CN116282611B - Method for treating industrial high-salt uranium-containing wastewater - Google Patents
Method for treating industrial high-salt uranium-containing wastewater Download PDFInfo
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- CN116282611B CN116282611B CN202111561410.XA CN202111561410A CN116282611B CN 116282611 B CN116282611 B CN 116282611B CN 202111561410 A CN202111561410 A CN 202111561410A CN 116282611 B CN116282611 B CN 116282611B
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- containing wastewater
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 174
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000002351 wastewater Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000000706 filtrate Substances 0.000 claims abstract description 85
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000011282 treatment Methods 0.000 claims abstract description 68
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 6
- 238000011221 initial treatment Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 29
- 238000001728 nano-filtration Methods 0.000 claims description 29
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 230000001105 regulatory effect Effects 0.000 claims description 15
- 239000008394 flocculating agent Substances 0.000 claims description 13
- 239000002893 slag Substances 0.000 abstract description 18
- 230000002829 reductive effect Effects 0.000 abstract description 13
- 239000000843 powder Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 37
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000000292 calcium oxide Substances 0.000 description 13
- 235000012255 calcium oxide Nutrition 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- -1 NH 4 + Chemical class 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 238000006115 defluorination reaction Methods 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- 239000001110 calcium chloride Substances 0.000 description 7
- 229910001628 calcium chloride Inorganic materials 0.000 description 7
- 238000005121 nitriding Methods 0.000 description 7
- 229920002401 polyacrylamide Polymers 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000002285 radioactive effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Chemical class 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
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- 238000005065 mining Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002354 radioactive wastewater Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- 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
- G21F9/10—Processing by flocculation
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (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 method for treating industrial high-salt uranium-containing wastewater, which comprises the following steps: step 1, carrying out primary treatment on high-salt uranium-containing wastewater by adopting ultrasonic waves; step 2, filtering the reaction liquid after preliminary treatment, and detecting filtrate; and 3, carrying out post-treatment on the filtrate according to the detection result of the filtrate. The method for treating industrial high-salt uranium-containing wastewater greatly shortens the wastewater treatment time, reduces the input amount and slag amount of zero-valent iron powder, and reduces the production cost and the stockpiling cost; meanwhile, the treated wastewater does not need to be subjected to standing treatment, the suction filtration process can be directly carried out, the process time is shortened, a sedimentation tank is not required to be installed, and the occupied area is reduced.
Description
Technical Field
The invention relates to the technical field of nuclear industry wastewater treatment, in particular to a method for treating industrial high-salt uranium-containing wastewater.
Background
Among the numerous water pollution, radioactive wastewater pollution is the type of pollution that is most harmful to the environment and humans. With the development of the atomic energy industry and the wide application of nuclear fuel circulation and nuclear technology, such as uranium mining, uranium smelting, retirement of uranium mining facilities and the like, the amount of radioactive uranium-containing wastewater closely related to the uranium mining, uranium smelting and retirement is gradually increased.
Currently, radionuclides in world radioactive wastewater can enter underground water organizations, and have great influence on industrial and agricultural and human health. Because uranium produces uranium pollution to a container for containing uranium products in the process of processing production and storage and transportation of uranium products, a high-pressure water gun is generally adopted, a certain acid solution is matched for cleaning, then an alkali solution is matched for cleaning, in the cleaning process, uranium enters a cleaning solution through hydrolysis to form high-concentration uranium-containing wastewater, the uranium content in the wastewater is generally up to the level of 'g/L', the highest uranium content can reach 5g/L, and the conventional uranium removal means cannot meet the requirement of uranium removal.
In recent years, zero-valent iron has an active chemical property, a reducing effect, a coagulation adsorption effect and an electrolysis effect, and is widely applied to the treatment of uranium-containing polluted water as an important and low-cost effective material. However, in the application process, the problems of large iron powder addition amount, high treatment cost, large radioactive slag amount, difficult filtration and the like exist in many cases, and in addition, if the treated uranium-containing wastewater contains other metal ions (high salt) and the content is high, the uranium removal effect and the consumption of the iron powder are greatly affected.
Therefore, it is necessary to provide a method for rapidly and efficiently treating industrial high-salt uranium-containing wastewater, which has low treatment cost and small amount of radioactive slag generated, weakens or eliminates the influence of other metal ions (high salt) in the wastewater on uranium removal, and can enable the treated uranium-containing wastewater to reach the discharge standard in a shorter time.
Disclosure of Invention
In order to overcome the problems, the inventor makes intensive researches and designs a method for treating industrial high-salt uranium-containing wastewater, which adopts ultrasonic wave to strengthen zero-valent iron to treat the uranium-containing wastewater, and combines a nanofiltration membrane to further remove uranium, so that the wastewater treatment time is greatly shortened, the input amount of zero-valent iron is reduced, the slag amount is reduced, the production cost and the stacking cost are reduced, and the uranium-containing wastewater can be treated to reach the discharge standard in a shorter time; meanwhile, the resource utilization is realized, and the desalting process is avoided, thereby completing the invention.
In particular, it is an object of the present invention to provide the following aspects:
The invention provides a method for treating industrial high-salt uranium-containing wastewater, which comprises the following steps:
step 1, carrying out primary treatment on high-salt uranium-containing wastewater by adopting ultrasonic waves;
step 2, filtering the reaction liquid after preliminary treatment, and detecting filtrate;
and 3, carrying out post-treatment on the filtrate according to the detection result of the filtrate.
The content of uranium in the high-salt uranium-bearing wastewater is as follows: each liter of wastewater contains 1.0-6.0 g.
Wherein the pH value of the high-salt uranium-containing wastewater is 0-14, but the high-salt uranium-containing wastewater does not comprise 0.
Wherein step1 comprises the following sub-steps:
step 1-1, regulating the pH value of high-salt uranium-containing wastewater;
and step 1-2, adding iron powder, and performing ultrasonic treatment.
