CN113461133A - Uranium-containing wastewater treatment agent and method for treating uranium-containing wastewater - Google Patents
Uranium-containing wastewater treatment agent and method for treating uranium-containing wastewater Download PDFInfo
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 118
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004065 wastewater treatment Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 18
- 239000010445 mica Substances 0.000 claims description 18
- 229910052618 mica group Inorganic materials 0.000 claims description 18
- 239000011707 mineral Substances 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 159000000003 magnesium salts Chemical class 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 229960002261 magnesium phosphate Drugs 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 35
- 235000010755 mineral Nutrition 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 238000003795 desorption Methods 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- -1 uranyl ions Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000013049 sediment Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000005289 uranyl group Chemical group 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000012442 analytical experiment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- GREUUUYDPWBLBH-UHFFFAOYSA-N magnesium uranium Chemical compound [Mg][U] GREUUUYDPWBLBH-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VBWSWBQVYDBVGA-NAHFVJFTSA-N uranium-234;uranium-235;uranium-238 Chemical compound [234U].[235U].[238U] VBWSWBQVYDBVGA-NAHFVJFTSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a uranium-containing wastewater treating agent and a method for treating uranium-containing wastewater. The treating agent is used for treating uranium-containing wastewater, and the uranium removal rate is high and can reach 98.4 percent at most; the method has the advantages of simple process flow, wide applicable pH range, easily controlled reaction conditions, strong operability and practical application prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a uranium-containing wastewater treatment agent and a method for treating uranium-containing wastewater.
Background
Uranium is a natural radioactive heavy metal element, and due to the radioactivity of uranium, radioactive radiation damage can be caused to human bodies, animals and plants, and if the uranium is discharged into the environment, extremely serious harm can be caused to the environment, organisms and human health.
The uranium-containing wastewater mainly comes from mining and hydrometallurgy wastewater of uranium ores, uranium refining and nuclear fuel manufacturing wastewater, reactor operation wastewater, post-treatment wastewater of reactor fuel, wastewater generated by radioisotope production and the like. In addition, plants, nuclear power plants, laboratories, nuclear warfare, abnormal nuclear accidents, etc. all produce uranium-containing wastewater.
The uranium-bearing wastewater mainly has the following characteristics: (1) uranium is a natural radioactive element with long decay time, so the uranium-containing wastewater belongs to radioactive wastewater. (2) The uranium-bearing wastewater has complex components and various varieties and contains a large amount of heavy gold such as uranium, radium and the likeAnd belongs to radioactive elements and other toxic and harmful chemical substances. (3) The uranium in the wastewater mainly coexists with other metal compounds or oxides in two valence states of U (IV) and U (VI), wherein the U (IV) is easy to remove and precipitates because the U (IV) can form a stable complex with inorganic carbon; and U (VI) is usually uranyl ion (UO)2 2+) In the form of (A), UO2 2+The uranium-bearing wastewater has good solubility and is not easy to remove, and the removal of the uranium-bearing wastewater is mostly referred to the removal of U (VI) and compounds thereof. The common uranium-bearing wastewater treatment method comprises biological extraction, an adsorption method, complex precipitation, membrane separation, chemical reduction and the like. The adsorption method utilizes an adsorbent material to adsorb and fix U (VI) in a solution into a solid phase, so that the migration of U (VI) is reduced, but the problems of disposal and secondary pollution of the adsorbed material are faced; the stable U (IV) is reduced by a chemical reduction method and is easily oxidized to form U (VI) which is easily dissolved and migrated after being exposed to air; compared with the traditional separation technology (such as adsorption, extraction, distillation and the like), the membrane separation technology has the advantages of high efficiency, convenient operation, space saving, low energy consumption, strong material adaptability, simple device and operation and the like, but has the problems of high cost, limited membrane pollution and treatment capacity and the like.
Disclosure of Invention
The invention aims to provide a uranium-containing wastewater treatment agent and a method for treating uranium-containing wastewater, aiming at overcoming the problems of difficulty in treatment and complex treatment process of uranium-containing wastewater in the prior art. The invention relates to a method for treating uranium-containing wastewater by simulating a mineralization reaction process of natural uranium and phosphate, and providing a method for treating uranium-containing wastewater by using minerals of uranium, magnesium and magnesium, forming precipitates with uranyl ions and absorbing and inducing uranyl to form magnesium-uranium-mica through uranium mica precipitates based on a new ecological restoration concept that uranium pollution returns to natural minerals. Soluble magnesium salt and phosphate ions are provided for magnesium ions and phosphate ions, and uranyl ions are reformed into magnesium-uranium-mica mineral sediment, formed solid sediment adsorbs the uranyl ions through the surface adsorption effect, fixed removal of the uranyl ions in the wastewater is achieved, the problem of wastewater uranyl pollution is solved, and the pollutants return to natural minerals to be stably controlled for a long time.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a uranium-bearing wastewater treating agent is one or two of magnesium salt and phosphate.
