CN112520924A - Recycling and resource treatment method for alkaline wastewater in tantalum-niobium hydrometallurgy - Google Patents
Recycling and resource treatment method for alkaline wastewater in tantalum-niobium hydrometallurgy Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 45
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 88
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 35
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 35
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 30
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 30
- 239000012452 mother liquor Substances 0.000 claims abstract description 27
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 24
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 229910052758 niobium Inorganic materials 0.000 claims description 19
- 239000010955 niobium Substances 0.000 claims description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 7
- 239000001095 magnesium carbonate Substances 0.000 claims description 7
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012245 magnesium oxide Nutrition 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000008235 industrial water Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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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 recycling and resource treatment method of alkaline wastewater in tantalum-niobium hydrometallurgy, wherein the alkaline wastewater in tantalum-niobium hydrometallurgy is ammonia-introduced neutralization mother liquor and washing wastewater thereof; the method comprises the following steps: (1) recycling the washing wastewater; (2) removing fluorine by precipitation of magnesium compound; (3) concentrating and recovering ammonium sulfate. According to the invention, through three processes of washing wastewater recycling, magnesium compound precipitation defluorination and ammonium sulfate concentration recovery, industrial water in tantalum-niobium production is greatly reduced, two byproducts of magnesium fluoride and ammonium sulfate are produced while environmental pollution is solved, the full recovery of valuable resources in wastewater is realized, and the method has the characteristics of simple process and easiness in application, and is suitable for industrial production.
Description
Technical Field
The invention relates to a recycling and resource treatment method of alkaline wastewater in tantalum-niobium hydrometallurgy.
Background
The waste water containing high fluorine, sulfate and ammonia nitrogen generated by tantalum-niobium smelting is the main threat of the industry to environmental pollution. The waste water is roughly divided into two types, one type is acid-containing residual liquid at the front section of the production process, and accounts for about 5 percent of the waste water generated in the smelting of tantalum and niobium; one is alkaline waste water generated by neutralizing and washing liquid ammonia at the later stage of the process, and accounts for about 95 percent of the total amount of the waste liquid. Wherein the water consumption of the latter stage and the salt content in the waste water are very surprising, about 150 tons of deionized water are consumed for every 1 ton of niobium oxide produced, and waste liquid containing about 1.4 tons of ammonium fluoride and 1.1 tons of ammonium sulfate is produced. As fluorine belongs to scarce resources and is a planned quota export product in China, the method reduces the water consumption in the production of tantalum and niobium and has great economic and social benefits for recovering the fluorine in the wastewater.
In the prior art, the treatment of tantalum-niobium hydrometallurgy wastewater roughly comprises methods such as quicklime neutralization, distillation, ion exchange resin adsorption and the like. The most common treatment is lime treatment to solidify the free fluoride ions in the form of calcium fluoride, which results in solid residues that cannot be recycled and require large amounts of site stacking and landfilling. Although the distillation of the fluorine-containing waste liquid is an effective recovery method, as reported by Lianmni et al, various ammonia nitrogen waste water generated by tantalum-niobium hydrometallurgy is classified according to ammonia nitrogen concentration, and is subjected to distillation, condensation, crystallization, stripping and ion exchange with zeolite as an adsorbent (Lianmni, Wangma, etc.: experimental research on a method for removing ammonia nitrogen from tantalum-niobium hydrometallurgy waste water [ J ], industrial water treatment: 2011, 31(3):53-56), the distillation method needs to use corrosion-resistant materials, so that the equipment price is high, and the distillation separation is often insufficient, so that the distillation method is difficult to apply in terms of the operation cost of the equipment. Other methods also include ion exchange resin adsorption as proposed in "a method for treating and recycling wastewater from tantalum-niobium hydrometallurgy" (201410788647.5) and "a method for preparing rare earth polishing powder and recovering ammonium salt from fluorine-containing wastewater from niobium-tantalum" (201510136808.7) and remove fluorine by using rare earth precipitation, but these methods have many problems such as poisoning and aging of resin, rare earth is a key strategic resource in China, and the like, resulting in poor practicability. And the method adopts a passive treatment mode for the process production wastewater, so that the total water consumption of a factory is not reduced, and even some wastewater treatment methods consume a large amount of deionized water, which is extremely unfavorable for the environmental benefit of factory operation.
