼龙、聚丙烯酸、聚甲基丙烯酸、丙烯酸共聚物、甲基丙烯酸共聚物或弱酸型阳离子交换树脂。所述的弱酸型阳离子交换树脂是指含有 羧酸基
Figure PCTCN2015089919-appb-000008
的树脂，可以为含有脂肪族羧酸的树脂或含有芳香族羧酸的树脂；所述的含有脂肪族羧酸的树脂优选烷基或环烷基连接羧基的脂肪族羧酸树脂；所述的含有芳香族羧酸的树脂优选苯环连接羧基的芳香族羧酸树脂。所述的苯环连接羧基的芳香族羧酸树脂例如羧基化聚苯乙烯树脂。所述的环烷基连接羧基的脂肪族羧酸树脂例如环戊基甲酸树脂。所述的烷基连接羧基的脂肪族羧酸树脂例如羧基化聚苯乙烯树脂。In the present invention, the "containing group"
Figure PCTCN2015089919-appb-000004
or
Figure PCTCN2015089919-appb-000005
Material" for various types of groups
Figure PCTCN2015089919-appb-000006
or
Figure PCTCN2015089919-appb-000007
Inorganic materials or organic polymer materials. The inorganic material may be an inorganic material conventionally used in the art, preferably activated carbon or magnetic iron oxide. The organic polymer material may be a conventional organic polymer material in the art, preferably polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), nylon, polyacrylic acid, polymethacrylic acid, acrylic acid. Copolymer, methacrylic acid copolymer or weak acid type cation exchange resin. The weak acid type cation exchange resin means a carboxylic acid group
Figure PCTCN2015089919-appb-000008
The resin may be a resin containing an aliphatic carboxylic acid or a resin containing an aromatic carboxylic acid; the resin containing an aliphatic carboxylic acid is preferably an aliphatic carboxylic acid resin having an alkyl group or a cycloalkyl group bonded to a carboxyl group; The aromatic carboxylic acid-containing resin is preferably an aromatic carboxylic acid resin in which a benzene ring is bonded to a carboxyl group. The aromatic carboxylic acid resin in which a benzene ring is bonded to a carboxyl group is, for example, a carboxylated polystyrene resin. The cycloalkyl group-bonded aliphatic carboxylic acid resin such as a cyclopentylic acid resin. The alkyl group-bonded aliphatic carboxylic acid resin is, for example, a carboxylated polystyrene resin.
本发明中，所述的含基团
Figure PCTCN2015089919-appb-000009
的有机高分子材料优选聚乙烯接枝聚丙烯酸、聚乙烯接枝聚甲基丙烯酸、聚丙烯接枝聚马来酸、聚偏氟乙烯接枝聚丙烯酸、聚偏氟乙烯接枝聚甲基丙烯酸、聚乙烯共混聚丙烯酸、聚乙烯共混聚甲基丙烯酸、交联聚丙烯酸、交联聚甲基丙烯酸、羧基化聚苯乙烯树脂、环戊基甲酸树脂、聚甲基丙烯酸材料、丙烯酸共聚物或甲基丙烯酸共聚物。In the present invention, the group containing group
Figure PCTCN2015089919-appb-000009
The organic polymer material is preferably polyethylene grafted polyacrylic acid, polyethylene grafted polymethacrylic acid, polypropylene grafted polymaleic acid, polyvinylidene fluoride grafted polyacrylic acid, polyvinylidene fluoride grafted polymethacrylic acid. Polyethylene blended polyacrylic acid, polyethylene blended polymethacrylic acid, crosslinked polyacrylic acid, crosslinked polymethacrylic acid, carboxylated polystyrene resin, cyclopentylcarboxylic acid resin, polymethacrylic acid material, acrylic acid copolymerization Or methacrylic acid copolymer.
所述的含基团
Figure PCTCN2015089919-appb-000010
的有机高分子材料优选聚甲基丙烯酸缩水甘油酯树脂材料。所述的含
Figure PCTCN2015089919-appb-000011
的无机材料优选苯甲酸修饰的磁性氧化铁或马来酸修饰活性炭。Group containing group
Figure PCTCN2015089919-appb-000010
The organic polymer material is preferably a polyglycidyl methacrylate resin material. Said
Figure PCTCN2015089919-appb-000011
The inorganic material is preferably benzoic acid modified magnetic iron oxide or maleic acid modified activated carbon.
本发明中，所述的铀酰离子吸附材料形态为颗粒状、纤维丝状、毡状、薄膜状或凝胶状。In the present invention, the uranyl ion adsorbing material has a granular form, a fiber filament shape, a felt shape, a film shape or a gel form.
本发明中，所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的方式可以为浸置式或流动通过式。若采用流动通过式，则所述的含铀酰离子的水溶液的流速优选5mL-2000mL/min和/或流经管线横截面的线速度优选0.1-350cm/s，更优选20mL/min和/或0.86cm/s。若采用浸置式，则优选还伴有震荡过程。In the present invention, in the adsorption, the uranyl ion adsorbing material may be in contact with the aqueous solution containing uranyl ions in an immersion or flow-through manner. If flow-through is employed, the flow rate of the uranyl ion-containing aqueous solution is preferably from 5 mL to 2000 mL/min and/or the linear velocity through the cross section of the line is preferably from 0.1 to 350 cm/s, more preferably 20 mL/min and/or 0.86 cm/s. If an immersion type is employed, it is preferably accompanied by an oscillating process.
本发明中，所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的时间以接近材料吸附饱和容量为佳，一般可按照实际使用时的需求进行选择，可以为1小时～90天,或者2小时～50天，或者24小时 ～42天，或者20～30天。In the present invention, when the adsorption is performed, the contact time of the uranyl ion adsorbing material with the aqueous solution containing the uranyl ion is preferably close to the adsorption capacity of the material, and generally can be selected according to the demand in actual use. , can be 1 hour to 90 days, or 2 hours to 50 days, or 24 hours ~42 days, or 20 to 30 days.
本发明中，所述的吸附的温度可以为本领域中该类操作的常规温度，可以为0～80℃，例如0～40℃，再例如10℃～30℃，优选25℃。In the present invention, the adsorption temperature may be a conventional temperature for such operation in the art, and may be 0 to 80 ° C, for example, 0 to 40 ° C, and further, for example, 10 to 30 ° C, preferably 25 ° C.
本发明中，所述的吸附结束后优选还包括将所述的铀酰离子吸附材料取出的步骤。In the present invention, preferably, after the end of the adsorption, the step of taking out the uranyl ion adsorbing material is further included.
本发明中，所述的吸附结束后，将所述的铀酰离子吸附材料取出后还可对该铀酰离子吸附材料进行脱附。所述的脱附的步骤和条件均可按照本领域的常规进行选择。In the present invention, after the adsorption is completed, the uranyl ion adsorbing material may be desorbed after the uranyl ion adsorbing material is taken out. The steps and conditions of the desorption can be selected as conventional in the art.
所述的脱附优选包括以下步骤：将吸附后的铀酰离子吸附材料浸泡于盐酸水溶液中0-3小时，随后取出用去离子水清洗，即可。所述的盐酸水溶液优选为0.01-0.5mol/L的盐酸水溶液。所述的清洗优选清洗3次。The desorption preferably comprises the steps of: immersing the adsorbed uranyl ion adsorbing material in an aqueous hydrochloric acid solution for 0 to 3 hours, and then taking it out and washing it with deionized water. The aqueous hydrochloric acid solution is preferably an aqueous solution of hydrochloric acid of 0.01 to 0.5 mol/L. The washing is preferably carried out 3 times.
