CN102930914A - Processing method of radioactive waste liquid containing uranium - Google Patents
Processing method of radioactive waste liquid containing uranium Download PDFInfo
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- CN102930914A CN102930914A CN2012104355776A CN201210435577A CN102930914A CN 102930914 A CN102930914 A CN 102930914A CN 2012104355776 A CN2012104355776 A CN 2012104355776A CN 201210435577 A CN201210435577 A CN 201210435577A CN 102930914 A CN102930914 A CN 102930914A
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- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 23
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002901 radioactive waste Substances 0.000 title abstract description 8
- 238000003672 processing method Methods 0.000 title abstract 4
- 230000002285 radioactive effect Effects 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 20
- 235000018553 tannin Nutrition 0.000 claims abstract description 15
- 229920001864 tannin Polymers 0.000 claims abstract description 15
- 239000001648 tannin Substances 0.000 claims abstract description 15
- 235000011511 Diospyros Nutrition 0.000 claims abstract description 9
- 244000236655 Diospyros kaki Species 0.000 claims abstract description 9
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 6
- 239000000941 radioactive substance Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims 1
- 239000010808 liquid waste Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 24
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 13
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 13
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- -1 iron ion Chemical class 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 abstract 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 5
- 239000012085 test solution Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
技术领域 technical field
本发明涉及低放射性废液处理，具体是一种含有铀（U）元素放射性废液的处理方法。 The invention relates to the treatment of low-radioactive waste liquid, in particular to a treatment method for radioactive waste liquid containing uranium (U) element.
背景技术 Background technique
含有放射性元素的废液很容易污染环境，如不及时处理，将会对环境和人类造成危害。铀（U）是天然放射性元素，低浓度含U废水包括U的矿山水、核工业铀矿冶的科研、生产排放的废水、核电站排放的废水等[1-2]。含有U等放射性元素废液的现有处理方法主要采取放射性元素与氢氧化铁共沉淀法[2]。其主要步骤有：在含有放射性元素废液中，添加氯化铁溶液，搅拌均匀后，加入氢氧化钠等碱性溶液中和，产生氢氧化铁溶胶。氢氧化铁是粒状物，放射性元素被氢氧化铁溶胶颗粒吸附，并与氢氧化铁形成共沉淀，然后对废液过滤，将放射性物质与氢氧化铁一同滤掉。由于氢氧化铁胶状颗粒细小，通常粒径小于10μm，利用过滤氢氧化铁溶胶的方法将放射性元素完全去除非常困难。为了使废液中的放射性元素含量低于安全值，需要按上述方法反复操作，这不仅会增加人力和运行成本，还将会增加放射性废弃物的存放面积和保管成本。 The waste liquid containing radioactive elements is easy to pollute the environment. If it is not disposed of in time, it will cause harm to the environment and human beings. Uranium (U) is a natural radioactive element. Low-concentration U-containing wastewater includes mine water, nuclear industry uranium mining and metallurgy research, production wastewater, and nuclear power plant wastewater [1-2] . The existing treatment method of waste liquid containing radioactive elements such as U mainly adopts co-precipitation method of radioactive elements and ferric hydroxide [2] . The main steps include: adding ferric chloride solution to waste liquid containing radioactive elements, stirring evenly, adding alkaline solution such as sodium hydroxide for neutralization, and producing ferric hydroxide sol. Ferric hydroxide is granular, and radioactive elements are adsorbed by ferric hydroxide sol particles, and form co-precipitation with ferric hydroxide, and then filter the waste liquid to filter out radioactive substances and ferric hydroxide. Due to the fine colloidal particles of ferric hydroxide, usually less than 10 μm in size, it is very difficult to completely remove radioactive elements by filtering ferric hydroxide sol. In order to make the content of radioactive elements in the waste liquid lower than the safe value, it is necessary to repeat the above method, which will not only increase manpower and operating costs, but also increase the storage area and storage cost of radioactive waste.
发明内容 Contents of the invention
本发明的目的是要提供一种从含铀放射性元素废液中去除放射性元素铀的方法，该方法不仅能对放射性元素铀含量高的废水进行处理，而且也适用于放射性元素铀含量极低的废水处理。 The purpose of the present invention is to provide a method for removing radioactive element uranium from uranium-containing radioactive element waste liquid. waste water treatment.