Disclosure of Invention
The invention aims to provide a recycling and resource treatment method of alkaline wastewater in tantalum-niobium hydrometallurgy, which solves the problems in the background art, can greatly reduce the industrial water consumption of tantalum-niobium hydrometallurgy by recycling the washing wastewater to the maximum extent, can effectively separate and recover valuable elements in the tantalum-niobium hydrometallurgy wastewater, and really realizes zero pollution and zero emission of the alkaline wastewater in the industry.
The technical scheme adopted for achieving the purpose is that the method for recycling and resource treatment of the alkaline wastewater in tantalum-niobium hydrometallurgy is characterized in that the alkaline wastewater in tantalum-niobium hydrometallurgy is ammonia-introduced neutralization mother liquor and washing wastewater thereof; the method comprises the following steps:
(1) recycling washing wastewater: introducing ammonia to neutralize the neutralized mother liquor after precipitating tantalum and niobium and the first washing wastewater to directly enter a magnesium compound precipitation defluorination process; the rest washing wastewater of each time is separately collected, the second washing water is collected and used for the first washing water of the next batch, and the third washing water is collected and used for the second washing water of the next batch, and is sequentially recycled for washing the tantalum-niobium products of the next batch;
(2) precipitation and fluorine removal of magnesium compounds: adding magnesium compound into the mother liquor and the first washing waste water at 50-95 deg.CoC, fully precipitating fluorine to generate magnesium fluoride, and filtering to obtain magnesium fluoride;
(3) concentrating and recovering ammonium sulfate: the solution after separating magnesium fluoride is concentrated and crystallized to recover ammonium sulfate as a byproduct.
Further, the washing water obtained after ammonia is introduced to neutralize and precipitate the tantalum and niobium in the step (1) is separately collected, the washing water is collected according to the second washing water and used for the first washing water of the next batch, and the washing water of the third washing water and used for the second washing water of the next batch are sequentially recycled and used as the washing water of the tantalum and niobium products of the next batch until the washing water is used and fresh purified water is added for washing.
Further, the magnesium compound in the step (2) is derived from various magnesium-containing compounds, and the magnesium-containing compounds are magnesium carbonate, magnesium sulfate, magnesium oxide, magnesium hydroxide or a combination of one or more of magnesite; the addition amount of the magnesium compound is calculated according to the molar ratio of the magnesium compound to the fluorine content in the wastewater of 1:2 to 1.5: 2.
Advantageous effects
Compared with the prior art, the invention has the following advantages.
1. According to the invention, the washing wastewater is recycled, and the magnesium compound is precipitated to remove fluorine and the ammonium sulfate is concentrated and recovered to treat the wastewater, so that the washing water is greatly reduced, valuable elements in the wastewater are completely recovered, and zero pollution and zero discharge of alkaline wastewater in tantalum-niobium hydrometallurgy are really realized;
2. the treatment method provided by the invention has the advantages of simple required equipment, low investment, stable process and easiness in operation, and compared with the prior art, the treatment method provided by the invention is more economic and more environment-friendly, and is more suitable for industrial production.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a process flow chart of the method for recycling alkaline wastewater and treating resources in tantalum-niobium hydrometallurgy.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples, which are only for the purpose of illustrating the present invention and are not to be construed as limiting the scope of the present invention.
A recycling and resource treatment method for alkaline wastewater in tantalum-niobium hydrometallurgy is provided, wherein the alkaline wastewater in tantalum-niobium hydrometallurgy is ammonia-introduced neutralization mother liquor and washing wastewater thereof; as shown in fig. 1, the method comprises the steps of:
(1) recycling washing wastewater: introducing ammonia to neutralize the neutralized mother liquor after precipitating tantalum and niobium and the first washing wastewater to directly enter a magnesium compound precipitation defluorination process; the rest washing wastewater of each time is separately collected, the second washing water is collected and used for the first washing water of the next batch, and the third washing water is collected and used for the second washing water of the next batch, and is sequentially recycled for washing the tantalum-niobium products of the next batch;
(2) precipitation and fluorine removal of magnesium compounds: adding magnesium compound into the mother liquor and the first washing waste water at 50-95 deg.CoC, fully precipitating fluorine to generate magnesium fluoride, and filtering to obtain magnesium fluoride;
(3) concentrating and recovering ammonium sulfate: the solution after separating magnesium fluoride is concentrated and crystallized to recover ammonium sulfate as a byproduct.