本发明中，所述的铀酰离子吸附材料可以为采用本领域中常规的物理或化学的方法制备得到的含有基团
Figure PCTCN2015089919-appb-000012
或
Figure PCTCN2015089919-appb-000013
的材料。所述的物理方法可以为共混，所述的化学方法可以为共聚、接枝聚合或者交联。In the present invention, the uranyl ion adsorbing material may be a group containing a group prepared by a physical or chemical method conventional in the art.
Figure PCTCN2015089919-appb-000012
or
Figure PCTCN2015089919-appb-000013
s material. The physical method may be blending, and the chemical method may be copolymerization, graft polymerization or crosslinking.
在不违背本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。The above preferred conditions can be arbitrarily combined without departing from the ordinary knowledge in the art, that is, preferred embodiments of the present invention.
本发明所用试剂和原料均市售可得。The reagents and starting materials used in the present invention are commercially available.
本发明中，所述的室温是指环境温度，为0～40℃。In the present invention, the room temperature refers to an ambient temperature of 0 to 40 °C.
本发明的积极进步效果在于：传统认可的低浓度铀酰离子富集材料是偕胺肟类螯合材料。但偕胺肟基材料具有上述缺陷。本发明纠正了一种技术偏见，在该领域传统上一直认为对铀的吸附应选择可以与铀进行螯合的基团，也一直以此方向开展研究实践，而本发明则重新认识含基团
Figure PCTCN2015089919-appb-000014
或
Figure PCTCN2015089919-appb-000015
的材料从低浓度铀酰离子水溶液中富集铀的应用前景。本发明使用一种低生产成本的铀酰离子吸附材料，可以从低浓度铀酰离子水溶液中富集铀元素， 避免使用有毒化合物丙烯腈，生产过程中对环境污染小。本发明的铀酰离子吸附材料对钒的吸附容量低，不会因材料的钒中毒而降低材料的吸附容量和重复使用效率，吸附率高(对铀的吸附容量最高能够达到7.57mg/g)、材料稳定性好、重复使用效率高(平均循环使用10次吸附容量损失仅5％、100次后对铀的吸附容量依然很高。The positive progress of the present invention is that the conventionally recognized low concentration uranyl ion-enriched material is an amidoxime-based chelating material. However, amidoxime-based materials have the above drawbacks. The present invention corrects a technical bias in which it has traditionally been believed that the adsorption of uranium should select a group that can chelate with uranium, and research practice has been conducted in this direction, and the present invention has re-recognized the group-containing group.
Figure PCTCN2015089919-appb-000014
or
Figure PCTCN2015089919-appb-000015
The application prospects of materials enriched in uranium from low concentrations of uranyl ion aqueous solution. The invention uses a uranyl ion adsorption material with low production cost, can enrich uranium element from a low concentration uranyl ion aqueous solution, avoids the use of the toxic compound acrylonitrile, and has little environmental pollution during the production process. The uranyl ion adsorbing material of the invention has low adsorption capacity for vanadium, does not reduce the adsorption capacity and re-use efficiency of the material due to vanadium poisoning of the material, and has high adsorption rate (the adsorption capacity for uranium can reach up to 7.57 mg/g) Good material stability and high reusability (the average adsorption capacity of uranium is still very high after only 10 times of 10 times of adsorption capacity loss.
具体实施方式detailed description
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。The invention is further illustrated by the following examples, which are not intended to limit the invention. The experimental methods in the following examples which do not specify the specific conditions are selected according to conventional methods and conditions, or according to the product specifications.
实施例1PE接枝聚丙烯酸薄膜材料对浓缩海水中铀酰离子的吸附Example 1 Adsorption of uranyl ions in concentrated seawater by PE grafted polyacrylic acid film material
1、取浓缩海水5L，其中各离子浓度(以元素计)分别为：UO2 2+330ppb，VO3 -152ppb，Fe3+141ppb，Co2+5.3ppb，Ni2+101ppb，Cu2+65ppb，Zn2+408ppb，Pb2+34.6ppb，Mg2+1.2×105ppb，Ca2+0.6×105ppb。1. Take 5L of concentrated seawater, wherein each ion concentration (in terms of elements) is: UO 2 2+ 330ppb, VO 3 - 152ppb, Fe 3+ 141ppb, Co 2+ 5.3ppb, Ni 2+ 101ppb, Cu 2+ 65ppb , Zn 2+ 408 ppb, Pb 2+ 34.6 ppb, Mg 2+ 1.2×10 5 ppb, Ca 2+ 0.6×10 5 ppb.
2、在其中投加0.1g PE接枝聚丙烯酸薄膜材料，室温(25℃)下震荡吸附24小时。2. 0.1 g of PE grafted polyacrylic acid film material was added thereto, and oscillated for 24 hours at room temperature (25 ° C).
3、将PE接枝聚丙烯酸薄膜材料取出，测试PE接枝聚丙烯酸薄膜材料上各离子吸附容量见表1：3. The PE grafted polyacrylic acid film material was taken out, and the adsorption capacity of each ion on the PE grafted polyacrylic acid film material was tested as shown in Table 1:
表1 PE接枝聚丙烯酸薄膜材料对各离子的吸附量表Table 1 Adsorption scale of each ion for PE grafted polyacrylic acid film material
Figure PCTCN2015089919-appb-000016
Figure PCTCN2015089919-appb-000016
实施例2PE接枝聚丙烯酸薄膜材料对海水中铀酰离子的吸附Example 2 Adsorption of Uranyl Ions in Seawater by PE Grafted Polyacrylic Film Materials
1、海水以20ml/min(线速度0.86cm/s)的流速通过PE接枝聚丙烯酸薄膜材料，25℃吸附42天(6周)。其中，海水中各离子浓度见表2： 1. Seawater was grafted onto the polyacrylic acid film material by PE at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s), and adsorbed at 25 ° C for 42 days (6 weeks). Among them, the concentration of each ion in seawater is shown in Table 2:
表2 海水中各离子浓度Table 2 Concentrations of various ions in seawater
元素element UU VV FeFe CoCo NiNi CuCu ZnZn PbPb MgMg CaCa
浓度(ppb)Concentration (ppb) 3.53.5 1.91.9 40.640.6 0.30.3 1.11.1 5.45.4 8.28.2 31.631.6 1.2×105 1.2×10 5 0.6×105 0.6×10 5
2、将PE接枝聚丙烯酸薄膜材料取出，测试PE接枝聚丙烯酸薄膜材料上各离子吸附容量见表3：2. The PE grafted polyacrylic acid film material was taken out, and the adsorption capacity of each ion on the PE grafted polyacrylic acid film material was tested as shown in Table 3:
表3 PE接枝聚丙烯酸薄膜材料对各离子的吸附量表Table 3 Adsorption amount of each ion of PE grafted polyacrylic acid film material
Figure PCTCN2015089919-appb-000017
Figure PCTCN2015089919-appb-000017
实施例3PE接枝聚甲基丙烯酸薄膜材料对海水中铀酰离子的吸附Example 3 Adsorption of uranyl ions in seawater by PE grafted polymethacrylic acid film material
1、将PE接枝聚甲基丙烯酸薄膜材料在25℃海水中放置50天，海水中各离子浓度同实施例2。1. The PE grafted polymethacrylic acid film material was placed in seawater at 25 ° C for 50 days, and the concentration of each ion in seawater was the same as in Example 2.
