CN103739048A - Defluorination medicine and preparation method thereof - Google Patents
Defluorination medicine and preparation method thereof Download PDFInfo
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- CN103739048A CN103739048A CN201310569409.0A CN201310569409A CN103739048A CN 103739048 A CN103739048 A CN 103739048A CN 201310569409 A CN201310569409 A CN 201310569409A CN 103739048 A CN103739048 A CN 103739048A
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- rare earth
- medicament
- defluorination
- chloride
- wastewater
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- 239000003814 drug Substances 0.000 title claims abstract description 87
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 90
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 42
- 239000002351 wastewater Substances 0.000 claims abstract description 37
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- -1 rare earth chloride Chemical class 0.000 claims description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 48
- 150000002500 ions Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- 239000011737 fluorine Substances 0.000 description 16
- 229910052731 fluorine Inorganic materials 0.000 description 16
- 239000002594 sorbent Substances 0.000 description 12
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 7
- 238000005272 metallurgy Methods 0.000 description 6
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000000274 adsorptive effect Effects 0.000 description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 4
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XIRHLBQGEYXJKG-UHFFFAOYSA-H praseodymium(3+);tricarbonate Chemical compound [Pr+3].[Pr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XIRHLBQGEYXJKG-UHFFFAOYSA-H 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 3
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- BOTHRHRVFIZTGG-UHFFFAOYSA-K praseodymium(3+);trifluoride Chemical compound F[Pr](F)F BOTHRHRVFIZTGG-UHFFFAOYSA-K 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a wastewater defluorination medicine. The defluorination medicine is characterized in that the defluorination medicine contains rare earth elements and also contains polyacrylamide. The defluorination principle of the medicine is characterized in that fluorinions are removed through an ion precipitation method, the fluorinions combine with rare earth element ions to form a fluorinated rare earth precipitate, fluorinated rare earth is insoluble in water, and the fluorinions in water is removed through an ion co-precipitation effect, so the medicine has a very good selectivity, and the generated fluorinated rare earth is recovered to realize rare earth smelting. The defluorination medicine is suitable for removing low concentration fluorinion pollution factors in wastewater, and has the advantages of good defluorination effect, stability and low processing cost, and the generated fluorinated rare earth is recoverable.
Description
Technical field
The present invention relates to a kind of fluoride waste process field, relate in particular to and be specifically related to FLUORIDE REMOVAL IN WASTEWATER medicament and the preparation method that rare-earth compound is main component.
Background technology
Fluorine is one of trace element of needed by human, and the suitable fluorine mass concentration of tap water is 0.5-1.0mg/L.When tap water lacks fluorine, easily suffer from dental caries; If but long-term drinking fluorine mass concentration is higher than the water of 1.0mg/L, can cause dental fluorosis disease; The water that long-term drinking fluorine mass concentration is 3-6mg/L, can cause osteofluorosis.China's Fluorine Containing Groundwater is widely distributed, especially in northwest arid area, approximately has 70,000,000 people to drink the water that fluorine content exceeds standard, and causes fluorosis in various degree.Industrial, in the waste water of the industry such as fluorine-containing ore extraction, Metal smelting, aluminium processing, coke, glass, electronics, plating, chemical fertilizer, agricultural chemicals discharge, often contain the fluorochemical of high density, cause environmental pollution.Defluorinating process research is the important topic of domestic and international environmental protection and health field always.
Fluoride waste, most domestic factory there is no perfect treatment facility at present, and the fluorine in wastewater content discharging exceedes discharging standards, serious environment pollution.According to national sewage comprehensive emission standard, fluorinion concentration should be less than 10mg/L, and in the emission standard of part industry standard or special discharge areas, fluorinion concentration should be less than 2mg/L, and drinking water standard requires fluorinion concentration to require below 1mg/L.Conventional FLUORIDE REMOVAL IN WASTEWATER medicament is roughly divided into two classes, i.e. calcium salt precipitation method defluorination medicament and absorption method defluorination medicament both at home and abroad at present.