Preferably, the magnesium salt comprises at least one of magnesium nitrate and magnesium chloride; more preferably, the magnesium salt is magnesium nitrate.
Preferably, the phosphate comprises at least one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate and calcium dihydrogen phosphate; more preferably, the phosphate is sodium dihydrogen phosphate.
In some preferred embodiments of the invention, the treating agent is a mixture of magnesium nitrate and sodium dihydrogen phosphate.
The invention also aims to provide a method for treating uranium-containing wastewater by using the uranium-containing wastewater treatment agent, which specifically comprises the following steps:
1) mixing the treating agent with uranium-containing wastewater for reaction;
2) separating the mixture after the reaction in the step 1) to obtain solid slag and residual liquid, and removing the solid slag to remove uranium.
Preferably, the pH value of the reaction in the step 1) is 2-11; further preferably, the pH is 3 to 7.
Preferably, in the method for treating uranium-containing wastewater, the regulator for regulating the reaction pH in the step 1) is at least one of hydrochloric acid, sulfuric acid, nitric acid, lime, limestone, dolomite, sodium hydroxide and sodium carbonate; further preferably, the pH adjuster is at least one of nitric acid and sodium hydroxide.
Preferably, the reaction time of the reaction in the step 1) is 1-3 h; more preferably, the reaction time is 1.5 to 2.5 hours.
Preferably, in the method for treating the uranium-containing wastewater, the molar ratio of Mg in magnesium salt and P in phosphate to U in the uranium-containing wastewater in the step 1) is (0-3): (0-5): 1, the molar numbers of Mg in the magnesium salt and P in the phosphate are not 0 at the same time; further preferably, the molar ratio of Mg in magnesium salt, P in phosphate and U in uranium-containing wastewater is 0.5: (1-4): 1; still further preferably, the molar ratio of Mg in magnesium salt, P in phosphate and U in uranium-containing wastewater is 0.5:1: 1.
preferably, the uranium concentration of the uranium-containing wastewater in the step 1) is 20-1000 mg/L; further preferably, the uranium concentration of the uranium-containing wastewater is 40-800 mg/L.
Preferably, in the method for treating the uranium-containing wastewater, the reaction process in the step 1) needs to be oscillated; the oscillation is performed in an oscillator.
Preferably, in the method for treating the uranium-containing wastewater, the mode for removing the solid slag in the step 2) is filtration.
Preferably, the method for treating the uranium-containing wastewater comprises the following steps of 2), wherein solid slag in the step 2) is magnesium-uranium-mica mineral sediment; more preferably, the desorption rate of the magnesium-uranium-mica mineral sediment is more than or equal to 12 percent.
The method for determining the desorption rate of magnesium-uranium-mica mineral sediment comprises the following steps: adding the solid slag obtained in the step 2), namely the magnesium-uranium-mica mineral precipitate, into a 0.1mol/L sodium bicarbonate solution, adding 1.0g of magnesium-uranium-mica mineral precipitate into 1L of the sodium bicarbonate solution, reacting for 2 hours, and calculating the desorption rate of the magnesium-uranium-mica mineral precipitate according to the original uranium content of the magnesium-uranium-mica mineral and the uranium content in the solution after the reaction.
The invention has the beneficial effects that:
the method utilizes magnesium salt and/or phosphate precipitation-adsorption to induce uranium mineralization to treat uranium-containing wastewater, and has high uranyl ion removal rate which can reach 98.4 percent at most.
The treatment agent is applied to uranium-containing wastewater treatment, the formed magnesium-uranium-mica mineral precipitate has long-term stability and low desorption rate, and the desorption rate of the magnesium-uranium-mica mineral precipitate can be 12% at least.
The method for treating the uranium-bearing wastewater has the advantages of simple process flow, wide applicable pH range, easily controlled reaction conditions, strong operability and practical application prospect.