And (2) separately collecting the washing water after ammonia is introduced to neutralize and precipitate the tantalum and niobium in the step (1), collecting the washing water for the first time of the next batch according to the second washing water, and sequentially recycling the washing water for the second time of the next batch for the washing water of the tantalum and niobium product of the next batch until the washing water is used and then adding fresh purified water for washing.
The magnesium compound in the step (2) is derived from various magnesium-containing compounds, and the magnesium-containing compounds are magnesium carbonate, magnesium sulfate, magnesium oxide, magnesium hydroxide or one or a combination of more of magnesite; the addition amount of the magnesium compound is calculated according to the molar ratio of the magnesium compound to the fluorine content in the wastewater of 1:2 to 1.5: 2.
Example 1
Weighing 500 mL of niobium return water solution, neutralizing with NH3, filtering the obtained precipitate, washing with 50 mL of deionized water each time, combining the filtered neutralization mother liquor and the wastewater generated by the first washing, directly entering the next magnesium compound precipitation defluorination process, and separately collecting the rest wastewater generated by the second, third and sixth washing in different containers marked as A, B, C, D, E; detecting that the neutralization mother liquor obtained by filtering and the first washing wastewater contain F-7500 mg/L and NH 3-N13000 mg/L, adding magnesium sulfate into the neutralization mother liquor at normal temperature to generate magnesium fluoride precipitate, heating to 75 ℃ until the reaction is complete, aging for 2 hours, filtering and drying to obtain a magnesium fluoride byproduct, detecting that the filtrate contains F-5 mg/L and NH 3-N12400 mg/L, distilling, crystallizing, and centrifuging to obtain an ammonium sulfate byproduct.
The total amount of deionized washing water is 500 mL, and the content of the magnesium fluoride product is 99.2 percent by analysis; the content of the ammonium sulfate product is 99.6 percent by analysis.
Example 2
Weighing 500 mL of returned niobium aqueous solution, neutralizing with NH3, filtering the obtained precipitate, washing with wastewater in a container A, combining the wastewater generated this time with a neutralization mother liquor, directly entering the next magnesium compound precipitation defluorination process, continuing to wash for the second time with wastewater in a container B, washing for the third time with wastewater in a container C until the wastewater in a container D is washed for the fifth time, and finally washing for the sixth time with recovered distilled water, wherein the washing wastewater is still collected in different containers of A, B, C, D, E separately and is sequentially recycled as water for washing products of the next batch. Detecting that the neutralization mother liquor and the first washing wastewater obtained by filtering contain F-7520 mg/L and NH 3-N13180 mg/L, adding magnesium sulfate at normal temperature to generate magnesium fluoride precipitate, heating to 75 ℃ until the reaction is complete, aging for 2 hours, filtering, washing and drying to obtain magnesium fluoride, detecting that the filtrate contains F-7 mg/L and NH 3-N12370 mg/L, distilling, crystallizing and centrifuging to obtain an ammonium sulfate byproduct.
Only a small amount of fresh deionized water is needed, and the content of the magnesium fluoride product is 99.3 percent through analysis; the content of the ammonium sulfate product is 99.5 percent by analysis.
Example 3
500 mL of the returned niobium solution was measured and neutralized with NH3, and the wastewater was washed and treated with wastewater cycles as described in example 2, respectively. The neutralization mother liquor and the first washing wastewater obtained by filtering contain F-7525 mg/L and NH 3-N13195 mg/L, magnesium sulfate is added into the neutralization mother liquor and the first washing wastewater at normal temperature to generate magnesium fluoride precipitate, the temperature is raised to 75 ℃ until the reaction is complete, the magnesium fluoride precipitate is aged for 2 hours, and the magnesium fluoride is obtained by filtering, washing and drying, and the filtered mother liquor and the washing wastewater enter a process of concentrating and recovering ammonium sulfate. The solution obtained after the magnesium fluoride is removed by the filtration contains F-6 mg/L and NH 3-N12540 mg/L through detection, and the solution is distilled, crystallized and centrifuged to obtain an ammonium sulfate byproduct.