Wherein step2 comprises the sub-steps of:
Step 2-1, regulating the pH value of the reaction liquid after preliminary treatment in the step 1;
Step 2-2, adding a flocculating agent into the system in the step 2-1, and performing suction filtration to obtain a section of filtrate;
and 2-3, detecting uranium content of the first-stage filtrate.
Wherein,
In the step 2-1, the pH value of the reaction liquid after the preliminary treatment in the step 1 is adjusted to 8-12.
Wherein,
In the step 3, if the uranium content in the first-stage filtrate is less than 50 mug/L, performing nanofiltration membrane treatment on the first-stage filtrate;
If the uranium content in the first-stage filtrate is greater than 50 mug/L, the first-stage filtrate is subjected to ultrasonic treatment again.
Wherein,
If the uranium content of the first section of filtrate after nanofiltration membrane treatment is less than 7 mug/L, the solution control level is reached, and the subsequent treatment process can be carried out.
Wherein,
The ultrasonic treatment again comprises the following steps:
Step 3-1, adjusting the pH value of the first-stage filtrate;
Step 3-2, adding iron powder, and performing ultrasonic treatment again;
And 3-3, adding a flocculating agent, and filtering again to obtain a second-stage filtrate.
Wherein,
In the step 3-1, the pH value of the first-stage filtrate is regulated to 3-7.
The invention has the beneficial effects that:
(1) According to the method for treating industrial high-salt uranium-containing wastewater, an ultrasonic technology is combined with a zero-valent iron reduction technology, ultrasonic waves act on a high-salt uranium-containing solution added with iron powder to generate a large number of hydrogen free radicals H with extremely high reducibility, the H can perform uranium removal reaction in cooperation with the zero-valent iron powder, influence of other ions (high salt) in the solution on uranium removal is reduced, eliminated or shielded, meanwhile, the ultrasonic waves act on the solution to generate a large number of hydroxyl free radicals OH with strong oxidizability, the OH can synergistically oxidize part Fe 2+ generated by iron powder into Fe 3+ to generate more ferric hydroxide precipitates, adsorption coprecipitation of uranium in a solution system is enhanced, cavitation effect, mechanical effect and thermal effect generated by the ultrasonic wave action solution are added with heat transfer and mass transfer of ions in the solution, uranium removal reaction efficiency of the solution is improved, wastewater treatment time is greatly shortened, zero-valent iron powder input amount and slag amount are reduced, and production cost and stacking cost are lowered;
(2) According to the method for treating industrial high-salt uranium-containing wastewater, provided by the invention, the treated wastewater does not need to be subjected to standing treatment, the suction filtration process can be directly carried out, the process time is shortened, a sedimentation tank is not required to be arranged, and the occupied area is reduced;
(3) The method for treating industrial high-salt uranium-containing wastewater provided by the invention is easy to operate, low in energy consumption and pollution-free, and can treat the uranium-containing wastewater to reach the discharge standard in a shorter time;
(4) The method for treating industrial high-salt uranium-containing wastewater is suitable for treating the high-uranium-content wastewater, not only realizes resource utilization, but also avoids a desalting procedure, and reduces treatment cost.
Drawings
Fig. 1 shows a process flow diagram of a method of treating industrial high-salt uranium-containing wastewater according to a preferred embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following preferred embodiments and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The inventor researches and discovers that when ultrasonic waves propagate in a medium, a series of effects such as mechanics, heat and chemistry can be generated by the generated mechanical effect, cavitation effect and thermal effect, especially the acoustic cavitation effect generates a local high-temperature and high-pressure environment at the moment of cavitation nuclear explosion, and strong impact and high-speed micro-jet erosion are generated on the medium, so that a very special physical environment is provided for chemical reaction which is difficult to realize under general conditions, a chemical reaction channel is opened, and the progress of the chemical reaction is accelerated.
Accordingly, the present invention provides a method of treating industrial high salt uranium-containing wastewater, the method comprising the steps of:
step 1, carrying out primary treatment on high-salt uranium-containing wastewater by adopting ultrasonic waves;
step 2, filtering the reaction liquid after preliminary treatment, and detecting filtrate;
and 3, carrying out post-treatment on the filtrate according to the detection result of the filtrate.
In the invention, ultrasonic wave is adopted to strengthen zero-valent iron to treat uranium-containing wastewater, and simultaneously nanofiltration membrane is combined to further remove uranium, so that the content of fluorine in the wastewater after final treatment reaches the emission standard.
Without being bound by any theory, the principles of the present invention may be explained as follows: ultrasonic wave acts on the high-salt uranium-bearing solution added with iron powder to generate a large amount of hydrogen free radicals H with extremely strong reducibility, the H can cooperate with zero-valent iron powder to carry out uranium removal reaction, the influence of other ions (high salt) in the solution on the uranium removal effect is reduced, eliminated or shielded, meanwhile, the ultrasonic wave acts on the solution to generate a large amount of hydroxyl free radicals OH with strong oxidizability, the OH can cooperate with part of Fe 2+ generated by the iron powder to oxidize Fe 3+ to generate more ferric hydroxide precipitates, the adsorption coprecipitation of uranium in a solution system is enhanced, and the purpose of deep uranium removal is achieved.
The method for treating industrial high-salt uranium-containing wastewater is further described below, and the specific process flow can be seen in fig. 1:
and step 1, carrying out primary treatment on the high-salt uranium-containing wastewater by adopting ultrasonic waves.
In the invention, uranium-containing wastewater to be treated is industrial high-salt uranium-containing wastewater, particularly the high-salt uranium-containing wastewater contains higher-concentration salt substances, the salt substances are generally ammonium salts or metal salts, for example, the uranium-containing wastewater comprises metal cations such as NH 4 +、Fe3+、Na+ and the like, the concentration of the contained ammonium salts or metal salts can be 10-500g/L after measurement and conversion, for example, the concentration of NH 4 + ions can be 150-180g/L, the concentration of Fe 3+ ions can be 2-80g/L, and the concentration of Na + ions can be 5-100g/L.