Drawings
FIG. 1 shows that the molar ratio of magnesium, phosphorus and uranium elements (Mg/P/U) is (0-2): 1: graph of uranium removal at different pH at 1;
FIG. 2 shows that the molar ratio of magnesium, phosphorus and uranium elements (Mg/P/U) is 0.5: (0-4): graph of uranium removal at different pH at 1;
fig. 3 is an XRD pattern of a solid precipitate formed under the conditions of pH 3, pH 5 and pH 7 in example 7;
fig. 4 is an XRD pattern of a solid precipitate formed under the conditions of pH 9 and pH 11 in example 7;
fig. 5 is a graph of the desorption rate of uranium under different pH conditions for example 8.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either commercially available or available by methods known in the art, and unless otherwise specified, testing or testing procedures are routine in the art.
The magnesium salt used in the following examples is magnesium nitrate, the phosphate is sodium dihydrogen phosphate, the uranium-containing wastewater is simulated uranium-containing wastewater, and the preparation method of the simulated uranium-containing wastewater is as follows: 2.11g of UO are weighed out2(NO3)2·6H2And adding the O solid into a beaker for dissolving, transferring the O solid into a volumetric flask for constant volume to 1000ml, preparing 1g/L uranium stock solution, and preparing 40-800mg/L uranium solution with the concentration required by the experiment respectively.
Example 1
Setting the molar ratio (Mg/P/U) of different magnesium, phosphorus and uranium elements as 0:1:1, 0.5:1:1, 1:1:1, 1.5:1:1 and 2:1:1, controlling the initial uranium concentration of the uranyl ion solution to be 40Mg/L and the pH value of the solution to be 3, placing the solution in a vibrator for reaction for 2 hours, and forming a small amount of solid precipitate and clarifying the solution. And filtering by using a microporous filter membrane to obtain filtrate, analyzing the concentration of the residual uranium in the filtrate, and obtaining the highest uranium removal rate of 77.9%, wherein the uranium removal rate is shown in figure 1.
Example 2
Setting the molar ratio (Mg/P/U) of different magnesium, phosphorus and uranium elements as 0:1:1, 0.5:1:1, 1:1:1, 1.5:1:1 and 2:1:1, controlling the initial uranium concentration of the uranyl ion solution to be 40Mg/L and the pH value of the solution to be 5, placing the solution in a shaker for reaction for 2 hours to form a solid precipitate, and turning the solution turbid. And filtering by using a microporous filter membrane to obtain filtrate, analyzing the concentration of the residual uranium in the filtrate, and obtaining the highest uranium removal rate of 94.3%, wherein the uranium removal rate is shown in figure 1.
Example 3
Setting the molar ratio (Mg/P/U) of different magnesium, phosphorus and uranium elements as 0:1:1, 0.5:1:1, 1:1:1, 1.5:1:1 and 2:1:1, controlling the initial uranium concentration of the uranyl ion solution to be 40Mg/L, controlling the pH value of the solution to be 7, 9 and 11, placing the solution in a vibrator for reaction for 2 hours, forming no obvious solid precipitate, and clarifying the solution. Filtering with microporous membrane to obtain filtrate, analyzing the concentration of residual uranium in the filtrate, and determining the uranium removal rate below 55%, which is shown in figure 1.
Example 4
Setting the molar ratio (Mg/P/U) of different magnesium, phosphorus and uranium elements to be 0.5:0:1, 0.5:1:1, 0.5:2:1, 0.5:3:1 and 0.5:4:1, controlling the initial concentration of uranium in the uranyl ion solution to be 40Mg/L and the pH value of the solution to be 3, placing the solution in a vibrator for reaction for 2 hours, forming a small amount of solid precipitate, and clarifying the solution. And filtering by using a microporous filter membrane to obtain filtrate, analyzing the concentration of residual uranium in the filtrate, and obtaining the highest uranium removal rate of 90.4% and the uranium removal rate shown in figure 2.
Example 5
Setting the molar ratio (Mg/P/U) of different magnesium, phosphorus and uranium elements as 0.5:0:1, 0.5:1:1, 0.5:2:1, 0.5:3:1 and 0.5:4:1, controlling the initial uranium concentration of the uranyl ion solution to be 40Mg/L and the pH value of the solution to be 5, placing the solution in a shaker for reaction for 2 hours to form a solid precipitate, and turning the solution turbid. Filtrate is obtained through the filtration of a microporous filter membrane, the concentration of residual uranium in the filtrate is analyzed, the highest uranium removal rate is 98.4%, and the uranium removal rate is shown in figure 2.