2、将PE接枝聚甲基丙烯酸薄膜材料取出，洗去表面附着泥沙和微生物，测试PE接枝聚甲基丙烯酸薄膜材料上各离子吸附容量见表4：2. The PE grafted polymethacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms. The adsorption capacity of each ion on the PE grafted polymethacrylic acid film material was as shown in Table 4:
表4 PE接枝聚甲基丙烯酸薄膜材料对各离子的吸附量表Table 4 Adsorption scale of each ion for PE grafted polymethacrylic acid film material
Figure PCTCN2015089919-appb-000018
Figure PCTCN2015089919-appb-000018
实施例4PE接枝聚丙烯酸薄膜材料对盐湖水中铀酰离子的吸附Example 4 Adsorption of Uranyl Ions in Salt Lake Water by PE Grafted Polyacrylic Film Materials
1、将PE接枝聚丙烯酸薄膜材料在25℃盐湖水中放置50天。其中，盐湖水中各离子浓度见表5：1. The PE grafted polyacrylic film material was placed in salt lake water at 25 ° C for 50 days. Among them, the ion concentration of salt lake water is shown in Table 5:
表5 盐湖水中各离子浓度 Table 5 Ion concentration in salt lake water
元素element UU VV FeFe CoCo NiNi CuCu ZnZn PbPb MgMg CaCa
浓度(ppb)Concentration (ppb) 832832 412412 980980 69.369.3 200200 10231023 16581658 12531253 6.6×106 6.6×10 6 7.6×106 7.6×10 6
2、将PE接枝聚丙烯酸薄膜材料取出，洗去表面附着泥沙和微生物，测试PE接枝聚丙烯酸薄膜材料上各离子吸附容量见表6：2. The PE grafted polyacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms. The adsorption capacity of each ion on the PE grafted polyacrylic acid film material was as shown in Table 6:
表6 PE接枝聚丙烯酸薄膜材料对各离子的吸附量表Table 6 Adsorption amount of each ion of PE grafted polyacrylic acid film material
Figure PCTCN2015089919-appb-000019
Figure PCTCN2015089919-appb-000019
实施例5PE接枝聚丙烯酸薄膜材料对海水淡化浓缩废水中铀酰离子的吸附Example 5 Adsorption of Uranyl Ions in Seawater Desalination Concentrated Wastewater by PE Grafted Polyacrylic Acid Film Materials
1、25℃海水淡化浓缩废水以20ml/min(线速度0.86cm/s)的流速通过PE接枝聚丙烯酸薄膜材料，吸附50天。其中，海水淡化浓缩废水中各离子浓度见表7：1, 25 ° C seawater desalination concentrated wastewater at a flow rate of 20ml / min (linear velocity 0.86cm / s) through PE grafted polyacrylic acid film material, adsorption for 50 days. Among them, the concentration of each ion in seawater desalination and concentrated wastewater is shown in Table 7:
表7 海水淡化浓缩废水中各离子浓度Table 7 Concentration of each ion in seawater desalination concentrated wastewater
元素element UU VV FeFe CoCo NiNi CuCu ZnZn PbPb MgMg CaCa
浓度(ppb)Concentration (ppb) 4.54.5 2.42.4 80.680.6 0.40.4 1.41.4 6.86.8 10.310.3 42.142.1 1.1×106 1.1×10 6 0.7×106 0.7×10 6
2、将PE接枝聚丙烯酸薄膜材料取出，洗去表面附着泥沙和微生物，测试PE接枝聚丙烯酸薄膜材料上各离子吸附容量见表8：2. The PE grafted polyacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms. The adsorption capacity of each ion on the PE grafted polyacrylic acid film material was as shown in Table 8:
表8 PE接枝聚丙烯酸薄膜材料对各离子的吸附量表Table 8 Adsorption scale of each ion for PE grafted polyacrylic acid film material
Figure PCTCN2015089919-appb-000020
Figure PCTCN2015089919-appb-000020
实施例6PP接枝聚马来酸纤维材料对海水中铀酰离子的吸附Example 6 adsorption of uranyl ion in seawater by PP grafted polymaleic acid fiber material
1、30℃海水以20ml/min(线速度0.86cm/s)的流速通过PP接枝聚马来 酸纤维材料，吸附30天。海水中各离子浓度同实施例2。1. 30 ° C seawater at a flow rate of 20 ml / min (linear velocity 0.86 cm / s) through PP grafted polyma Acid fiber material, adsorbed for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将PP接枝聚马来酸纤维材料取出，测试PP接枝聚马来酸纤维材料上各离子吸附容量见表9：2. The PP grafted polymaleic acid fiber material was taken out, and the adsorption capacity of each ion on the PP grafted polymaleic acid fiber material was tested as shown in Table 9:
表9 PP接枝聚马来酸纤维材料对各离子的吸附量表Table 9 Adsorption amount of each ion of PP grafted polymaleic acid fiber material
Figure PCTCN2015089919-appb-000021
Figure PCTCN2015089919-appb-000021
实施例7PVDF接枝聚丙烯酸颗粒材料对铀矿开采废水中铀酰离子的吸附Example 7 Adsorption of Uranyl Ions in Uranium Mining Wastewater by PVDF Grafted Polyacrylic Acid Granular Materials
1、30℃海水以20ml/min(线速度0.86cm/s)的流速通过PVDF接枝聚丙烯酸颗粒材料，吸附30天。铀矿开采废水中各离子浓度(以元素计)分别为：UO2 2+87ppb，VO3 -92ppb，Fe3+500ppb，Co2+7.8ppb，Ni2+200ppb，Cu2+80ppb，Zn2+398ppb，Pb2+50ppb，Mg2+2.5×103ppb，Ca2+5.3×104ppb。1. The seawater was grafted with PVDF at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) at 30 ° C for 30 days. The concentration of each ion in the uranium mining wastewater (in terms of elements) is: UO 2 2+ 87ppb, VO 3 - 92ppb, Fe 3+ 500ppb, Co 2+ 7.8ppb, Ni 2+ 200ppb, Cu 2+ 80ppb, Zn 2 + 398 ppb, Pb 2+ 50 ppb, Mg 2+ 2.5×10 3 ppb, Ca 2+ 5.3×10 4 ppb.