The content of uranium in the high-salt uranium-bearing wastewater is as follows: each liter of wastewater contains 1.0-6.0 g.
Further, the high-salt uranium-containing wastewater also comprises fluorine, and the fluorine content is 0.5-10 g per liter of wastewater.
Wherein the uranium exists in the form of UO 2 2+ and the fluorine exists in the form of F -.
Wherein the pH value of the high-salt uranium-containing wastewater is 0-14, but the high-salt uranium-containing wastewater does not comprise 0.
Preferably, step 1 comprises the sub-steps of:
and step 1-1, regulating the pH value of the high-salt uranium-containing wastewater.
According to a preferred embodiment of the invention, the pH of the uranium-containing wastewater is adjusted using one or more of nitric acid, sulfuric acid, oxalic acid, sodium hydroxide solution, potassium hydroxide solution, lime milk, quicklime solution and soda lime solution.
In a further preferred embodiment, nitric acid or sodium hydroxide solution is used to adjust the pH of the high salt uranium containing wastewater,
Preferably, the concentration of the nitric acid is 30-70%, preferably 30-40%, for example 30%;
The concentration of the sodium hydroxide solution is 10 to 50%, preferably 20 to 40%, for example 40%.
In the invention, the concentration of the nitric acid and sodium hydroxide solution is mass fraction.
In a still further preferred embodiment, the pH of the adjusted high salt uranium containing wastewater is between 3 and 7, preferably between 3 and 6, more preferably 3.5.
In the invention, the pH value of the high-salt uranium-containing wastewater is firstly adjusted to the range, so that the subsequent hydrogen free radical and hydroxyl free radical synergistic uranium removal reaction generated by the iron powder and ultrasonic wave action is facilitated.
And step 1-2, adding iron powder, and performing ultrasonic treatment.
According to a preferred embodiment of the present invention, the added iron powder has a zero valent iron content of 50wt.% to 98wt.%, preferably 70wt.% to 98wt.%, more preferably 98wt.%.
Preferably, the particle size of the added iron powder is 80-300 mesh, preferably 160-260 mesh, e.g. about 200 mesh.
In a further preferred embodiment, the ratio of the additive amount of the industrial high-salt uranium-containing wastewater to the additive amount of the iron powder is: the addition amount of iron powder in each liter of wastewater is 0.2-1.0 g;
preferably, the iron powder is added in an amount of 0.8g per liter of wastewater.
According to the invention, under the action of ultrasonic waves, the addition proportion of the industrial high-salt uranium-containing wastewater to the iron powder is selected, so that the hexavalent soluble uranium can be comprehensively and effectively utilized, promoted and subjected to synergistic and coupling effects with the reducing hydrogen free radicals generated by the ultrasonic-action high-salt uranium-containing solution system, and the reduction of the hexavalent soluble uranium into tetravalent insoluble uranium can be completed together; meanwhile, ferrous ions and ferric ions are generated in the process of reducing hexavalent uranium by iron powder, and hydroxyl free radicals OH with oxidability generated when ultrasonic waves act on a high-salt uranium-containing solution system oxidize the generated ferrous ions into ferric ions, so that more Fe (OH) 3 is generated under alkaline conditions; in addition, under the cavitation effect, mechanical effect and thermal effect of ultrasonic waves, fe (OH) 3 flocculation particles are beneficial to grow up, the specific surface area is increased, flocculation, adsorption and precipitation effects are enhanced, tetravalent uranium generated by capturing, flocculation, adsorption and coprecipitation is promoted in the process, and the aim of removing uranium is fulfilled.
The inventor also finds that sodium ions in the added sodium hydroxide for adjusting the pH value can capture residual unreacted complete hexavalent uranium ions in the solution, generate sodium diuranate precipitate which is difficult to dissolve in water, flocculate and adsorb on the surface of ferric hydroxide, enter a slag phase and achieve the purpose of deep uranium removal.
Therefore, the method for treating industrial high-salt uranium-containing wastewater disclosed by the invention is characterized in that the method is not unilateral for removing uranium by utilizing iron powder, but is used for removing uranium by utilizing the iron powder, generating reductive hydrogen free radical by ultrasonic waves, generating strong oxidative hydroxyl free radical oxidation ferrous ion by ultrasonic waves to strengthen and promote flocculation-adsorption-precipitation effect for removing uranium, adjusting pH to strengthen reaction efficiency, and simultaneously capturing insoluble matters generated by utilizing sodium ions with pH adjusted to remove uranium by utilizing hexavalent soluble ions, so that the aim of deep removing uranium is achieved by synergistic and coupling combined action.
According to a preferred embodiment of the present invention, the ultrasonic treatment is performed at room temperature with a stirring rate of 60 to 180rpm,
Preferably, the power of the ultrasonic wave is 100W to 6000W, preferably 200W to 2000W, more preferably 300W to 1500W, such as 550W.
In the invention, the ultrasonic wave with the power range is selected, so that uranium can be removed rapidly and deeply. When the power of the ultrasonic wave is lower than 100W, preferably lower than 200W, the ultrasonic wave has too low action intensity, which can prolong the cooperative uranium removal process time and reduce the total amount of uranium-containing wastewater; when the power of the ultrasonic wave is higher than 6000W, preferably higher than 2000W, the generated tetravalent uranium precipitate is re-dissolved, and the uranium content of the treated wastewater is increased.
In a further preferred embodiment, the frequency of the ultrasonic wave is 20 to 25kHz, preferably 20 to 22kHz, more preferably 20kHz.
In a further preferred embodiment, the treatment time of the ultrasonic wave is 20 to 50min, preferably 25 to 40min, more preferably 30min.