Example 6
Setting the molar ratio (Mg/P/U) of different magnesium, phosphorus and uranium elements as 0.5:0:1, 0.5:1:1, 0.5:2:1, 0.5:3:1 and 0.5:4:1, controlling the initial uranium concentration of the uranyl ion solution to be 40Mg/L, controlling the pH value of the solution to be 7, 9 and 11, placing the solution in a vibrator for reaction for 2 hours, forming no obvious solid precipitate, and clarifying the solution. Filtering with microporous membrane to obtain filtrate, analyzing the concentration of residual uranium in the filtrate, and determining the uranium removal rate below 60%, which is shown in FIG. 2.
Example 7
In order to collect the components for analysis of the precipitate, magnesium, phosphorus and uranium elements are mixed according to a molar ratio (Mg/P/U) of 0.5:1:1, the initial concentration of uranium in the uranyl ion solution is 800Mg/L, the pH value of the solution is controlled to be 3, 5, 7, 9 and 11, the solution is placed in a shaker for reaction for 2 hours, then a filter residue and a filtrate are obtained by filtration through a microporous filter membrane, the components of the filter residue are analyzed, and XRD patterns of the filter residue obtained under the conditions of pH 3, pH 5 and pH 7 are shown in figure 3, and magnesium-uranium-mica minerals are obtained under the conditions of pH 3, pH 5 and pH 7. The XRD pattern of the solid precipitate formed under the conditions of pH 9 and pH 11 is shown in fig. 4, and the diffraction peak is broad, and the uranium mica substance is not pure and is mostly amorphous.
Example 8
Precipitates formed in different pH systems of example 7 were collected and subjected to analytical experiments. Taking 0.05g of precipitate under different pH conditions, adding 50ml of 0.1mol/L NaHCO according to the adding amount of 1.0g/L3And reacting for 2 hours in the solution, and measuring the concentration of the resolved uranium in the solution. As can be seen from fig. 5, the solid desorption rate is low under the conditions of pH 3, pH 5 and pH 7, the desorption rate is less than 15% at pH 3, 12% at pH 5 and 27% at pH 7, which proves that the stability of the magnesium-uranium mica mineral is good, and the desorption rate is high because amorphous substances are formed under the conditions of pH 9 and pH 11.
According to the invention, magnesium salt, phosphate and uranium-containing wastewater are mixed, soluble magnesium salt and phosphate can dissolve phosphate radical and magnesium ions, different pH values of uranium solutions are adjusted, magnesium-uranium-mica mineral precipitates are formed with uranyl ions, and uranium pollutants are further removed by formed solid precipitates through physical and chemical adsorption. The method for treating the uranium-containing wastewater by using the magnesium-uranium-mica mineral precipitate formed by precipitation of soluble magnesium salt, phosphate and uranyl ions has high uranyl ion removal rate and wide applicable pH range.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A uranium-bearing wastewater treatment agent is characterized in that the treatment agent is one or two of magnesium salt and phosphate.
2. A uranium containing wastewater treatment agent according to claim 1, wherein the magnesium salt comprises at least one of magnesium nitrate and magnesium chloride.
3. A uranium containing wastewater treatment agent according to claim 1, wherein the phosphate comprises at least one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, calcium dihydrogen phosphate.
4. The method for treating uranium-containing wastewater is characterized by comprising the following steps:
1) mixing the treating agent of claim 1 with uranium-containing wastewater to react;
2) separating the mixture after the reaction in the step 1) to obtain solid slag and residual liquid, and removing the solid slag to remove uranium.
5. A method of treating uranium containing wastewater according to claim 4, wherein the reaction in step 1) has a pH of 2 to 11.
6. A method for treating uranium-bearing waste water according to claim 4, wherein the pH regulator in the reaction in step 1) is at least one of hydrochloric acid, sulfuric acid, nitric acid, lime, limestone, dolomite, sodium hydroxide and sodium carbonate.
7. A method for treating uranium-containing wastewater according to claim 4, wherein the reaction time of the reaction in step 1) is 1-3 h.
8. A method for treating uranium-bearing waste water according to claim 4, wherein the molar ratio of Mg in magnesium salts and P in phosphate to U in uranium-bearing waste water in step 1) is (0-3): (0-5): 1, the molar number of Mg in the magnesium salt and the molar number of P in the phosphate are not 0 at the same time.
9. A method for treating uranium-containing wastewater according to claim 4, wherein the uranium concentration of the uranium-containing wastewater in step 1) is 20-1000 mg/L.
10. A method for treating uranium-bearing wastewater according to claim 4, wherein the solid slag in step 2) is magnesium-uranium-mica mineral precipitate.
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CN115432688A (en) * | 2022-09-22 | 2022-12-06 | 东华理工大学 | Calcium-changed uranium mica product and preparation method thereof |
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