Calcium salt mainly contains CaO, CaCl
2, Ca (OH)
2deng, by adding calcium salt, be main pharmaceutical chemicals, form that Calcium Fluoride (Fluorspan) precipitation or Calcium Fluoride (Fluorspan) are adsorbed in formed throw out and coprecipitation.The method is simple, processing is convenient, and expense is low, but lime solubleness is low, can only add with milk sap, and the CaF producing
2precipitation is wrapped in Ca (OH)
2the surface of particle, make it to be fully utilized, thereby consumption is large.Fluorine in wastewater content after treatment generally can only drop to 20-50mg/L, can not reach the primary standard stipulating in < < integrated wastewater discharge standard > >.And existing body refuse sedimentation slow, dehydration difficulty, processes the large volume exhaust thing cycle long, the shortcomings such as the inadaptable continuous blow-down of processing continuously.
Absorption method defluorination medicament mainly contains activated alumina, clinoptilolite, activated magnesia etc., in recent years, has also reported the higher sorbent materials of adsorption capacity of fluoride ion such as hydroxyapatite, zirconium white and cerous hydroxide.Conventional sorbent material is as less of 0.06-2.0mg/g in the fluorine adsorptive capacity of clinoptilolite and activated magnesia, and treatment effect is poor.The fluorine adsorptive capacity of calcium phosphate powder and activated magnesia reaches 3.5-10mg/g, but easily runs off in use procedure.And take cerium and lanthanum as rare earth element hydrous oxide and the rare earth salts of representative, the negatively charged ion such as the fluorine in water, arsenate are had to stronger avidity, thereby the sorbent material take rare earth element as main adsorption component, because its adsorptive capacity is large, pollute the little and easy to operate concern both domestic and external that obtained.Rare earth element is to be caused by the relevant protonation reaction of its surface hydroxyl as the ion-exchange of sorbent material to adsorption property, and its defluorination mechanism is all the F in coordinated water and the solution on metal ion
-exchange, and most rare earth as sorbent material be all by rare earth loaded on the fibrous material of high surface area, because Fibriform adsorbents has larger specific surface area and stronger physical strength, and the coordination ability of rare earth and F-is strong, so in conjunction with making rare-earth oxide there is higher loading capacity to the fluorion in water, stronger adsorption selectivity, sorbent material fluorine adsorptive capacity reaches 30mg/g.
Rare earth class sorbent material, protonation reaction is only surface adsorption and expensive, although can regenerate, regeneration effect is general, processing cost is high.The sorbent material of reporting in addition the carrier surface carrier band cerous hydroxides such as aluminium or titanium is better to fluorion adsorption effect, but no matter which kind of absorption method, rare earth compound is due to its unique fluorine affinity, not only can effectively remove fluorine excessive in water body, can improve traditional filter material surface tissue simultaneously, increase filter material surface adsorption potential, for the removal of other impurity in water, also there is good effect as heavy metal ion and part mineral ion, therefore all cannot carry out the selective adsorption of fluorion, the adsorption efficiency of sorbent material is lower, especially when waste water contains oily substance, during organic pollution materials, sorbent material can be saturated rapidly, almost cannot normally work.Therefore use sorbent material to carry out defluorination processing, cost costliness, regeneration difficulty and be subject to the condition restriction of other pollution factor in waste water while using cannot normally be used in production reality.
Summary of the invention
For above-mentioned the deficiencies in the prior art, it is the defluorination medicament of main component that the object of the invention is to provide a kind of rare earth compound, with and preparation method thereof, be applicable in waste water, the removal of the low dose fluoride ionic soil factor, be characterized in that defluorination effect is good and stable, processing cost is low, and the rare earth fluoride of generation is recyclable.
The problem existing for solving above-mentioned prior art, reaches described object, and the technical scheme that the present invention takes is: a kind of FLUORIDE REMOVAL IN WASTEWATER medicament, it is characterized in that, and in described defluorination medicament, contain rare earth element.
Further, described rare earth element is rare earth chloride or carbonated rare earth.
Further, the defluorination medicament that described rare earth chloride forms is the aqueous solution, and rare earth chloride accounts for the 1-65% of defluorination medicament total mass, is preferably 5-10%, the preferred Lanthanum trichloride of described rare earth chloride, Cerium II Chloride, praseodymium chloride or Neodymium trichloride.