2、将PVDF接枝聚丙烯酸颗粒材料取出，测试PVDF接枝聚丙烯酸颗粒材料上各离子吸附容量见表10：2. The PVDF grafted polyacrylic acid granule material was taken out, and the adsorption capacity of each ion on the PVDF grafted polyacrylic acid granule material was tested as shown in Table 10:
表10 PVDF接枝聚丙烯酸颗粒材料对各离子的吸附量表Table 10 Adsorption scale of each ion for PVDF grafted polyacrylic acid particulate material
Figure PCTCN2015089919-appb-000022
Figure PCTCN2015089919-appb-000022
实施例8PE共混聚丙烯酸毡状材料对海水中铀酰离子的吸附Example 8 Adsorption of uranyl ions in seawater by PE blended polyacrylic felt material
1、25℃海水以20ml/min(线速度0.86cm/s)的流速通过PE共混聚丙烯酸毡状材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater of 25 ° C was blended with PE at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) through PE, and adsorbed for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将PE共混聚丙烯酸毡状材料取出，测试PE共混聚丙烯酸毡状材料 上各离子吸附容量见表11：2. Remove the PE blended polyacrylic felt material and test the PE blend polyacrylic felt material. The adsorption capacity of each ion is shown in Table 11:
表11 PE共混聚丙烯酸毡状材料对各离子的吸附量表Table 11 Adsorption amount of each ion of PE blended polyacrylic felt material
Figure PCTCN2015089919-appb-000023
Figure PCTCN2015089919-appb-000023
实施例9交联聚甲基丙烯酸凝胶材料对海水中铀酰离子的吸附Example 9 Adsorption of Uranyl Ions in Seawater by Crosslinked Polymethacrylic Acid Gel Materials
1、20℃海水以20ml/min(线速度0.86cm/s)的流速通过交联聚甲基丙烯酸凝胶材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater at 20 ° C was passed through a cross-linked polymethacrylic acid gel material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将交联聚甲基丙烯酸凝胶材料取出，测试交联聚甲基丙烯酸凝胶材料上各离子吸附容量见下表12：2. Remove the cross-linked polymethacrylic acid gel material and test the adsorption capacity of each ion on the cross-linked polymethacrylic acid gel material as shown in Table 12 below:
表12 交联聚甲基丙烯酸凝胶材料对各离子的吸附量表Table 12 Adsorption scale of each ion for cross-linked polymethacrylic acid gel material
Figure PCTCN2015089919-appb-000024
Figure PCTCN2015089919-appb-000024
实施例10羧基化聚苯乙烯树脂材料对海水中铀酰离子的吸附Example 10 Adsorption of Uranyl Ions in Seawater by Carboxylated Polystyrene Resin Materials
1、15℃海水以20ml/min(线速度0.86cm/s)的流速通过羧基化聚苯乙烯树脂材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater at 15 ° C was passed through a carboxylated polystyrene resin material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将羧基化聚苯乙烯树脂材料取出，测试羧基化聚苯乙烯树脂材料上各离子吸附容量见表13：2. The carboxylated polystyrene resin material is taken out, and the adsorption capacity of each ion on the carboxylated polystyrene resin material is shown in Table 13:
表13 羧基化聚苯乙烯树脂材料对各离子的吸附量表Table 13 Adsorption amount of each ion for carboxylated polystyrene resin material
Figure PCTCN2015089919-appb-000025
Figure PCTCN2015089919-appb-000025
实施例11环戊基甲酸树脂材料对海水中铀酰离子的吸附Example 11 Adsorption of Uranyl Ions in Seawater by Cyclopentyl Carboxylate Resin Materials
1、10℃海水以20ml/min(线速度0.86cm/s)的流速通过环戊基甲酸树脂材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater at 10 ° C was passed through a cyclopentylcarboxylic acid resin material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将环戊基甲酸树脂材料取出，测试环戊基甲酸树脂材料上各离子吸附容量见表14：2. The cyclopentyl carboxylic acid resin material is taken out, and the adsorption capacity of each ion on the cyclopentyl carboxylic acid resin material is shown in Table 14:
表14 环戊基甲酸树脂材料对各离子的吸附量表Table 14 Adsorption amount of each ion of cyclopentyl carboxylic acid resin material
Figure PCTCN2015089919-appb-000026
Figure PCTCN2015089919-appb-000026
实施例12聚丙烯酸酯水解产物聚丙烯酸材料对海水中铀酰离子的吸附Example 12 Adsorption of Uranyl Ions in Seawater by Polyacrylic Acid Hydrolysate Polyacrylic Acid Materials
1、25℃海水以20ml/min(线速度0.86cm/s)的流速通过聚丙烯酸酯水解产物聚丙烯酸材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater of 25 ° C was passed through a polyacrylate hydrolyzate polyacrylic acid material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for adsorption for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将聚丙烯酸酯水解产物聚丙烯酸材料取出，测试聚丙烯酸酯水解产物聚丙烯酸材料上各离子吸附容量见表15：2. The polyacrylic acid hydrolyzate polyacrylic acid material is taken out, and the adsorption capacity of each ion on the polyacrylic acid hydrolyzate polyacrylic acid material is tested as shown in Table 15:
表15 聚丙烯酸酯水解产物聚丙烯酸材料对各离子的吸附量表Table 15 Adsorption Table of Polyacrylate Hydrolysate Polyacrylic Acid Material for Each Ion
Figure PCTCN2015089919-appb-000027
Figure PCTCN2015089919-appb-000027
实施例13苯甲酸修饰磁性氧化铁颗粒材料对海水中铀酰离子的吸附Example 13 Adsorption of Uranyl Ions in Seawater by Benzoic Acid Modified Magnetic Iron Oxide Particle Materials
1、25℃海水以20ml/min(线速度0.86cm/s)的流速通过苯甲酸修饰磁性氧化铁颗粒材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater was modified with benzoic acid at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) at 25 ° C for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将苯甲酸修饰磁性氧化铁颗粒材料取出，测试苯甲酸修饰磁性氧化铁颗粒材料上各离子吸附容量见表16： 2. The benzoic acid modified magnetic iron oxide particulate material was taken out, and the adsorption capacity of each ion on the benzoic acid modified magnetic iron oxide particulate material was tested as shown in Table 16:
表16 苯甲酸修饰磁性氧化铁颗粒材料对各离子的吸附量表Table 16 Adsorption scale of each ion for benzoic acid modified magnetic iron oxide particulate material
Figure PCTCN2015089919-appb-000028
Figure PCTCN2015089919-appb-000028
实施例14马来酸修饰活性炭材料对海水中铀酰离子的吸附Example 14 Adsorption of Uranyl Ions in Seawater by Maleic Acid Modified Activated Carbon Materials
1、30℃海水以20ml/min(线速度0.86cm/s)的流速通过马来酸修饰活性炭材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater was modified with maleic acid at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) at 30 ° C for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将马来酸修饰活性炭材料取出，测试马来酸修饰活性炭材料上各离子吸附容量见表17：2. The maleic acid modified activated carbon material was taken out and tested. The adsorption capacity of each ion on the maleic acid modified activated carbon material is shown in Table 17:
表17 马来酸修饰活性炭材料对各离子的吸附量表Table 17 Adsorption amount of each ion by maleic acid modified activated carbon material
Figure PCTCN2015089919-appb-000029
Figure PCTCN2015089919-appb-000029
实施例15聚甲基丙烯酸缩水甘油酯树脂材料对海水中铀酰离子的吸附Example 15 Adsorption of Uranyl Ions in Seawater by Polyglycidyl Methacrylate Resin Material
1、25℃海水以20ml/min(线速度0.86cm/s)的流速通过聚甲基丙烯酸缩水甘油酯材料，吸附30天。海水中各离子浓度同实施例2。1. The seawater at 25 ° C was passed through a polyglycidyl methacrylate material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将聚甲基丙烯酸缩水甘油酯材料取出，测试聚甲基丙烯酸缩水甘油酯材料上各离子吸附容量见表18：2. The polyglycidyl methacrylate material was taken out and tested for the adsorption capacity of each ion on the polyglycidyl methacrylate material. See Table 18:
表18 聚甲基丙烯酸缩水甘油酯材料对各离子的吸附量表Table 18 Adsorption scale of each ion of polyglycidyl methacrylate material
Figure PCTCN2015089919-appb-000030
Figure PCTCN2015089919-appb-000030
实施例16甲基丙烯酸共聚物材料对海水中铀酰离子的吸附 Example 16 Adsorption of Uranyl Ions in Seawater by Methacrylic Acid Copolymer Materials
1、海水以20ml/min(线速度0.86cm/s)的流速通过甲基丙烯酸共聚物材料，25℃吸附20天。海水中各离子浓度同实施例2。1. Seawater was passed through a methacrylic copolymer material at a flow rate of 20 ml/min (linear velocity of 0.86 cm/s) and adsorbed at 25 ° C for 20 days. The concentration of each ion in seawater was the same as in Example 2.