实现本发明目的的技术方案是： The technical scheme that realizes the object of the present invention is:
将铁离子或亚铁离子溶液加入含铀放射性元素的废液中，通过调节废水溶液的pH值，形成氢氧化铁胶体，再加入涩柿单宁，使氢氧化铁胶体沉淀，放射性元素因与氢氧化铁胶体共沉淀或被氢氧化铁胶体吸附而被分离。 Add ferric ion or ferrous ion solution to the waste liquid containing uranium radioactive elements, adjust the pH value of the waste water solution to form ferric hydroxide colloid, then add astringent persimmon tannin to precipitate ferric hydroxide colloid, radioactive elements are mixed with Ferric hydroxide colloid co-precipitates or is separated by adsorption of ferric hydroxide colloid.
一种含铀放射性废液的处理方法，包括如下步骤： A treatment method for uranium-containing radioactive waste liquid, comprising the steps of:
（1）在含有放射性元素铀的废液中，加入铁离子或亚铁离子溶液； (1) Add iron ion or ferrous ion solution to the waste liquid containing radioactive element uranium;
（2）加入氢氧化钠溶液或者氢氧化钾溶液或者氨水调节pH值至5.0～7.0，使铁离子完全形成胶体后； (2) Add sodium hydroxide solution or potassium hydroxide solution or ammonia water to adjust the pH value to 5.0-7.0, so that the iron ions can completely form a colloid;
（3）加入涩柿单宁，搅拌、静置、过滤，将废液中的放射性物质铀去除。 (3) Add astringent persimmon tannin, stir, stand still, and filter to remove the radioactive substance uranium in the waste liquid.
本方法还可以用于对含Pu等等放射性元素废液的净化。 The method can also be used to purify waste liquid containing radioactive elements such as Pu.
所述铁离子溶液可以是氯化铁或硫酸铁溶液；所述亚铁离子溶液可以是氯化亚铁或硫酸亚铁溶液；所述涩柿单宁包括可溶性单宁和不溶性单宁。 The iron ion solution may be ferric chloride or ferric sulfate solution; the ferrous ion solution may be ferrous chloride or ferrous sulfate solution; the persimmon tannin includes soluble tannin and insoluble tannin.
本发明的优点是：该方法可用于含有U元素、Pu元素等放射性元素废液的净化，放射性元素的去除率可达100%，U元素、Pu元素等放射性元素的浓度可以低到10ppm。步骤简单，成本较低，减轻环境污染。 The advantages of the present invention are: the method can be used to purify waste liquid containing radioactive elements such as U element and Pu element, the removal rate of radioactive elements can reach 100%, and the concentration of radioactive elements such as U element and Pu element can be as low as 10ppm. The steps are simple, the cost is low, and the environmental pollution is reduced.
具体实施方式 Detailed ways
将U3O8溶于稀硝酸中，配制成含U元素为10ppm的溶液作为标准溶液。测得该标准溶液的放射线量为6.962×102 mmBq/cc。将日常检验的放射性废液的pH值调整为7.0，过滤后，作为试验液，测得其放射线量为5.262×102 mmBq/cc。 Dissolve U 3 O 8 in dilute nitric acid, and prepare a solution containing 10 ppm of U element as a standard solution. The radiation dose of the standard solution was measured to be 6.962×10 2 mmBq/cc. Adjust the pH value of the radioactive waste liquid for daily inspection to 7.0, filter it, and use it as the test liquid. The measured radiation dose is 5.262×10 2 mmBq/cc.
取上述标准液100ml，加入4g氯化铁，搅拌均匀，作为A号液。取上述试验液100ml加入4g氯化铁，搅拌均匀，作为C号液。分别向A号液和C号液中加入氢氧化钠溶液，调节pH=5.0，再分别加入0.5克柿单宁，搅拌1小时，过滤。测定滤液中的U元素含量，A号液滤液的U含量为1.6%，C号液的U元素含量为2.1%。由此可见，废液中的U元素没有完全去除。 Take 100ml of the above standard solution, add 4g of ferric chloride, stir evenly, and use it as No. A solution. Take 100ml of the above test solution and add 4g of ferric chloride, stir evenly, and use it as No. C solution. Add sodium hydroxide solution to liquid A and liquid C respectively, adjust pH=5.0, then add 0.5 g of persimmon tannin, stir for 1 hour, and filter. The U element content in the filtrate was measured, the U content of the A No. liquid filtrate was 1.6%, and the U element content of the C No. liquid was 2.1%. It can be seen that the U element in the waste liquid has not been completely removed.
