CN109399669A - A method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder - Google Patents
A method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder Download PDFInfo
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- CN109399669A CN109399669A CN201811282610.XA CN201811282610A CN109399669A CN 109399669 A CN109399669 A CN 109399669A CN 201811282610 A CN201811282610 A CN 201811282610A CN 109399669 A CN109399669 A CN 109399669A
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- Prior art keywords
- useless
- product
- complex salt
- water
- tantalum powder
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 69
- 150000003839 salts Chemical class 0.000 title claims abstract description 61
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000006227 byproduct Substances 0.000 title claims abstract description 38
- 239000011734 sodium Substances 0.000 title claims abstract description 38
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 37
- 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 title claims abstract description 36
- 230000009467 reduction Effects 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000012452 mother liquor Substances 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 27
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000001110 calcium chloride Substances 0.000 claims abstract description 19
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 19
- 230000001376 precipitating effect Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- 238000005056 compaction Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- -1 compound salt Chemical class 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 150000002500 ions Chemical class 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000011698 potassium fluoride Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000012047 saturated solution Substances 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000005649 metathesis reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 abstract description 65
- 239000011775 sodium fluoride Substances 0.000 abstract description 32
- 235000013024 sodium fluoride Nutrition 0.000 abstract description 32
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 7
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 7
- 239000004571 lime Substances 0.000 abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 4
- 229940053652 fluorinse Drugs 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 24
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 16
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000011833 salt mixture Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/02—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/28—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- C02F1/52—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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The present invention relates to a kind of methods of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder.The present invention is using tantalum after cooling and compound salt reaction product as raw material, and removing floats on the complex salt by-product that gives up above tantalum powder first, can obtain sodium fluoride precipitating and composite compaction technique after removing the water-soluble filtering of product；Resultant product can obtain closely saturation Fluorinse after ball milling, dissolution after removing, and metal chloride is added after above two solution is merged and carries out precipitation reaction, obtain metal fluoride precipitating and fluorine-containing mother liquor；When using calcium chloride for precipitating reagent, it is mother liquid obtained can direct emission, when the use of magnesium chloride or aluminium chloride being precipitating reagent, mother liquor through after simple purified treatment can direct emission, can arrange mother liquor can carry out reverse osmosis regeneration treatment.The method of the present invention reduces wash water dosage, has recycled value product, solved the problems, such as that lime consumption is big, while being also easy that fluorine ion is made to reach discharge standard, and present invention process step is simple, is suitable for industrial application.
Description
Technical field
The invention belongs to metallurgical technology fields, more particularly to a kind of giving up for processing sodium reduction production tantalum powder is compound
The method of salt by-product and useless wash water.
Background technique
Metal tantalum is that the fields such as aerospace, electronic chip, high-end imaging, high energy equipment, Precision Machining are indispensable
Metal and skeleton replace most excellent metal.The main method for producing metal tantalum is " sodium reduction process ", sodium reduction
Legal system tantalum powder method using metal sodium reduction potassium floutaramite, obtains tantalum powder, by-product is molten mainly using NaCl and NaF as diluent
Salt mixture, metallurgical Ta powder Na reduction reaction formula are as follows:
K2TaF7+ Na+NaCl=Ta+KF+NaF+NaCl
The useless complex salt by-product of sodium reduction production tantalum powder is gained fused salt mixing by-product after sodium reduction legal system tantalum powder.
Appearance is generally white porosity bulk, is mingled with light blue and lavender, corrosivity is strong；Main component be KF, NaCl, NaF and
KCl。
Tantalum and the present processing method of the compound abraum salt mixture of KF+NaF+NaCl+KCl are to use deionization after pulverizing and jevigating
Water-solubleization washes away compound abraum salt, environmentally harmful F ion lime precipitation in the wash water containing complex salt, which exists
Following problems: 1) wash water dosage is very more；2) there is no recovery product；3) lime consumption is very big, and generates a large number of lime slag, makes
The problems such as at stacking, transporting；4) so that waste water is reached discharge standard (F≤10mg/L) sizable difficulty.
Summary of the invention
The technical problem to be solved by the present invention is to the useless complex salt by-product processing for existing sodium reduction production tantalum powder
Wash water dosage present in technique is more, non-recovery product, the problems such as lime consumption is big, discharge of wastewater is up to standard difficult, provides a kind of place
The method for managing the useless complex salt by-product and useless wash water of sodium reduction production tantalum powder.