The present inventors have found that the reaction is performed for 20 to 50 minutes, preferably 25 to 40 minutes, more preferably 30 minutes, under the ultrasonic waves in the above power range and frequency range, and that the effect of removing uranium by depth is optimal. When the ultrasonic time is less than 25min, especially less than 20min, incomplete uranium removal reaction can be caused; when the ultrasonic time is higher than 40min, especially higher than 50min, the generated tetravalent uranium is dissolved back, and the uranium removing effect is affected.
The inventor of the invention has found through a great deal of research that the high-salt uranium-containing wastewater treated by the method has corrosive ions, which cause corrosion to ultrasonic treatment equipment to a certain extent.
In order to reduce corrosion of the wastewater solution to equipment, the ultrasonic workpiece is preferably subjected to corrosion prevention treatment in the invention so as to improve the corrosion resistance and prolong the service life.
Preferably, the preservative treatment is performed according to a method comprising the steps of:
and i, cleaning the ultrasonic workpiece.
Wherein the ultrasonic workpiece is preferably an ultrasonic probe.
According to a preferred embodiment of the invention, the ultrasonic workpiece is ultrasonically cleaned to remove oil from the surface of the workpiece.
Preferably, the washing is carried out with sodium hydroxide solution having a concentration of 0.5 to 1.5M, preferably 1M.
And ii, nitriding the cleaned ultrasonic workpiece.
In the invention, the nitriding treatment is carried out on the ultrasonic workpiece by adopting a nitriding furnace, and the method preferably comprises the following substeps:
step ii-1, heating the nitriding furnace to a certain temperature, and preserving heat;
step ii-2, filling ammonia gas into the furnace, and keeping the temperature for a period of time;
and ii-3, cooling.
In step ii-1, the nitriding furnace is heated to 500-600 ℃, preferably 550 ℃, and the temperature is kept.
In the step ii-2, after filling ammonia gas into the furnace, the furnace temperature is kept between 550 ℃ and 800 ℃ and kept constant for 1 to 3 hours.
In the step ii-3, after the constant temperature is maintained for a period of time, the temperature is reduced and cooled, and the corresponding ultrasonic workpiece subjected to corrosion prevention treatment is obtained.
The inventor researches and discovers that the service life of the ultrasonic workpiece is obviously prolonged through the anti-corrosion treatment.
And step 2, filtering the reaction liquid after the preliminary treatment, and detecting the filtrate.
Preferably, step 2 comprises the sub-steps of:
and 2-1, regulating the pH value of the reaction liquid after the preliminary treatment in the step 1.
According to a preferred embodiment of the present invention, the pH of the reaction solution after the preliminary treatment in step 1 is adjusted using one or more of sodium hydroxide solution, potassium hydroxide solution, lime cream, quicklime solution and soda lime solution.
Preferably, the pH value of the reaction solution after the preliminary treatment in step 1 is adjusted by using a sodium hydroxide solution, the mass fraction of which is 20-60%, preferably 50%.
In a further preferred embodiment, the pH of the reaction solution after the preliminary treatment in step 1 is adjusted to 8 to 12, for example 10.
And 2-2, adding a flocculating agent into the system in the step 2-1, and performing suction filtration to obtain a section of filtrate.
According to a preferred embodiment of the invention, the flocculant is selected from one or more of polyethylene, polypropylene, polyacrylamide, quaternary ammonium salts, aluminium sulphate (Al (SO 4)3·18H2 O), alum (Al 2(SO4)3·K2SO4·24H2 O), sodium aluminate (NaAlO 3), ferric trichloride (Fe-Cl 3·6H2 O), ferrous sulphate (FeSO 4·6H2 O) and ferric sulphate (Fe 2(SO4)3·2H2 O), preferably polyacrylamide.
Preferably, the concentration of the flocculant is 0.5-3%, preferably 1%.
Wherein the concentration of the flocculant is mass fraction.
In the invention, after adding the flocculant, stirring for 1-5 min, and then carrying out suction filtration on the mixed solution to obtain a first-stage filtrate and a first-stage filter residue.
According to the method for treating industrial high-salt uranium-containing wastewater, disclosed by the invention, the treated wastewater does not need to be subjected to standing treatment, the suction filtration process can be directly carried out, the process time is shortened, a sedimentation tank is not required to be installed, and the occupied area is reduced.
And 2-3, detecting uranium content of the first-stage filtrate.
In the present invention, the uranium content in the first filtrate is preferably detected by an ICP method.
And 3, carrying out post-treatment on the filtrate according to the detection result of the filtrate.
According to a preferred embodiment of the invention, through the above detection, if the uranium content in the first filtrate is less than 50 μg/L, performing nanofiltration membrane treatment on the first filtrate;
If the uranium content in the first-stage filtrate is greater than 50 mug/L, the first-stage filtrate is subjected to ultrasonic treatment again.
According to a preferred embodiment of the invention, the nanofiltration membrane treatment is carried out with nanofiltration membranes having a retention rate of more than 95% during permeation.
Preferably, the molecular weight of the nanofiltration membrane interception material is 200-1000 Da.
More preferably, the nanofiltration membrane is operated at a pressure of 3.5 to 30bar.
In a further preferred embodiment, if the uranium content of the first filtrate after nanofiltration membrane treatment is less than 7 mug/L, the uranium content reaches a solution control level, and the subsequent treatment process can be carried out;
if the uranium content of the first-stage filtrate after nanofiltration membrane treatment is greater than 7 mug/L, carrying out ultrasonic treatment again until the uranium content is less than 7 mug/L.
In the present invention, the subsequent treatment step after reaching the control level is preferably a defluorination step.
Preferably, the defluorination process comprises the following steps:
Step i, adding calcium oxide into filtrate reaching a solution control level, and performing ultrasonic reaction;
Step ii, adding calcium chloride into the reaction system of the step i, and carrying out ultrasonic reaction again;
and iii, regulating the pH value of the reaction system, adding a flocculating agent, and carrying out solid-liquid separation.