Further, the defluorination medicament that described carbonated rare earth forms is Powdered, and carbonated rare earth accounts for defluorination medicament total mass: be more than or equal to 80%, and be less than 100%, described carbonated rare earth is preferably Phosbloc, cerous carbonate, praseodymium carbonate or neodymium carbonate.
Further, in described defluorination medicament, also contain polyacrylamide, quality is 0.1 ‰-1 ‰ of defluorination medicament total mass.
Further, the addition of described polyacrylamide: massfraction is 0.1 ‰-0.2 ‰ in the defluorination medicament that contains rare earth chloride, the massfraction in the defluorination medicament that contains carbonated rare earth is 0.5 ‰-1 ‰.
The preparation method of the defluorination medicament that a kind of rare earth chloride forms is as follows:
(1) according to the massfraction preparation re chloride of 1-65%, and mix;
(2) in the re chloride described in step (1), by 0.1 ‰ of gross weight-0.2 ‰, add flocculation agent, mix, making rare earth chloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
The preparation method of the defluorination medicament defluorination medicament that a kind of carbonated rare earth forms is as follows:
The carbonated rare earth of described dosage ratio is mixed with polyacrylamide, stir.
A kind of rare earth chloride form the using method of defluorination medicament: fluoride waste water inlet fluorinion concentration is lower than 50mg/L, pH value is controlled at neutral 7 left and right, according to the mass ratio 0.24-0.25 of fluorion and rare earth chloride, add rare earth chloride defluorination medicament, stir 30min, fully reaction, standing sedimentation 60min, the precipitation of formation is carried out solid-liquid separation after reclaiming, and is further used for rare-earth smelting.
The defluorination medicament using method that a kind of carbonated rare earth forms is as follows:
Fluoride waste fluorinion concentration is lower than 50mg/L, pH value is controlled at 2.5 left and right, according to the mass ratio 0.22-0.29 of fluorion and carbonated rare earth, add carbonated rare earth defluorination medicament, stir 30min, fully reaction, standing sedimentation 60min, carries out solid-liquid separation after the rare earth fluoride precipitation of formation reclaims, and is further used for rare-earth smelting.
Medicament of the present invention, its defluorination principle is to belong to ion precipitation method to remove fluorion, fluorion is combined with rare earth element ion and is formed rare earth fluoride precipitation, rare earth fluoride is water insoluble, by the coprecipitated effect of ion, remove the fluorion in water, therefore have good selectivity, the rare earth fluoride of generation reclaims for rare-earth smelting.Reactional equation is as follows:
F
-+Re
3+→ReF
3
Beneficial effect of the present invention is:
(1) routine of defluorination medicament of the present invention adds, can make waste water fluorinion concentration≤5mg/L after treatment, lower than the first discharge standard (10mg/L is following) of regulation in < < integrated wastewater discharge standard > > (GB8978-2002), lower than the special emission limit stipulating in < < rare-earth industry pollutant emission standard > > (8 mg/L are following).
(2) slightly excessive the adding of defluorination medicament of the present invention, can make waste water fluorinion concentration≤2mg/L after treatment, lower than the special emission limit of fluorion (2 mg/L are following) (10mg/L is following) of regulation in < < copper, nickel, cobalt emission of industrial pollutants standard > > (GB25467-2010).
(3) defluorination medicament of the present invention has selectivity to the removal of fluorinion in waste water, can not be subject in waste water other pollution factor as the impact of the pollution factors such as oil, COD, SS, can realize the fluoride ion removing under non-strong alkaline condition.
(4) defluorination medicament of the present invention is to reach by the coprecipitated mode of ion the object of removing fluorion, rare earth element ion in medicament and fluorion form rare earth fluoride precipitation, rare earth fluoride precipitation is water insoluble, nitric acid, hydrochloric acid, sulfuric acid, and chemical property is highly stable; The rare earth fluoride throw out generating can be back to rare-earth smelting, again make the raw material that rare earth chloride is produced as defluorination medicament after solid-liquid separation, and rare earth element without running off, greatly reduces cost for wastewater treatment in defluorination process.