Only a small amount of fresh deionized water is needed, and the content of the magnesium fluoride product is 99.1 percent after analysis; the content of the ammonium sulfate product is 99.2 percent by analysis.
Example 4
500 mL of the returned niobium solution was measured and neutralized with NH3, and the wastewater was washed and treated with wastewater cycles as described in example 2, respectively. The neutralization mother liquor and the first washing wastewater obtained by filtering contain F-7534 mg/L and NH 3-N13217 mg/L, magnesium carbonate is added into the neutralization mother liquor and the first washing wastewater at normal temperature to generate magnesium fluoride precipitate, the temperature is raised to 75 ℃ until the reaction is complete, the reaction is aged for 2 hours, and the magnesium fluoride is obtained by filtering, washing and drying, and the filtered mother liquor and the washing wastewater enter a process of concentrating and recycling ammonium sulfate. The solution obtained after the magnesium fluoride is removed by the filtration contains F-5 mg/L and NH 3-N12535 mg/L through detection, and the solution is distilled, crystallized and centrifuged to obtain an ammonium sulfate byproduct.
Only a small amount of fresh deionized water is needed, and the content of the magnesium fluoride product is 99.3 percent through analysis; the content of the ammonium sulfate product is 99.4 percent by analysis.
Example 5
500 mL of the returned niobium solution was measured and neutralized with NH3, and the wastewater was washed and treated with wastewater cycles as described in example 2, respectively. The neutralization mother liquor and the first washing wastewater obtained by filtering contain F-7529 mg/L and NH 3-N13202 mg/L, magnesium oxide is added into the neutralization mother liquor and the first washing wastewater at normal temperature to generate magnesium fluoride precipitate, the temperature is raised to 75 ℃ until the reaction is complete, the reaction is aged for 2 hours, and the magnesium fluoride is obtained by filtering, washing and drying, and the filtered mother liquor and the washing wastewater enter a process of concentrating and recycling ammonium sulfate. The solution obtained after the magnesium fluoride is removed by filtration contains F-7 mg/L and NH 3-N12543 mg/L by detection, and the ammonium sulfate byproduct is obtained by distillation crystallization and centrifugation.
Only a small amount of fresh deionized water is needed, and the content of the magnesium fluoride product is 99.4 percent after analysis; the content of the ammonium sulfate product is 99.3 percent by analysis.
Example 6
500 mL of the returned niobium solution was measured and neutralized with NH3, and the wastewater was washed and treated with wastewater cycles as described in example 2, respectively. The neutralization mother liquor and the first washing wastewater obtained by filtering contain F-7530 mg/L and NH 3-N13198 mg/L, magnesium hydroxide is added into the neutralization mother liquor and the first washing wastewater at normal temperature to generate magnesium fluoride precipitate, the temperature is raised to 75 ℃ until the reaction is complete, the reaction is aged for 2 hours, and the magnesium fluoride is obtained by filtering, washing and drying, and the filtered mother liquor and the washing wastewater enter a process of concentrating and recycling ammonium sulfate. The solution obtained after the magnesium fluoride is removed by the filtration contains F-7 mg/L and NH 3-N12546 mg/L through detection, and the solution is distilled, crystallized and centrifuged to obtain an ammonium sulfate byproduct.
Only a small amount of fresh deionized water is needed, and the content of the magnesium fluoride product is 99.2 percent after analysis; the content of the ammonium sulfate product is 99.1 percent by analysis.
The invention can greatly reduce the consumption of fresh deionized water after adopting the circulating washing. The recycling frequency of the washing wastewater and the quality of the ammonium sulfate prepared by distilling and crystallizing the magnesium fluoride and the ammonium sulfate are not influenced by the variety of the adopted magnesium compound, the whole recovery process has no discharge of waste residues and waste liquid, only two byproducts of the magnesium fluoride and the ammonium sulfate are produced, and the content of the product can reach more than 99 percent and reach the first-grade industrial standard.
Claims (3)
Priority Applications (1)
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