Wherein, in the step i, the added calcium oxide is as follows: the amount of calcium oxide is 0.5 to 6.0g, preferably 1 to 4.5g, more preferably 1.5 to 3.0g, per liter of filtrate;
In step i, the power of the ultrasonic reaction is 100-2000W, preferably 200-1000W, more preferably 200-550W, and the frequency is 20-25 Hz; the time of the ultrasonic reaction is 2 to 15 minutes, preferably 3 to 10 minutes, such as 3 minutes, 5 minutes or 10 minutes.
In the step ii, the addition amount of the calcium chloride is as follows: the amount of calcium chloride is 0.5 to 2.5g, preferably 0.8 to 2.0g, more preferably 1.0 to 1.5g, per liter of filtrate;
In step ii, the power of the ultrasonic reaction is 100-2000W, preferably 200-1000W, more preferably 200-550W, and the frequency is 20-25 Hz; the time for the second ultrasonic reaction is 3 to 20 minutes, preferably 5 to 15 minutes, such as 5 minutes, 10 minutes or 15 minutes.
In the step iii, the pH value of the reaction system is regulated to be 6.5-7.6;
The flocculant is polyaluminum chloride, and the addition amount is as follows: 250 to 450mg, preferably 300 to 400mg, more preferably 350mg, of fluorine wastewater per liter is added.
According to a preferred embodiment of the invention, if the uranium content of the first filtrate is greater than 50. Mu.g/L, the first filtrate is subjected to ultrasound again,
The ultrasonic treatment again comprises the following steps:
and 3-1, adjusting the pH value of the first-stage filtrate.
According to a preferred embodiment of the invention, the pH of the primary filtrate is adjusted with one or more of nitric acid, sulfuric acid, oxalic acid, sodium hydroxide solution, potassium hydroxide solution, lime milk, quicklime solution and quicklime solution, preferably with nitric acid.
Preferably, the concentration of the nitric acid is 30% to 70%, preferably 30% to 40%, for example 30%.
In a further preferred embodiment, the pH of the primary filtrate is adjusted to a value of 3 to 7, preferably 4.
And 3-2, adding iron powder, and performing ultrasonic treatment again.
According to a preferred embodiment of the present invention, the added iron powder has a zero valent iron content of 50wt.% to 99wt.%, preferably 75wt.% to 99wt.%, more preferably 98wt.%.
In a further preferred embodiment, the ratio of the added amount of the first filtrate to the iron powder is: the adding amount of the iron powder in each 5-16L of one section of filtrate is 5g;
Preferably, the addition amount of the iron powder is 5g in each 7-13L of one section of filtrate;
In the invention, the reason for selecting the adding proportion of the first section of filtrate and the iron powder is as follows: the cavitation of ultrasonic wave can avoid the agglomeration of iron powder, open the parcel of removing uranium product to the iron powder, and remove uranium through the synergism between strong reducibility hydrogen free radical that the effect solution produced and the iron powder, can reduce the iron powder quantity by a wide margin, promotes the purification degree of depth.
According to a preferred embodiment of the present invention, the ultrasonic treatment is performed again at room temperature with a stirring rate of 60 to 180rpm,
Preferably, the power of the ultrasonic wave is 100W to 6000W, preferably 200W to 2000W, more preferably 300W to 1500W, such as 550W.
In a further preferred embodiment, the frequency of the ultrasonic wave is 20 to 25kHz, preferably 20 to 22kHz, more preferably 20kHz.
In a further preferred embodiment, the treatment time of the ultrasonic wave is 20 to 50min, preferably 25 to 40min, more preferably 30min.
And 3-3, adding a flocculating agent, and filtering again to obtain a second-stage filtrate.
According to a preferred embodiment of the invention, the pH of the reaction system in step 3-2 is adjusted with one or more of sodium hydroxide solution, potassium hydroxide solution, lime milk, quicklime solution and quicklime solution, preferably with sodium hydroxide solution, before the addition of the flocculant.
Preferably, the mass fraction of the sodium hydroxide solution is 20% -60%, preferably 50%.
In a further preferred embodiment, the pH of the reaction system in step 3-2 is adjusted to a value of 8 to 10, for example 10.
According to a preferred embodiment of the invention, the flocculant is selected from one or more of polyethylene, polypropylene, polyacrylamide, polyaluminum chloride, quaternary ammonium salts, aluminium sulphate (Al (SO 4)3·18H2 O), alum (Al 2(SO4)3·K2SO4·24H2 O), sodium aluminate (NaAlO 3), ferric trichloride (Fe-Cl 3·6H2 O), ferrous sulphate (FeSO 4·6H2 O) and ferric sulphate (Fe 2(SO4)3·2H2 O), preferably polyacrylamide.
Preferably, the concentration of the flocculant is 0.5-3%, preferably 1%.
In the invention, after adding the flocculant, stirring and then carrying out suction filtration on the mixed solution to obtain second-stage filtrate and second-stage filter residues.
According to a preferred embodiment of the invention, the uranium content of the second filtrate is detected, and if the uranium content in the second filtrate is less than 50 mug/L, the second filtrate is subjected to nanofiltration membrane treatment;
if the uranium content in the second-stage filtrate is greater than 50 mug/L, carrying out ultrasonic treatment on the second-stage filtrate again, namely repeating the steps 3-1 to 3-3 until the uranium content is less than 50 mug/L.
In the invention, the two-stage filtrate subjected to nanofiltration membrane treatment is performed according to the nanofiltration membrane treatment method, and when the uranium content of the two-stage filtrate subjected to nanofiltration membrane treatment is less than 7 mug/L, the solution control level is reached, and the subsequent treatment process (defluorination process) can be performed; and when the uranium content of the two-stage filtrate treated by the nanofiltration membrane is more than 7 mug/L, carrying out ultrasonic treatment again, namely repeating the steps 3-1 to 3-3 until the uranium content is less than 7 mug/L.