(5) defluorination medicament of the present invention is applied in FLUORIDE REMOVAL IN WASTEWATER process, when the rare earth fluoride purity that forms under certain waste water quality condition is higher, can be applicable to precursor and produces.
(6) precipitate particles of the formation of the fluorion in this defluorination medicament and waste water rare earth fluoride is thin, the settling time is longer, the present invention has added polyacrylamide as flocculation agent in defluorination medicament, avoid because using inorganic salts flocculation agent, be combined with fluorinion in waste water and form precipitation, cause in rare earth fluoride precipitation and carry a large amount of impurity secretly, be convenient to the recovery of rare earth fluoride, shortened the sedimentary settling time of rare earth fluoride, improved effect of settling, reduce the investment of defluorination precipitation apparatus.
(7) compared with prior art, defluorination medicament of the present invention, the rare earth fluoride precipitation that forms recoverable by rare earth element ion and fluorion is removed fluorion, guaranteeing on water outlet fluorion basis up to standard, can realize the recycling of fluorion, defluorination medicament rare earth elements, the difficult problem such as the use cost costliness having avoided using rare-earth compound as sorbent material being brought, adsorbent reactivation weak effect.
Embodiment
Embodiment 1
Defluorination medicament preparation method of the present invention is as follows:
Raw material: lanthanum chloride solution (content 60%), polyacrylamide (particulate state, content 90%), pure water.
Preparation: the lanthanum chloride solution that (1) water is 60% by content is diluted to 5%, and mixes.
(2) in the lanthanum chloride solution of 5% described in step (1), 0.2 ‰ add polyacrylamide in proportion, mix, and stir 1h, and making Lanthanum trichloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
Be applied to certain rare earth metallurgy degree of depth defluorination, water inlet fluorinion concentration is 48mg/L, and pH value is 7.14, and quantity discharged is 10m
3/ d, adds Lanthanum trichloride defluorination medicament 3.88kg/m
3, water outlet fluorinion concentration is 4.01mg/L, and water outlet pH value is 6.86, and the yield of lanthanum fluoride is 1.26kg/d, and the rate of recovery is 83.4%.
Embodiment 2
Raw material: solution of cerium chloride by oxidation (content 65%), polyacrylamide (particulate state, content 92%), pure water.
Preparation: the solution of cerium chloride by oxidation that (1) water is 65% by content is diluted to 10%, and mixes.
(2) in the solution of cerium chloride by oxidation of 10% described in step (1), 0.1 ‰ add polyacrylamide in proportion, mix, and stir 1h, and making Cerium II Chloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
Be applied to certain rare earth metallurgy degree of depth defluorination, water inlet fluorinion concentration is 44mg/L, and pH is 7.02, and quantity discharged is 12m
3/ d, adds Cerium II Chloride defluorination medicament 1.73kg/m
3, water outlet fluorinion concentration is 3.91mg/L, and pH value is 6.72, and the yield of cerium fluoride is 1.344kg/d, and the rate of recovery is 83.6%.
Embodiment 3
Raw material: praseodymium chloride solution (content 56%), polyacrylamide (particulate state, content 88%), pure water.
Preparation: the praseodymium chloride solution dilution to 5% that (1) water is 65% by content, and mix.
(2) in the praseodymium chloride solution of 5% described in step (1), 0.1 ‰ add polyacrylamide in proportion, mix, and stir 1h, and making praseodymium chloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
Be applied to certain waste gas containing fluoride absorption liquid defluorination, water inlet fluorinion concentration is 52mg/L, and pH is 6.89, and quantity discharged is 10m
3/ d, adds praseodymium chloride defluorination medicament 4.31kg/m
3, water outlet fluorinion concentration is 4.5mg/L, and pH value is 6.52, and the yield of praseodymium fluoride is 1.09kg/d, and the rate of recovery is 85.6%.
Embodiment 4
Raw material: neodymium chloride solution (content 66%), polyacrylamide (particulate state, content 90%), pure water.