2、将甲基丙烯酸共聚物材料取出，测试甲基丙烯酸共聚物材料上各离子吸附容量见表19：2. The methacrylic acid copolymer material was taken out and the adsorption capacity of each ion on the methacrylic acid copolymer material was tested as shown in Table 19:
表19 甲基丙烯酸共聚物材料对各离子的吸附量表Table 19 Adsorption amount of each ion of methacrylic acid copolymer material
Figure PCTCN2015089919-appb-000031
Figure PCTCN2015089919-appb-000031
实施例17聚甲基丙烯酸材料对海水中铀酰离子的吸附Example 17 Adsorption of Uranyl Ions in Seawater by Polymethacrylic Materials
1、海水以20ml/min(线速度0.86cm/s)的流速通过聚甲基丙烯酸材料，25℃吸附20天。海水中各离子浓度同实施例2。1. Seawater was passed through a polymethacrylic material at a flow rate of 20 ml/min (linear velocity 0.86 cm/s) and adsorbed at 25 ° C for 20 days. The concentration of each ion in seawater was the same as in Example 2.
2、将聚甲基丙烯酸材料取出，测试聚甲基丙烯酸材料上各离子吸附容量见表20：2. The polymethacrylic acid material is taken out, and the adsorption capacity of each ion on the polymethacrylic acid material is shown in Table 20:
表20 聚甲基丙烯酸材料对各离子的吸附量表Table 20 Adsorption scale of each ion of polymethacrylic acid material
Figure PCTCN2015089919-appb-000032
Figure PCTCN2015089919-appb-000032
实施例18PE接枝聚丙烯酸薄膜材料对配制海水中铀酰离子的吸附Example 18 PE grafted polyacrylic acid film material for adsorption of uranyl ions in seawater
1、取配制海水5L，其中各离子浓度(以元素计)分别为：UO2 2+1.2ppb，VO3 -0.8ppb，Fe3+1ppb，Co2+0.05ppb，Ni2+0.5ppb，Cu2+0.07ppb，Zn2+1.7ppb，Pb2+0.06ppb，Mg2+1.2×105ppb，Ca2+0.6×105ppb。1. Prepare 5L of seawater, wherein each ion concentration (in terms of elements) is: UO 2 2+ 1.2ppb, VO 3 - 0.8ppb, Fe 3+ 1ppb, Co 2+ 0.05ppb, Ni 2+ 0.5ppb, Cu 2+ 0.07 ppb, Zn 2+ 1.7 ppb, Pb 2+ 0.06 ppb, Mg 2+ 1.2×10 5 ppb, Ca 2+ 0.6×10 5 ppb.
2、在其中投加0.1g PE接枝聚丙烯酸薄膜材料，室温(25℃)下震荡吸附24小时。2. 0.1 g of PE grafted polyacrylic acid film material was added thereto, and oscillated for 24 hours at room temperature (25 ° C).
3、将PE接枝聚丙烯酸薄膜材料取出，测试PE接枝聚丙烯酸薄膜材料 上各离子吸附容量见表21：3. The PE grafted polyacrylic acid film material is taken out to test the PE grafted polyacrylic acid film material. The adsorption capacity of each ion is shown in Table 21:
表21 PE接枝聚丙烯酸薄膜材料对各离子的吸附量表Table 21 Adsorption amount of each ion of PE grafted polyacrylic acid film material
Figure PCTCN2015089919-appb-000033
Figure PCTCN2015089919-appb-000033
实施例19PE接枝聚丙烯酸薄膜材料对浓缩海水中铀酰离子的吸附脱附循环Example 19 adsorption grafting desorption cycle of uranyl ion in concentrated seawater by PE grafted polyacrylic acid film material
1、取浓缩海水5L，其中各离子浓度(以元素计)分别为：UO2 2+330ppb，VO3 -152ppb，Fe3+141ppb，Co2+5.3ppb，Ni2+101ppb，Cu2+65ppb，Zn2+408ppb，Pb2+34.6ppb，Mg2+1.2×105ppb，Ca2+0.6×105ppb。1. Take 5L of concentrated seawater, wherein each ion concentration (in terms of elements) is: UO 2 2+ 330ppb, VO 3 - 152ppb, Fe 3+ 141ppb, Co 2+ 5.3ppb, Ni 2+ 101ppb, Cu 2+ 65ppb , Zn 2+ 408 ppb, Pb 2+ 34.6 ppb, Mg 2+ 1.2×10 5 ppb, Ca 2+ 0.6×10 5 ppb.
2、在其中投加0.1g PE接枝聚丙烯酸薄膜材料，25℃震荡吸附2小时。2. 0.1 g of PE grafted polyacrylic acid film material was added thereto, and adsorbed at 25 ° C for 2 hours.
3、将PE接枝聚丙烯酸薄膜材料取出，测试吸附后浓缩海水中铀酰离子浓度，计算PE接枝聚丙烯酸薄膜材料吸附容量。3. The PE grafted polyacrylic acid film material was taken out, and the concentration of uranyl ions in the concentrated seawater after adsorption was tested to calculate the adsorption capacity of the PE grafted polyacrylic acid film material.
4、将PE接枝聚丙烯酸薄膜材料用0.5M HCl浸泡3小时。4. The PE grafted polyacrylic film material was immersed in 0.5 M HCl for 3 hours.
5、将PE接枝聚丙烯酸薄膜材料取出，用去离子水清洗3次。5. The PE grafted polyacrylic acid film material was taken out and washed 3 times with deionized water.
6、重复步骤1-5，进行下一次吸附脱附。6. Repeat steps 1-5 for the next adsorption desorption.
7、按步骤1-6每循环10次，测量PE接枝聚丙烯酸薄膜材料的吸附容量，见表22：7. Measure the adsorption capacity of the PE grafted polyacrylic acid film material by 10 times per step 1-6, as shown in Table 22:
表22 PE接枝聚丙烯酸薄膜材料对U的吸附量表Table 22 Adsorption scale of U for PE grafted polyacrylic acid film material
Figure PCTCN2015089919-appb-000034
Figure PCTCN2015089919-appb-000034
实验结果表明，本发明的材料平均每10个循环对U的吸附量有约5％的损失，而偕胺肟基材料按本实施例的方法进行测试后，每个循环就有约5％的损失。 The experimental results show that the material of the present invention has an average loss of about 5% of U adsorption per 10 cycles, and the amidoxime based material is tested by the method of this embodiment, and each cycle has about 5%. loss.
实施例20PE接枝聚甲基丙烯酸薄膜材料对海水中铀酰离子的吸附Example 20 adsorption of uranyl ions in seawater by PE grafted polymethacrylic acid film material
1、海水以5mL/min(线速度0.216cm/s)的流速通过PE接枝聚甲基丙烯酸薄膜材料，25℃吸附50天。海水中各离子浓度同实施例2。1. Seawater was grafted through a PE grafted polymethacrylic acid film material at a flow rate of 5 mL/min (linear velocity 0.216 cm/s) and adsorbed at 25 ° C for 50 days. The concentration of each ion in seawater was the same as in Example 2.