The purpose of the present invention is achieved by the following technical programs:
There is provided it is a kind of processing sodium reduction production tantalum powder useless complex salt by-product and useless wash water method, specifically include with
Lower step:
S1. it removes: taking tantalum and compound salt reaction product, the complex salt by-product that gives up above tantalum powder will be floated on by the way of removing
The slave reaction product of object picks；The method of the present invention is preferably using the method removed by hand；
S2. it converts: deionized water is added in the useless complex salt removed in step S1 and carries out that double decomposition conversion occurs in ball milling
Reaction, is obtained by filtration NaF product and composite compaction technique；This process be able to achieve KF+NaCl be changed into NaF+KCl double decomposition it is anti-
It answers, so that F ion be allowed to be concentrically formed the low NaF product of solubility；
S3. dissolve: in step S1 it is unstripped go out tantalum and compound salt reaction product, carry out ball milling and water-soluble, be obtained by filtration
Tantalum powder and composite compaction technique, the composite compaction technique are the near saturated solution of NaF；
S4. aqueous solution merges: composite compaction technique obtained by step S2 and step S3 being merged, is the near saturated solution of NaF；
S5. metal chloride precipitates: metal chloride is added as heavy in the near saturated solution of the NaF after step S4 merging
Shallow lake agent carries out precipitation reaction, then filters and elutes, and obtains the mother that metal fluoride precipitating is 1~4000PPM with F ion concentration
Liquid；Most F ions have been settled as value product at this time；
In the technical scheme, when metal chloride uses calcium chloride in step S5, first will before carrying out precipitation reaction
The pH value of mixed solution is adjusted to 9~13, then be added calcium chloride carry out precipitation reaction, obtain metal fluoride precipitating and Han Fu≤
The mother liquor of 10ppm, the fluorine-containing mother liquor adjustment pH can be discharged directly after being 6~9；When precipitating reagent uses other in step S5
When metal chloride, mother liquid obtained middle F ion concentration is 20~4000PPM, needs to continue fluorine-containing mother liquor following S6 purification
Step；
S6. mother liquor purification: the mother liquid obtained pH of step S5 is adjusted to 9~13, appropriate calcium chloride is added and PAC is sunk
It forms sediment and reacts, be separated by filtration to obtain CaF2And CaSO4Mixture precipitation and F Wei≤5PPm tail washings, are adjusted to 6~9 for tail washings pH after filtering,
This tail washings has reached discharge standard, can discharge.
Scientific design production stage of the present invention, the method that use creative first is removed by hand will float on useless above tantalum powder
Complex salt by-product picks, which is potassium fluoride and sodium chloride, such as table Fig. 1 and table 1
Shown, the present invention does not add other and adds using the metathesis reaction and its difference of solubility in water of potassium fluoride and sodium chloride
Add agent, directly carry out water-soluble generation metathesis reaction, the salt-mixture that sodium fluoride product and sodium fluoride saturation is then obtained by filtration is molten
Liquid；Ball milling and water-soluble processing, master in the useless complex salt by-product of residue are carried out to rear remaining useless complex salt by-product is picked by hand
Contain tantalum powder and useless complex salt, ball milling, it is water-soluble after the near saturated solution of sodium fluoride can be obtained；Finally above-mentioned two step is obtained fluorine-containing
The mixing salt solution for changing sodium, which merges, carries out integrated treatment, and the metal chlorides such as calcium chloride, magnesium chloride or aluminium chloride are added and are sunk
It forms sediment and reacts, most fluorine ion settlements are become into value product；At this point, when the metal chloride is calcium chloride,
It is mother liquid obtained without carry out purified treatment can direct emission, when the metal chloride is magnesium chloride or aluminium chloride, gained is female
Liquid need to can direct emission through simple purifying step.Last gained can the tail washings of direct emission recycled using reverse osmosis
Deionized water is produced to reverse osmosis water, then through ion exchange water system, realizes the regeneration cycle of water in present invention process.
The method of the present invention reduces wash water dosage, has recycled value product, solved the problems, such as large quantities of lime slag simultaneously
Also it is easy that fluorine ion is made to reach discharge standard.
The physicochemical properties of the related compound of the present invention of table 1
Preferably, precipitating reagent is one of chloride of calcium metal, aluminium or magnesium or a variety of in step S5.