Preparation: the neodymium chloride solution that (1) water is 66% by content is diluted to 10%, and mixes.
(2) in the neodymium chloride solution of 10% described in step (1), 0.2 ‰ add polyacrylamide in proportion, mix, and stir 1h, and making Neodymium trichloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
Be applied to certain waste gas containing fluoride absorption liquid defluorination, water inlet fluorinion concentration is 56mg/L, and pH is 6.72, and quantity discharged is 8m
3/ d, adds Neodymium trichloride defluorination medicament 2.3kg/m
3, water outlet fluorinion concentration is 4.8mg/L, and pH value is 6.41, and the yield of neodymium fluoride is 1.17kg/d, and the rate of recovery is 81%.
Embodiment 5
Raw material: lanthanum chloride solution (content 60%), polyacrylamide (particulate state, content 90%), pure water.
Preparation: the lanthanum chloride solution that (1) water is 60% by content is diluted to 1%, and mixes.
(2) in the lanthanum chloride solution of 1% described in step (1), 0.1 ‰ add polyacrylamide in proportion, mix, and stir 1h, and making Lanthanum trichloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
Be applied to certain rare earth metallurgy degree of depth defluorination, water inlet fluorinion concentration is 48mg/L, and pH value is 7.14, and quantity discharged is 10m
3/ d, adds Lanthanum trichloride defluorination medicament 19.4kg/m
3, water outlet fluorinion concentration is 4.21mg/L, and water outlet pH value is 6.92, and the yield of lanthanum fluoride is 1.21kg/d, and the rate of recovery is 80.3%.
Embodiment 6
Raw material: solution of cerium chloride by oxidation (content 65%), polyacrylamide (particulate state, content 92%), pure water.
Preparation: in described 65% solution of cerium chloride by oxidation, 0.2 ‰ add polyacrylamide in proportion, mixes, and stirs 1h, and making Cerium II Chloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component.
Be applied to certain rare earth metallurgy degree of depth defluorination, water inlet fluorinion concentration is 44mg/L, and pH is 7.02, and quantity discharged is 12m
3/ d, adds Cerium II Chloride defluorination medicament 0.27kg/m
3, water outlet fluorinion concentration is 3.96mg/L, and pH value is 6.68, and the yield of cerium fluoride is 1.336kg/d, and the rate of recovery is 80.5%.
Embodiment 7
Raw material: Phosbloc (Powdered, 80%), polyacrylamide (particulate state, 90%)
Ratio according to 0.2 ‰ is mixed Phosbloc with polyacrylamide, stir.
Be applied to certain rare earth metallurgy degree of depth defluorination, water inlet fluorinion concentration is 48mg/L, and pH value is 2.56, and quantity discharged is 10m
3/ d, adds Phosbloc defluorination medicament 0.206kg/m
3, water outlet fluorinion concentration is 4.98mg/L, and water outlet pH value is 5.2, and the yield of lanthanum fluoride is 1.19kg/d, and the rate of recovery is 80.5%.
Embodiment 8
Raw material: cerous carbonate (Powdered, 92%), polyacrylamide (particulate state, 89%)
Ratio according to 0.1 ‰ is mixed cerous carbonate with polyacrylamide, stir.
Be applied to certain rare earth metallurgy degree of depth defluorination, water inlet fluorinion concentration is 44mg/L, and pH is 2.6, and quantity discharged is 12m
3/ d, adds cerous carbonate defluorination medicament 0.161kg/m
3, water outlet fluorinion concentration is 4.2mg/L, and pH value is 5.0, and the yield of cerium fluoride is 1.255kg/d, and the rate of recovery is 82%.
Embodiment 9
Raw material: praseodymium carbonate (Powdered, 99%), polyacrylamide (particulate state, 92%)
Ratio according to 0.1 ‰ is mixed praseodymium carbonate with polyacrylamide, stir.