2、将PE接枝聚甲基丙烯酸薄膜材料取出，洗去表面附着泥沙和微生物，测试PE接枝聚甲基丙烯酸薄膜材料上各离子吸附容量见表23：2. The PE grafted polymethacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms. The adsorption capacity of each ion on the PE grafted polymethacrylic acid film material was as shown in Table 23:
表23 PE接枝聚甲基丙烯酸薄膜材料对各离子的吸附量表Table 23 Adsorption amount of each ion for PE grafted polymethacrylic acid film material
Figure PCTCN2015089919-appb-000035
Figure PCTCN2015089919-appb-000035
实施例21PE接枝聚甲基丙烯酸薄膜材料对海水中铀酰离子的吸附Example 21 adsorption of uranyl ions in seawater by PE grafted polymethacrylic acid film material
1、海水流速320cm/s，通过PE接枝聚甲基丙烯酸薄膜材料，25℃吸附50天。海水中各离子浓度同实施例2。1. The seawater flow rate is 320 cm/s, and the polyglycolic acid film material is grafted by PE, and adsorbed at 25 ° C for 50 days. The concentration of each ion in seawater was the same as in Example 2.
2、将PE接枝聚甲基丙烯酸薄膜材料取出，洗去表面附着泥沙和微生物，测试PE接枝聚甲基丙烯酸薄膜材料上各离子吸附容量见表23：2. The PE grafted polymethacrylic acid film material was taken out, and the surface was attached with sediment and microorganisms. The adsorption capacity of each ion on the PE grafted polymethacrylic acid film material was as shown in Table 23:
表23 PE接枝聚甲基丙烯酸薄膜材料对各离子的吸附量表Table 23 Adsorption amount of each ion for PE grafted polymethacrylic acid film material
Figure PCTCN2015089919-appb-000036
Figure PCTCN2015089919-appb-000036
对比例1偕胺肟化聚乙烯纤维对海水中铀酰离子的吸附Comparative Example 1 Adsorption of Uranyl Ions in Seawater by Amidoxime Deuterated Polyethylene Fibers
1、25℃海水以20ml/min通过偕胺肟化聚乙烯纤维材料(按照文献Xing,Z.；Hu,J.；Wang,M.；Zhang,W.；Li,S.；Gao,Q.；Wu,G.Science China Chemistry 2013,56,1504制备的偕胺肟化聚乙烯纤维材料，本发明引用该文献的全文)，吸附30天。海水中各离子浓度同实施例2。1. 25 ° C seawater at 20 ml / min through amidoxime deuterated polyethylene fiber material (according to the literature Xing, Z.; Hu, J.; Wang, M.; Zhang, W.; Li, S.; Gao, Q. Wu, G. Science China Chemistry 2013, 56, 1504 prepared by the guanamine-deuterated polyethylene fiber material, the full text of which is cited in the present invention, adsorbed for 30 days. The concentration of each ion in seawater was the same as in Example 2.
2、将偕胺肟化聚乙烯纤维材料取出，测试偕胺肟化聚乙烯纤维材料上各离子吸附容量见表23： 2. The guanamine-deuterated polyethylene fiber material was taken out, and the adsorption capacity of each ion on the guanamine-deuterated polyethylene fiber material was as shown in Table 23:
表23 偕胺肟化聚乙烯纤维材料对各离子的吸附量表Table 23 Adsorption amount of each ion of guanamine-deuterated polyethylene fiber material
Figure PCTCN2015089919-appb-000037
Figure PCTCN2015089919-appb-000037
对比例2偕胺肟化聚乙烯纤维对海水中铀酰离子的吸附Comparative Example 2 Adsorption of Uranyl Ions in Seawater by Amidoxime Deuterated Polyethylene Fibers
1、25℃海水以20ml/min通过偕胺肟化聚乙烯纤维材料(按照文献Xing,Z.；Hu,J.；Wang,M.；Zhang,W.；Li,S.；Gao,Q.；Wu,G.Science China Chemistry 2013,56,1504制备的偕胺肟化聚乙烯纤维材料，本发明引用该文献的全文)，吸附42天海水中各离子浓度同实施例2。1. 25 ° C seawater at 20 ml / min through amidoxime deuterated polyethylene fiber material (according to the literature Xing, Z.; Hu, J.; Wang, M.; Zhang, W.; Li, S.; Gao, Q. Wu, G. Science China Chemistry 2013, 56, 1504 prepared guanamine-deuterated polyethylene fiber material, the full text of which is cited in the present invention, and the concentration of each ion in seawater adsorbed for 42 days is the same as in Example 2.
2、将偕胺肟化聚乙烯纤维材料取出，测试偕胺肟化聚乙烯纤维材料上各离子吸附容量见表24：2. The amidoxime deuterated polyethylene fiber material was taken out, and the adsorption capacity of each ion on the guanamine-deuterated polyethylene fiber material was as shown in Table 24:
表24 偕胺肟化聚乙烯纤维材料对各离子的吸附量表Table 24 Adsorption amount of each ion of guanamine-deuterated polyethylene fiber material
Figure PCTCN2015089919-appb-000038
Figure PCTCN2015089919-appb-000038
虽然以上描述了本发明的具体实施方式，但是本领域的技术人员应当理解，这些仅是举例说明，在不背离本发明的原理和实质的前提下，可以对这些实施方式做出多种变更或修改。因此，本发明的保护范围由所附权利要求书限定。 While the invention has been described with respect to the preferred embodiments of the embodiments of the embodiments of the invention modify. Accordingly, the scope of the invention is defined by the appended claims.

Claims (13)

  1. 一种从含铀酰离子的水溶液中富集铀的方法，其特征在于其包括下述步骤：用铀酰离子吸附材料对含铀酰离子的水溶液进行吸附即可；所述的铀酰离子吸附材料为含基团
    Figure PCTCN2015089919-appb-100001
    的材料。    A method for enriching uranium from an aqueous solution containing uranyl ions, characterized in that it comprises the steps of: adsorbing an aqueous solution containing uranyl ions with a uranyl ion adsorbing material; and adsorbing the uranyl ion Material is a group
    Figure PCTCN2015089919-appb-100001
    s material.
  2. 如权利要求1所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的含铀酰离子的水溶液中铀酰离子的浓度大于或等于1ppb。A method of enriching uranium from an aqueous solution containing uranyl ions according to claim 1, wherein the concentration of uranyl ions in said aqueous solution containing uranyl ions is greater than or equal to 1 ppb.
  3. 如权利要求2所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的含铀酰离子的水溶液中铀酰离子的浓度为1ppb～1000ppb；所述的铀酰离子的浓度为1ppb～1000ppb的含铀酰离子的水溶液具体表现形式优选为自然界中的海水、盐湖水、海水淡化工程浓缩废水或铀矿开采废水。The method for enriching uranium from an aqueous solution containing uranyl ions according to claim 2, wherein the concentration of uranyl ions in the aqueous solution containing uranyl ions is from 1 ppb to 1000 ppb; The specific expression form of the uranyl ion-containing aqueous solution having an ion concentration of 1 ppb to 1000 ppb is preferably seawater in the natural world, salt lake water, seawater desalination project concentrated wastewater or uranium mining wastewater.