Preferably, step S1 stripping process, it is preferred to use the mode removed by hand is picked by the way of removing by hand
Useless complex salt accounts for the 1/4~1/2 of all useless complex salt gross masses, and the useless complex salt main ingredient removed by hand is fluorination
Potassium, sodium fluoride and sodium chloride.
Preferably, the mass ratio of step S2 conversion process, complex salt of giving up and deionized water is 1:0.9~1.2, described plus water
Amount is with enough NaCl and KF degree of being dissolved as.
It is further preferred that step S2 conversion process, the useless complex salt picked by hand carries out in ball (stick) grinding machine
Metathesis reaction；Still further preferably the ratio of grinding media to material of ball milling is 1:1.1~1.5, and Ball-milling Time is 0.5~4h.The amount of water
For the potassium fluoride and sodium chloride that can be completely dissolved in abraum salt.
Preferably, step S3 course of dissolution, the complex salt product mixed with tantalum powder that can not picked up by hand is together with tantalum powder
40~100 mesh are milled to, Ball-milling Time is 0.5~1.5h.
It is further preferred that step S3 course of dissolution, remaining ball milling tantalum powder and complex salt product are first molten after the removing
Solution again ball milling or while dissolution while ball milling or ball milling after be redissolved.
Preferably, step S6 mother liquor purification process, the quantity that calcium chloride is added is the 105~110% of theoretical amount, is added
The quantity of PAC is the 1~10% of calcium chloride amount.
Preferably, the invention also includes the regeneration of S7. tail washings: the tail washings that can be discharged that step S5 or S6 are obtained is with reverse osmosis
Method, recycling obtain 75~85% reverse osmosis water better than tap water quality, and the reverse osmosis water is by producing ion exchange
Water system obtains deionized water, realizes that the regeneration cycle of water uses.
It is further preferred that step S7 specifically: reduce Cl using single-stage reverse osmosis-、K+、Na+、Ca2+\Mg2+\Al3 +The content of ion obtains the raw water that ion exchange can be preferably carried out than tap water water number.
Still further preferably, the single-stage reverse osmosis process is reverse osmosis using common commercially available single-stage reverse osmosis equipment
Preceding tail water TDS is 500~2000, reverse osmosis rear Wei≤100 TDS Jiang.
The rod milling technique substitution of equality strength can be used in ball-milling technology involved in present invention process method.
Compared with the prior art, the beneficial effects of the present invention are:
(1) method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder of the invention, solves
The wash water dosage that the prior art produces tantalum powder is more, non-recovery value product, generates the problems such as large quantities of lime slag, meanwhile, lead to
Control process conditions are crossed to be easy to that F ion is made to reach discharge standard (F≤10mg/L).It is high fluorine-containing during present invention process
Simultaneously the waste water containing potassium, chloride ion by be converted into after recycling fluorination product salt low fluorine containing potassium, chlorine, calcium/or magnesium/or aluminium ion
Waste water, it is mother liquid obtained after precipitation reaction directly to arrange without carrying out purified treatment when the metal chloride is calcium chloride
It puts, it is mother liquid obtained after precipitation reaction to be through simple purifying step when the metal chloride is magnesium chloride or aluminium chloride
Can direct emission, the mother liquor or tail washings that can finally discharge use reverse osmosis-ion-exchange reclaiming, the circulation of water can be made
Utilization rate reaches 80% or more.
(2) present invention using sodium reduction production tantalum powder the different poor solubility of useless complex salt by-product each component away from compared with
Big feature implements the valuable recycling to main nuisance F ion step by step, can produce NaF CaF2Or NaF/AlF3
(MgF2) product.Wherein CaF2、AlF3、MgF2Three kinds can only choose any one kind of them, from value, AlF3>MgF2>CaF2, from operation
From the point of view of defluorination effect, using NaF CaF2Technique is preferable.
Detailed description of the invention
Attached drawing 1 is in kind after the tantalum of sodium reduction production tantalum powder in the embodiment of the present invention 1 and the cooling of compound salt reaction product
Figure.
Attached drawing 2 is the method for useless complex salt by-product and useless wash water that a kind of processing sodium reduction of the present invention produces tantalum powder
Process flow diagram.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, it is no intended to limit of the invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1
The present embodiment is specially a kind of method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder.