Preferably, the obtained first-stage filter residue or the mixture of the first-stage filter residue and the second-stage filter residue is subjected to drying treatment by a microwave drying system, and the dried filter residue is filled into a stainless steel tank body and is safely buried or stored according to national requirements.
And (3) the solution with the uranium content reaching the solution control level after nanofiltration membrane treatment enters an ultrasonic defluorination process, and the wastewater with the fluorine content reaching the standard and the solution control defluorination slag are obtained after defluorination treatment.
According to the method for treating industrial high-salt uranium-containing wastewater, provided by the invention, the ultrasonic wave is adopted to strengthen zero-valent iron to treat the high-salt uranium-containing wastewater, so that the resource utilization is realized, the desalting process is avoided, the treatment time is greatly shortened, the iron powder addition amount is reduced, the treatment cost is reduced, the generated radioactive slag amount is small, and the pressure of uranium removal and radioactive slag storage of the factory wastewater can be effectively shared.
Examples
The invention is further described below by means of specific examples, which are however only exemplary and do not constitute any limitation on the scope of protection of the invention.
Example 1
In the embodiment, 1500ml of industrial high-salt uranium-containing wastewater is taken, wherein the uranium content is 1.62g/L, the fluorine content is 4.5g/L, the salt content is NH4NO3、Fe2(SO4)3、Fe(NO3)3、NaNO3、Na2SO4,, the NH 4 + ion concentration is 150.2g/L, the Fe 3+ ion concentration is 23.5g/L, the Na + ion concentration is 50.4g/L, and the pH value is about 7.
As shown in fig. 1, the industrial high-salt uranium-containing wastewater is treated according to the following steps:
(1) Adjusting the pH value of the wastewater to 3.5 by adopting a nitric acid solution with the mass fraction of 30%, adding 0.8g of Fe powder into the solution with the pH value being adjusted, wherein the content of zero-valent iron in the iron powder is 98.1%, the granularity is about 200 meshes, placing the wastewater and the iron powder into an ultrasonic reactor, starting ultrasonic waves at room temperature and the stirring speed of 120rpm, wherein the power is 550W, the frequency is 20kHz, and performing ultrasonic treatment for 30min.
Wherein, the ultrasonic probe of the ultrasonic reactor is subjected to the following anti-corrosion treatment: ultrasonic cleaning is carried out on the probe by adopting a 1M sodium hydroxide solution to remove greasy dirt on the surface; placing the probe in a nitriding furnace, raising the furnace temperature to 550 ℃, preserving heat, then filling ammonia gas into the furnace, keeping the furnace temperature at 550-800 ℃, keeping the temperature for 2 hours, and cooling;
(2) And (3) adding a 40% sodium hydroxide solution into the system after the reaction in the step (1), regulating the pH value of the reaction solution to be 10, adding 1 drop of flocculating agent (polyacrylamide, 1%o), stirring for 5min, carrying out suction filtration on the reaction solution to obtain a section of filtrate and a section of filter residue, and detecting the uranium content in the section of filtrate by adopting an ICP method, wherein the result shows that the uranium content is 100.3 mug/L.
(3) Adding 30% nitric acid into a first-stage filtrate (1300 ml), adjusting the pH value of the filtrate to 4, adding 0.5g Fe powder with the zero-valent iron content of 98.1% and the granularity of about 200 meshes under the conditions of room temperature and stirring speed of 120rpm, placing the first-stage filtrate and the iron powder into an ultrasonic reactor, starting ultrasonic waves with the power of 400W and the frequency of 20kHz, and performing ultrasonic treatment for 30min;
And then adding 50% sodium hydroxide solution by mass fraction to adjust the pH of the reacted solution to 10, adding 1 drop of flocculating agent (polyacrylamide, 1%o), stirring for 5min, carrying out suction filtration to obtain second-stage filtrate and second-stage filter residue, and detecting the uranium content in the second-stage filtrate by adopting an ICP method, wherein the result shows that the uranium content is 8.3 mug/L.
The second-stage filtrate is treated by a nanofiltration membrane, the interception molecular weight of the nanofiltration membrane (manufacturer: shanghai Yiming filtration technology Co., ltd.) is in the range of 200-1000Da, the interception rate is more than 95% in the infiltration process, and the operation pressure of the nanofiltration membrane is 3.5-30bar; after nanofiltration membrane treatment, the uranium content in the second-stage filtrate is about 2.1 mug/L, so as to reach the control level; and returning the concentrated phase to a uranium removal process to carry out uranium removal treatment.
The uranium-containing slag phase obtained in the second-stage uranium removal procedure is the second-stage filter residue, the second-stage filter residue is combined with the first-stage filter residue, microwave drying treatment is carried out, and the microwave dried slag is placed into a stainless steel tank and is safely buried and stored according to national requirements.
The solution with uranium content reaching the solution control level after the nanofiltration membrane treatment enters an ultrasonic defluorination process, and the steps are as follows: adding CaO to carry out ultrasonic reaction (the power is 400W, the frequency is 20 kHz) for 5 minutes, wherein the adding amount of CaO is 1.5g/L; then adding calcium chloride for ultrasonic reaction for 15min, wherein the adding amount of the calcium chloride is 1.5g/L; after the reaction is finished, regulating the pH value of the solution to 7.6, adding flocculating agent polyaluminium chloride, slightly stirring, and carrying out solid-liquid separation to obtain wastewater with the fluorine content of 5mg/L which is controlled by solution and fluorine-removing slag which is controlled by solution, and carrying out microwave drying on the fluorine-containing slag and then carrying out stockpiling treatment according to common solid waste.
After the treatment, the uranium content in the dischargeable clear liquid is 2.1 mug/L, the solution control level is achieved, the fluorine content is lower than 10mg/L, and the discharge standard is achieved.