Be applied to certain waste gas containing fluoride absorption liquid defluorination, water inlet fluorinion concentration is 52mg/L, and pH is 2.53, and quantity discharged is 10m
3/ d, adds praseodymium carbonate defluorination medicament 0.194kg/m
3, water outlet fluorinion concentration is 4.6mg/L, and pH value is 5.19, and the yield of praseodymium fluoride is 1.342kg/d, and the rate of recovery is 81.5%.
Embodiment 10
Raw material: neodymium carbonate (Powdered, 91%), polyacrylamide (particulate state, 90%)
Ratio according to 0.2 ‰ is mixed neodymium carbonate with polyacrylamide, stir.
Be applied to certain waste gas containing fluoride absorption liquid defluorination, water inlet fluorinion concentration is 56mg/L, and pH is 2.42, and quantity discharged is 8m
3/ d, adds Neodymium trichloride defluorination medicament 0.233kg/m
3, water outlet fluorinion concentration is 4.4mg/L, and pH value is 5.2, and the yield of neodymium fluoride is 1.19kg/d, and the rate of recovery is 81.8%.
Claims (9)
1. a FLUORIDE REMOVAL IN WASTEWATER medicament, is characterized in that, in described defluorination medicament, contains rare earth element.
2. FLUORIDE REMOVAL IN WASTEWATER medicament according to claim 1, is characterized in that, described rare earth element be in lanthanum, cerium, praseodymium or neodymium any one or two or more.
3. FLUORIDE REMOVAL IN WASTEWATER medicament according to claim 2, is characterized in that, described rare earth element is at least one in rare earth chloride or carbonated rare earth.
4. FLUORIDE REMOVAL IN WASTEWATER medicament according to claim 3, is characterized in that, the defluorination medicament that described rare earth chloride forms is the aqueous solution, and rare earth chloride accounts for the 1-65% of defluorination medicament total mass.
5. FLUORIDE REMOVAL IN WASTEWATER medicament according to claim 3, is characterized in that, the defluorination medicament that described carbonated rare earth forms is Powdered, and carbonated rare earth accounts for defluorination medicament total mass: be more than or equal to 80%, and be less than 100%.
6. according to the FLUORIDE REMOVAL IN WASTEWATER medicament described in claim 1-5, it is characterized in that, in described defluorination medicament, also contain polyacrylamide, quality is 0.1 ‰-1 ‰ of defluorination medicament total mass.
7. FLUORIDE REMOVAL IN WASTEWATER medicament according to claim 6, it is characterized in that, the addition of described polyacrylamide: massfraction is 0.1 ‰-0.2 ‰ in the defluorination medicament that contains rare earth chloride, the massfraction in the defluorination medicament that contains carbonated rare earth is 0.5 ‰-1 ‰.
8. a preparation method for defluorination medicament claimed in claim 6, is characterized in that,
The preparation method of the defluorination medicament that A. rare earth chloride forms is as follows:
(1) according to the massfraction preparation re chloride of 1-65%, and mix;
(2) in the re chloride described in step (1), by 0.1 ‰ of gross weight-0.2 ‰, add flocculation agent, mix, making rare earth chloride is the FLUORIDE REMOVAL IN WASTEWATER medicament of main component;
The preparation method of the defluorination medicament defluorination medicament that B. carbonated rare earth forms is as follows: the carbonated rare earth of described dosage ratio is mixed with polyacrylamide, stir.
9. the using method of the defluorination medicament that prepared by method claimed in claim 8, is characterized in that,
A. rare earth chloride form the using method of defluorination medicament: pH value is controlled at neutral 7 left and right, according to the mass ratio 0.24-0.25 of fluorion and rare earth chloride, add rare earth chloride defluorination medicament, stir 30min, fully reaction, standing sedimentation 60min, the precipitation forming is carried out solid-liquid separation after reclaiming, and is further used for rare-earth smelting;
B. the defluorination medicament using method that carbonated rare earth forms is as follows: pH value is controlled at 2.5 left and right, according to the mass ratio 0.22-0.29 of fluorion and carbonated rare earth, add carbonated rare earth defluorination medicament, stir 30min, fully reaction, standing sedimentation 60min, after the rare earth fluoride precipitation forming reclaims, carry out solid-liquid separation, be further used for rare-earth smelting.
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