取上述标准液100ml，加入4g氯化铁，搅拌均匀，作为A号液。取上述试验液100ml加入4g氯化铁，搅拌均匀，作为C号液。分别向A号液和C号液中加入氢氧化钠溶液，调节pH=7.0，再分别加入0.5克按专利公开号为CN10132819制成的涩柿单宁，搅拌1小时，过滤。测定滤液中的U元素含量，A号液滤液的U含量为0%，C号液的U元素含量为0%。由此可见，废液中的U元素可以完全去除。 Take 100ml of the above standard solution, add 4g of ferric chloride, stir evenly, and use it as No. A solution. Take 100ml of the above test solution and add 4g of ferric chloride, stir evenly, and use it as No. C solution. Add sodium hydroxide solution to liquid A and liquid C respectively, adjust pH=7.0, then add 0.5 g of astringent persimmon tannin made according to patent publication No. CN10132819, stir for 1 hour, and filter. The U element content in the filtrate was measured, the U content of the A No. liquid filtrate was 0%, and the U element content of the C No. liquid was 0%. It can be seen that the U element in the waste liquid can be completely removed.
作为对比，在上述标准溶液中入4克氯化铁，为B号液；在上述试验液中加放4克氯化铁，为D号液。分别向B和D号液中加入氢氧化钠溶液，调节pH=5.0，然后分别过滤。测定滤液中的U元素含量，B号液滤液的U含量为1.1%，D号液的U元素含量为1.9%。在B号液和D号液中加入氢氧化钠溶液，调节pH=7.0, 然后分别过滤。测定滤液中的U元素含量，B号液滤液的U含量为1.0%，D号液的U元素含量为1.7%。由此可见，废液中的U元素没有完全去除。 As a comparison, add 4 grams of ferric chloride to the above-mentioned standard solution to form No. B solution; add 4 grams of ferric chloride to the above-mentioned test solution to form No. D solution. Add sodium hydroxide solution to No. B and D respectively, adjust pH=5.0, and then filter separately. The U element content in the filtrate was measured, the U content of the B No. liquid filtrate was 1.1%, and the U element content of the D No. liquid was 1.9%. Add sodium hydroxide solution to No. B solution and No. D solution, adjust pH=7.0, and then filter separately. The U element content in the filtrate was measured, the U content of the B No. liquid filtrate was 1.0%, and the U element content of the D No. liquid was 1.7%. It can be seen that the U element in the waste liquid has not been completely removed.
上述试验表明，没有添加涩柿单宁的试验液，对U元素也有很好的去除率，但不能实现完全去除。采用本发明提供的方法，可以达到U元素完全去除，使含有放射性元素铀的废液完全净化。 The above tests showed that the test solution without adding astringent persimmon tannin also had a good removal rate for U element, but it could not achieve complete removal. By adopting the method provided by the invention, the U element can be completely removed, and the waste liquid containing the radioactive element uranium can be completely purified.
Claims (4)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104215999A (en) * | 2013-05-30 | 2014-12-17 | 核工业北京地质研究院 | Seawater radionuclide analysis pretreatment method |
| CN108046400A (en) * | 2017-12-18 | 2018-05-18 | 江西晶安新资源有限公司 | A kind of neutralization method of acidity uranium-containing waste water |
| CN109147973A (en) * | 2018-08-01 | 2019-01-04 | 深圳聚纵科技有限公司 | The method of radioactive substance is recycled after a kind of nuclear power plant's nuclear fuel rod use |
| CN111204880A (en) * | 2020-01-21 | 2020-05-29 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under anaerobic condition |
| CN111270086A (en) * | 2018-12-04 | 2020-06-12 | 格林美（江苏）钴业股份有限公司 | Purification method of cobalt chloride solution |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104215999A (en) * | 2013-05-30 | 2014-12-17 | 核工业北京地质研究院 | Seawater radionuclide analysis pretreatment method |
| CN108046400A (en) * | 2017-12-18 | 2018-05-18 | 江西晶安新资源有限公司 | A kind of neutralization method of acidity uranium-containing waste water |
| CN109147973A (en) * | 2018-08-01 | 2019-01-04 | 深圳聚纵科技有限公司 | The method of radioactive substance is recycled after a kind of nuclear power plant's nuclear fuel rod use |
| CN111270086A (en) * | 2018-12-04 | 2020-06-12 | 格林美（江苏）钴业股份有限公司 | Purification method of cobalt chloride solution |
| CN111204880A (en) * | 2020-01-21 | 2020-05-29 | 西南科技大学 | Method for removing uranium in ryegrass-enriched degradation residual liquid by microorganisms under anaerobic condition |
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Application publication date: 20130213 |