Example 2
In the embodiment, 1500ml of high-salt uranium-containing wastewater is taken, the uranium content is 4.02g/L, the fluorine content is 1.5g/L, the salt content is NH4NO3、FeCl3、Fe(NO3)3、NaCl3、Na2SO4,NH4 +, the ion concentration is 180.7g/L, the ion concentration of Fe 3+ is 8.4g/L, the ion concentration of Na + is 70.6g/L, and the pH value is about 1.
As shown in fig. 1, the industrial high-salt uranium-containing wastewater is treated according to the following steps:
(1) Adjusting the pH value of the wastewater to 3.5 by adopting a sodium hydroxide solution with the mass fraction of 50%, adding 1.2g of Fe powder into the solution with the pH value being adjusted, wherein the content of zero-valent iron in the iron powder is 98.1%, the granularity is about 200 meshes, placing the wastewater and the iron powder into an ultrasonic reactor, starting ultrasonic waves at room temperature and the stirring speed of 120rpm, wherein the power is 700W, the frequency is 20kHz, and performing ultrasonic treatment for 30min.
(2) And (3) adding 50% sodium hydroxide solution into the system after the reaction in the step (1), regulating the pH value of the reaction solution to be 12, adding 1 drop of flocculating agent (polyaluminium chloride, 1%o), stirring for 5min, carrying out suction filtration on the reaction solution to obtain a section of filtrate and a section of filter residue, and detecting the uranium content in the section of filtrate by adopting an ICP method, wherein the result shows that the uranium content is 120.3 mug/L.
(3) Adding 30% nitric acid into a first-stage filtrate (1350 ml), regulating the pH value of the filtrate to 4.5, adding 0.8g Fe powder with the zero-valent iron content of 98.1% and the granularity of about 200 meshes under the conditions of room temperature and stirring speed of 120rpm, placing the first-stage filtrate and the iron powder into an ultrasonic reactor, starting ultrasonic waves with the power of 500W, the frequency of 20kHz, and carrying out ultrasonic treatment for 30min;
wherein, the ultrasonic probe of the ultrasonic reactor is subjected to the following anti-corrosion treatment: ultrasonic cleaning is carried out on the probe by adopting a 1M sodium hydroxide solution to remove greasy dirt on the surface; placing the probe in a nitriding furnace, raising the furnace temperature to 550 ℃, preserving heat, then filling ammonia gas into the furnace, keeping the furnace temperature at 550-800 ℃, keeping the temperature for 2 hours, and cooling;
And then adding 50% sodium hydroxide solution by mass fraction to adjust the pH of the reacted solution to 10, adding 1 drop of flocculating agent (polyacrylamide, 1%o), stirring for 5min, carrying out suction filtration to obtain second-stage filtrate and second-stage filter residue, and detecting the uranium content in the second-stage filtrate by adopting an ICP method, wherein the result shows that the uranium content is 38.5 mug/L.
The second-stage filtrate is treated by a nanofiltration membrane, the interception molecular weight of the nanofiltration membrane (manufacturer: shanghai Yiming filtration technology Co., ltd.) is in the range of 200-1000Da, the interception rate is more than 95% in the infiltration process, and the operation pressure of the nanofiltration membrane is generally 3.5-30bar; after nanofiltration membrane treatment, the uranium content in the second-stage filtrate is 2.8 mug/L, so as to reach the control level; and returning the concentrated phase to a uranium removal process to carry out uranium removal treatment.
The uranium-containing slag phase obtained in the second-stage uranium removal procedure is the second-stage filter residue, the second-stage filter residue is combined with the first-stage filter residue, microwave drying treatment is carried out, and the microwave dried slag is placed into a stainless steel tank and is safely buried and stored according to national requirements.
The solution with uranium content reaching the solution control level after the nanofiltration membrane treatment enters an ultrasonic defluorination process, and the steps are as follows: adding CaO to carry out ultrasonic reaction (the power is 400W, the frequency is 20 kHz) for 5 minutes, wherein the adding amount of CaO is 1.5g/L; then adding calcium chloride for ultrasonic reaction for 15min, wherein the adding amount of the calcium chloride is 1.5g/L; after the reaction is finished, regulating the pH value of the solution to 7.6, adding flocculating agent polyaluminium chloride, slightly stirring, and carrying out solid-liquid separation to obtain wastewater with the fluorine content of 7.2mg/L which is controlled by solution and fluorine-removing slag which is controlled by solution, and carrying out microwave drying on the fluorine-containing slag and then piling up the fluorine-containing slag according to common solid waste.
After the treatment, the uranium content in the dischargeable clear liquid is 2.8 mug/L, the solution control level is achieved, the fluorine content is lower than 10mg/L, and the discharge standard is achieved.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention.
Claims (6)
1. A method for treating industrial high-salt uranium-containing wastewater, the method comprising the steps of:
step 1, carrying out primary treatment on high-salt uranium-containing wastewater by adopting ultrasonic waves;
step 2, filtering the reaction liquid after preliminary treatment, and detecting filtrate;
step 3, carrying out post-treatment on the filtrate according to the detection result of the filtrate;
In the step 3, if the uranium content in the first-stage filtrate is less than 50 mug/L, performing nanofiltration membrane treatment on the first-stage filtrate;
If the uranium content in the first-stage filtrate is greater than 50 mug/L, carrying out ultrasonic treatment on the first-stage filtrate again;
the ultrasonic treatment again comprises the following steps:
Step 3-1, regulating the pH value of the filtrate;
Step 3-2, adding iron powder, and performing ultrasonic treatment again;
step 3-3, adding a flocculating agent, and filtering again to obtain filtrate;
Step1 comprises the following sub-steps:
step 1-1, regulating the pH value of high-salt uranium-containing wastewater;
step 1-2, adding iron powder, and performing ultrasonic treatment;
step2 comprises the following sub-steps:
Step 2-1, regulating the pH value of the reaction liquid after preliminary treatment in the step 1;
Step 2-2, adding a flocculating agent into the system in the step 2-1, and performing suction filtration to obtain a section of filtrate;
and 2-3, detecting uranium content of the first-stage filtrate.