  4. 如权利要求1～3中至少一项所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的“含基团
    Figure PCTCN2015089919-appb-100002
    的材料”为含基团
    Figure PCTCN2015089919-appb-100003
    的无机材料或有机高分子材料。    Method for enriching uranium from an aqueous solution containing uranyl ions according to at least one of claims 1 to 3, characterized in that said "containing group"
    Figure PCTCN2015089919-appb-100002
    Group of materials
    Figure PCTCN2015089919-appb-100003
    Inorganic materials or organic polymer materials.
  5. 如权利要求4所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的无机材料为活性炭或磁性氧化铁；The method for enriching uranium from an aqueous solution containing uranyl ions according to claim 4, wherein the inorganic material is activated carbon or magnetic iron oxide;
    和/或，and / or,
    所述的有机高分子材料为聚乙烯、聚丙烯、聚偏氟乙烯、尼龙、聚丙烯酸、聚甲基丙烯酸、丙烯酸共聚物、甲基丙烯酸共聚物或弱酸型阳离子交换树脂。The organic polymer material is polyethylene, polypropylene, polyvinylidene fluoride, nylon, polyacrylic acid, polymethacrylic acid, acrylic copolymer, methacrylic acid copolymer or weak acid type cation exchange resin.
  6. 如权利要求5所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的弱酸型阳离子交换树脂为含有脂肪族羧酸的树脂或含有芳香族羧酸的树脂；所述的含有脂肪族羧酸的树脂优选烷基或环烷基链接羧基的 脂肪族羧酸树脂；所述的含有芳香族羧酸的树脂优选苯环链接羧基的芳香族羧酸树脂；所述的苯环链接羧基的芳香族羧酸树脂优选羧基化聚苯乙烯树脂；所述的环烷基链接羧基的脂肪族羧酸树脂优选环戊基甲酸树脂；所述的烷基链接羧基的脂肪族羧酸树脂优选羧基化聚苯乙烯树脂。The method for enriching uranium from an aqueous solution containing uranyl ions according to claim 5, wherein the weak acid cation exchange resin is a resin containing an aliphatic carboxylic acid or a resin containing an aromatic carboxylic acid; The aliphatic carboxylic acid-containing resin is preferably an alkyl group or a cycloalkyl-linked carboxyl group. The aromatic carboxylic acid resin; the aromatic carboxylic acid-containing resin is preferably an aromatic carboxylic acid resin having a benzene ring-linked carboxyl group; and the aromatic carboxylic acid resin having a benzene ring-linked carboxyl group is preferably a carboxylated polystyrene resin; The cyclocarboxylic acid-bonded carboxyl group-containing aliphatic carboxylic acid resin is preferably a cyclopentylic acid resin; and the alkyl-carboxylated aliphatic carboxylic acid resin is preferably a carboxylated polystyrene resin.
  7. 如权利要求4～6中至少一项所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的含基团
    Figure PCTCN2015089919-appb-100004
    的有机高分子材料为聚乙烯接枝聚丙烯酸、聚乙烯接枝聚甲基丙烯酸、聚丙烯接枝聚马来酸、聚偏氟乙烯接枝聚丙烯酸、聚偏氟乙烯接枝聚甲基丙烯酸、聚乙烯共混聚丙烯酸、聚乙烯共混聚甲基丙烯酸、交联聚丙烯酸、交联聚甲基丙烯酸、羧基化聚苯乙烯树脂、环戊基甲酸树脂、聚甲基丙烯酸材料、丙烯酸共聚物或甲基丙烯酸共聚物；    Method for enriching uranium from an aqueous solution containing uranyl ions according to at least one of claims 4 to 6, characterized in that said group-containing group
    Figure PCTCN2015089919-appb-100004
    The organic polymer material is polyethylene grafted polyacrylic acid, polyethylene grafted polymethacrylic acid, polypropylene grafted polymaleic acid, polyvinylidene fluoride grafted polyacrylic acid, polyvinylidene fluoride grafted polymethacrylic acid. Polyethylene blended polyacrylic acid, polyethylene blended polymethacrylic acid, crosslinked polyacrylic acid, crosslinked polymethacrylic acid, carboxylated polystyrene resin, cyclopentylcarboxylic acid resin, polymethacrylic acid material, acrylic acid copolymerization Or methacrylic acid copolymer;
    和/或，and / or,
    所述的含基团
    Figure PCTCN2015089919-appb-100005
    的有机高分子材料为聚甲基丙烯酸缩水甘油酯树脂材料；    Group containing group
    Figure PCTCN2015089919-appb-100005
    The organic polymer material is a polyglycidyl methacrylate resin material;
    和/或，and / or,
    所述的含
    Figure PCTCN2015089919-appb-100006
    的无机材料为苯甲酸修饰的磁性氧化铁或马来酸修饰活性炭。    Said
    Figure PCTCN2015089919-appb-100006
    The inorganic material is benzoic acid modified magnetic iron oxide or maleic acid modified activated carbon.
  8. 如权利要求1～7中至少一项所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的铀酰离子吸附材料形态为颗粒状、纤维丝状、毡状、薄膜状或凝胶状；The method for enriching uranium from an aqueous solution containing uranyl ions according to at least one of claims 1 to 7, wherein the uranyl ion adsorbing material has a granular form, a fiber filament shape, and a felt shape. , film or gel;
    和/或，and / or,
    所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的方式为浸置式或流动通过式；In the adsorption, the uranyl ion adsorbing material is in contact with the aqueous solution containing uranyl ions in an immersion or flow-through manner;
    和/或， and / or,
    所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的时间以达到材料吸附饱和容量为准；In the adsorption, the uranyl ion adsorbing material is in contact with the uranyl ion-containing aqueous solution for a time to achieve a material adsorption saturation capacity;
    和/或，and / or,
    所述的吸附的温度为0～80℃；The adsorption temperature is 0 to 80 ° C;
    和/或，and / or,
    所述的铀酰离子吸附材料采用物理或化学的方法制备得到。The uranyl ion adsorbing material is prepared by physical or chemical methods.
  9. 如权利要求8所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的时间为1小时～90天；The method for enriching uranium from an aqueous solution containing uranyl ions according to claim 8, wherein said uranyl ion adsorbing material is in contact with said aqueous solution containing uranyl ions during said adsorption The time is from 1 hour to 90 days;
    和/或，and / or,
    所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的方式若采用流动通过式，则所述的含铀酰离子的水溶液的流速为5mL-2000mL/min和/或流经管线横截面的线速度为0.1-350cm/s；若采用浸置式，则还伴有震荡过程；In the adsorption, when the uranyl ion adsorbing material is in contact with the aqueous solution containing uranyl ions, the flow rate of the aqueous solution containing uranyl ions is 5 mL-2000 mL/ Min and / or the linear velocity of the cross section through the pipeline is 0.1-350cm / s; if the dip type is used, it is accompanied by the oscillation process;
    和/或，and / or,
    所述的吸附的温度为0～40℃；The adsorption temperature is 0 to 40 ° C;
    和/或，and / or,
    所述的物理方法为共混；The physical method is blending;
    和/或，and / or,
    所述的化学方法为共聚、接枝聚合或者交联。The chemical method is copolymerization, graft polymerization or crosslinking.