2. The method for treating industrial high-salt uranium-containing wastewater according to claim 1, wherein the content of uranium in the high-salt uranium-containing wastewater is: each liter of wastewater contains 1.0-6.0 g.
3. The method of treating industrial high-salt uranium-containing wastewater according to claim 1, wherein the high-salt uranium-containing wastewater has a pH of 0to 14 but does not include 0.
4. The method for treating industrial high-salt uranium-containing wastewater of claim 1,
In the step 2-1, the pH value of the reaction liquid after the preliminary treatment in the step 1 is adjusted to 8-12.
5. The method for treating industrial high-salt uranium-containing wastewater of claim 1,
If the uranium content of the first section of filtrate after nanofiltration membrane treatment is less than 7 mug/L, the solution control level is reached, and the subsequent treatment process is carried out.
6. The method for treating industrial high-salt uranium-containing wastewater of claim 1,
In the step 3-1, the pH value of the first section of filtrate is adjusted to 3-7.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001174587A (en) * | 1999-12-20 | 2001-06-29 | Mitsubishi Nuclear Fuel Co Ltd | Decontamination method for liquid radioactive waste |
| CN101597113A (en) * | 2009-06-27 | 2009-12-09 | 南华大学 | A kind of treatment process of uranium-containing waste water |
| CN104538077A (en) * | 2013-12-06 | 2015-04-22 | 东华理工大学 | Method for treating acidic uranium-bearing wastewater with bone-based adsorbent |
| CN104835545A (en) * | 2015-03-19 | 2015-08-12 | 西南科技大学 | Method for deeply purifying and recovering hyperhaline fluoric-u radioactive waste solution |
| CN105036427A (en) * | 2015-07-01 | 2015-11-11 | 昆明理工大学 | Processing method of industrial uranium-containing wastewater |
| CN109289803A (en) * | 2018-09-29 | 2019-02-01 | 西南科技大学 | Polyamines base/amidoxime group modification polyfunctional group ion-exchange fibre method of preparation and use |
| CN109411106A (en) * | 2018-12-11 | 2019-03-01 | 核工业理化工程研究院 | The decontamination waste liquid near-zero release processing unit and its processing method of uranium-bearing and detergent |
| CN109741850A (en) * | 2018-12-27 | 2019-05-10 | 中核四0四有限公司 | A kind of processing unit and method of uranium purifying conversion apparatus for production line cleaning solution |
| CN113060780A (en) * | 2021-03-05 | 2021-07-02 | 绍兴文理学院 | Method for rapidly removing uranium in water by aging modified zero-valent iron |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101047985B1 (en) * | 2010-11-26 | 2011-07-13 | 한국지질자원연구원 | High efficient uranium leaching method using ultrasonic wave |
| US20210205779A1 (en) * | 2020-01-03 | 2021-07-08 | Secretary, Department Of Atomic Energy | Process for uranium removal from near neutral aqueous solutions by freshly prepared fine ferrihydrite generated during ultrasonic assisted corrosion of mild steel wool |
-
2021
- 2021-12-17 CN CN202111561410.XA patent/CN116282611B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001174587A (en) * | 1999-12-20 | 2001-06-29 | Mitsubishi Nuclear Fuel Co Ltd | Decontamination method for liquid radioactive waste |
| CN101597113A (en) * | 2009-06-27 | 2009-12-09 | 南华大学 | A kind of treatment process of uranium-containing waste water |
| CN104538077A (en) * | 2013-12-06 | 2015-04-22 | 东华理工大学 | Method for treating acidic uranium-bearing wastewater with bone-based adsorbent |
| CN104835545A (en) * | 2015-03-19 | 2015-08-12 | 西南科技大学 | Method for deeply purifying and recovering hyperhaline fluoric-u radioactive waste solution |
| CN105036427A (en) * | 2015-07-01 | 2015-11-11 | 昆明理工大学 | Processing method of industrial uranium-containing wastewater |
| CN109289803A (en) * | 2018-09-29 | 2019-02-01 | 西南科技大学 | Polyamines base/amidoxime group modification polyfunctional group ion-exchange fibre method of preparation and use |
| CN109411106A (en) * | 2018-12-11 | 2019-03-01 | 核工业理化工程研究院 | The decontamination waste liquid near-zero release processing unit and its processing method of uranium-bearing and detergent |
| CN109741850A (en) * | 2018-12-27 | 2019-05-10 | 中核四0四有限公司 | A kind of processing unit and method of uranium purifying conversion apparatus for production line cleaning solution |
| CN113060780A (en) * | 2021-03-05 | 2021-07-02 | 绍兴文理学院 | Method for rapidly removing uranium in water by aging modified zero-valent iron |
Non-Patent Citations (7)
| Title |
|---|
| Gold extraction using alternatives to cyanide: Ultrasonic reinforcement and its leaching kinetics;Gui, Qihao等;MINERALS ENGINEERING;20221130;第191卷;107939 * |
| 含铀废水超声波深度除铀工艺试验研究;胡锦明;中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑;20170415;C040-4 * |
| 张纯 ; 张伟 ; 周星火 ; .零价铁粉在含U(Ⅵ)废水处理中的应用研究.铀矿冶.2009,(第03期),全文. * |
| 纳滤技术在矿冶领域的应用研究进展;黄万抚;李英杰;李新冬;梁娟;陈洋;刘玉娇;;工业水处理;20161120(第11期);全文 * |
| 零价铁去除含铀废水中的铀;陈迪云;张志强;占永革;袁土贵;;广州大学学报(自然科学版);20120815(第04期);全文 * |
| 零价铁粉在含U(Ⅵ)废水处理中的应用研究;张纯;张伟;周星火;;铀矿冶;20090820(第03期);全文 * |
| 高效铀吸附材料的设计制备及性能研究;李楠;中国博士学位论文全文数据库 工程科技Ⅰ辑;20211115;B016-10 * |
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