  10. 如权利要求9所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：A method of enriching uranium from an aqueous solution containing uranyl ions as claimed in claim 9 wherein:
    所述的吸附时，所述的铀酰离子吸附材料与所述的含铀酰离子的水溶液接触的方式若采用流动通过式，则所述的含铀酰离子的水溶液的流速为20mL/min和/或0.86cm/s；In the adsorption, when the uranyl ion adsorbing material is in contact with the aqueous solution containing the uranyl ion, the flow rate of the aqueous solution containing the uranyl ion is 20 mL/min. / or 0.86cm / s;
    和/或， and / or,
    所述的吸附的温度为10℃～30℃。The adsorption temperature is from 10 ° C to 30 ° C.
  11. 如权利要求10所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的吸附的温度为25℃。A method of enriching uranium from an aqueous solution containing uranyl ions according to claim 10, wherein said adsorption temperature is 25 °C.
  12. 如权利要求1～11中至少一项所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的吸附结束后还包括将所述的铀酰离子吸附材料取出的步骤。The method for enriching uranium from an aqueous solution containing uranyl ions according to at least one of claims 1 to 11, characterized in that after the end of the adsorption, the uranyl ion adsorbing material is further removed. step.
  13. 如权利要求1～12中至少一项所述的从含铀酰离子的水溶液中富集铀的方法，其特征在于：所述的吸附结束后，将所述的铀酰离子吸附材料取出后，对该铀酰离子吸附材料进行脱附。 The method for enriching uranium from an aqueous solution containing uranyl ions according to at least one of claims 1 to 12, wherein after said adsorption is completed, said uranyl ion adsorbing material is taken out, The uranyl ion adsorbing material is desorbed.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106810600A (en) * 2017-02-14 2017-06-09 东华理工大学 Uranyl ion combination dodecapeptide
CN112892497A (en) * 2021-01-19 2021-06-04 江苏大学 Preparation method and application of basin-covering type hollow porous polymer microspheres
CN114960182A (en) * 2022-06-20 2022-08-30 海南大学 Biological-adhesion-resistant composite porous hydrogel material, preparation method thereof and application of biological-adhesion-resistant composite porous hydrogel material in treatment of wastewater containing heavy metal ions
CN115090270A (en) * 2022-06-07 2022-09-23 烟台哈尔滨工程大学研究院 Porous polymer uranium adsorption material and preparation method thereof
CN115404348A (en) * 2022-09-27 2022-11-29 北京万邦达环保技术股份有限公司 Comprehensive utilization method of brine
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104916342B (en) * 2015-05-11 2017-11-17 中国科学院上海应用物理研究所 A kind of method of the enriched uranium from the aqueous solution containing uranyl ion
CN105312041B (en) * 2015-11-13 2017-10-03 哈尔滨工程大学 A kind of modified loofah sponge extraction of uranium from seawater adsorbent and preparation method thereof
CN107818832B (en) * 2016-09-14 2020-06-19 南京理工大学 Method for removing uranyl ions by treating with asparagine modified protein amino chelate resin
CN106518794B (en) * 2016-10-13 2018-10-16 北京大学 A kind of metal-organic framework materials of carboxyl-functional and the preparation method and application thereof
CN106554454A (en) * 2016-11-29 2017-04-05 福州大学 A kind of preparation method and application of polyacrylic acid hydrogel adsorbing material
CN108404888B (en) * 2018-05-02 2020-12-11 中国科学院上海应用物理研究所 Method for adsorbing uranyl ions
CN109012627B (en) * 2018-08-03 2021-09-03 中国科学院上海应用物理研究所 Method for improving adsorption efficiency of adsorption material on uranyl ions and metal ion loaded adsorption material
CN113773444B (en) * 2021-09-08 2022-04-26 北京大学 Material and method for recycling trace uranium from seawater
CN114042439B (en) * 2021-12-15 2023-06-30 中国人民解放军96901部队23分队 Uranium-containing wastewater adsorbent and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933948A (en) * 2014-04-21 2014-07-23 南华大学 Grated loading method of nano Fe3O4 and beer saccharomycete and application thereof
CN104353416A (en) * 2014-11-07 2015-02-18 南京理工大学 Magnetic ordered mesopore composite material, as well as preparation and application thereof
CN104916342A (en) * 2015-05-11 2015-09-16 中国科学院上海应用物理研究所 Method for concentrating uranium from water solution with uranyl ions

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5331792A (en) * 1976-09-06 1978-03-25 Kanebo Ltd Preparation of heavy metal ion adsorbent
CN1013088B (en) * 1988-05-24 1991-07-10 煤炭科学研究总院南京研究所 Method for processing arch thin-wall case without mould
FR2797786B1 (en) * 1999-08-27 2001-10-05 Commissariat Energie Atomique PROCESS AND INSTALLATION FOR REMOVAL OF METAL CATIONS FROM A LIQUID BY POLYAZACYCLOALKANE RESINS GRAFTED ON A SUPPORT
CN101231899B (en) * 2008-02-25 2012-07-04 中国疾病预防控制中心辐射防护与核安全医学所 Magnetic particle extractive agent and method for isolating radionuclide
CN101357325B (en) * 2008-09-18 2012-05-23 福州大学 Globular cellulose chelate sorbent containing amidoxime group and carboxy and preparation method thereof
CN102505474B (en) * 2011-11-29 2013-12-18 中国科学院上海应用物理研究所 Modified ultrahigh molecular weight polyethylene fiber and preparation method thereof
CN102614842B (en) * 2012-03-21 2013-12-18 中国科学院上海应用物理研究所 Chelate fiber adsorbent for extracting uranium from seawater and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933948A (en) * 2014-04-21 2014-07-23 南华大学 Grated loading method of nano Fe3O4 and beer saccharomycete and application thereof
CN104353416A (en) * 2014-11-07 2015-02-18 南京理工大学 Magnetic ordered mesopore composite material, as well as preparation and application thereof
CN104916342A (en) * 2015-05-11 2015-09-16 中国科学院上海应用物理研究所 Method for concentrating uranium from water solution with uranyl ions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DONIA, A.M. ET AL.: "Removal of Uranium (VI) from Aqueous Solutions Using Glycidyl Methacrylate Chelating Resins", HYDROMETALLURGY, vol. 95, no. 3-4, 18 July 2008 (2008-07-18), pages 183 - 189, XP025746016 *
LI, XINGLIANG ET AL.: "Adsorption of Uranium by Carbon Materials from Aqueous Solutions", PROGRESS IN CHEMISTRY, vol. 23, no. 7, 31 July 2011 (2011-07-31) *
ZHOU, SHUKUI ET AL.: "Equilibrium, Kinetic and Thermodynamic Study of the Adsorption of Uranium (VI) onto Modified CMC", CHINA ENVIRONMENTAL SCIENCE, vol. 31, no. 9, 31 December 2011 (2011-12-31), pages 1467 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106810600A (en) * 2017-02-14 2017-06-09 东华理工大学 Uranyl ion combination dodecapeptide
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CN115090270A (en) * 2022-06-07 2022-09-23 烟台哈尔滨工程大学研究院 Porous polymer uranium adsorption material and preparation method thereof
CN115090270B (en) * 2022-06-07 2024-03-29 烟台哈尔滨工程大学研究院 Porous polymer uranium adsorption material and preparation method thereof
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CN115404348A (en) * 2022-09-27 2022-11-29 北京万邦达环保技术股份有限公司 Comprehensive utilization method of brine
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CN115463643B (en) * 2022-10-22 2023-05-12 海南大学 Rapid uranium absorption anti-pollution adsorbent and preparation method thereof

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