The present embodiment experimental raw are as follows: 200kg K2TaF7Sodium reduction reaction is carried out with 60kgNa and 75kgNaCl, obtains reaction product tantalum
And complex salt, it is solid, gross weight 335kg, as shown in Figure 1, part complex salt floats to the upper of reaction product after the product is cooling
Face.As shown in Fig. 2, the method for producing the useless complex salt by-product and useless wash water of tantalum powder for a kind of processing sodium reduction of the present embodiment
Process flow diagram, the present embodiment concrete operations are as follows:
S1. remove: removing picks upper layer by hand, weighs the useless complex salt weight 68kg picked, picks product detection to this
It knows to contain NaCl 31.1%, KF 24.5%, NaF 44.4%；
S2. convert: take the useless complex salt removed by hand to be crushed 50kg, add 66L deionized water, in the machine with stick: expect be
1:2 rod milling 3 hours, readily soluble NaCl and KF double decomposition during water mill were converted into the NaF and readily soluble KCl of indissoluble；By object
Material is discharged into filter filtering, then is eluted once with a small amount of deionized water, then by drying materials, 30kgNaF product is obtained, through lake
Southern chemical products quality supervision center analysis, NaF content reach 95%, and the NaF rate of recovery has reached 96.46% in the present embodiment；Filtering
Solution afterwards is the saturated solution of the NaF containing NaCl, KCL；
S3. it dissolves: taking the mixture 267kg of the useless complex salt and tantalum powder that can't check by hand, wherein the quality of tantalum powder is
92.32kg；It is crushed and is crushed together, then carry out ball milling to 60 mesh, Ball-milling Time about 30 minutes, add deionized water 2700L,
12 hours dissolution complex salts are stirred, are filtered into tantalum powder and composite compaction technique that NaF is closely saturated；
S4. aqueous solution merges: the composite compaction technique that the NaF of the saturated solution of the NaF of step S2 and step S3 is closely saturated
Merging is transferred in another stirred tank；
S5. metal chloride precipitates: being gradually added calcium chloride (anhydrous meter) 143.35kg under stirring, stirring allows chlorination for 3 hours
Calcium sufficiently dissolves and is converted into precipitating；It is put into filter to be filtered, filter cake is eluted with 10L deionized water, and drying obtains CaF2
Product 98.6kg；Precipitate C aF2Mother liquor sampling analysis F ion concentration, be 7.1mg/L；Can direct emission, the present embodiment is not necessarily to
Carry out step S6 mother liquor purification step.
S7. reverse osmosis regeneration treatment: S5 precipitate C aF is taken2Mother liquor take 1000ml, measuring TDS is 1600, and conductivity is
3200us/cm carries out the reverse osmosis test of single-stage, obtains 760ml reverse osmosis water outlet, and measuring TSD is 45, conductivity 90us/cm.
Water quality is better than the water quality of local tap water (conductivity is 150~270 μ s/cm), can recycle substitution tap water and go for producing
Ionized water.
Embodiment 2
The present embodiment is specially a kind of method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder,
As shown in Fig. 2, the method for the useless complex salt by-product and useless wash water of tantalum powder is produced for a kind of processing sodium reduction of the present embodiment
Process flow diagram.
The present embodiment is using raw material, step S1~step S4 with embodiment 1, and specific step is as follows for other:
S5. metal calcium precipitation: after merging is sufficiently stirred in step S4 merging solution, 920ml NaF content is taken
The near saturated solution of 37.83g/L, is added 94.724g calcium chloride (containing 6 crystallizations water), and precipitating, filtering, elution, drying obtain
31.14g CaF2Product, the F ion rate of recovery are up to 96.35%；Heavy CaF2Mother liquor 1.51mg/L containing F ion, lower than country
The discharge standard of 10mg/L, can direct emission；
S6. mother liquor purification: above-mentioned mother liquor adds 4g calcium chloride again and 0.4gPAC precipitates F ion, in the waste liquid after precipitating fluorine from
Son is reduced to 1.03mg/L, the more below discharge standard of country 10mg/L, but the range of decrease is little, illustrates using 1 method of embodiment, once
Precipitating can make wastewater to reach standard.
Embodiment 3
The present embodiment is specially a kind of method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder,
As shown in Fig. 2, the method for the useless complex salt by-product and useless wash water of tantalum powder is produced for a kind of processing sodium reduction of the present embodiment
Process flow diagram.
The present embodiment raw material, step S1~step S4 are with embodiment 1, and specific step is as follows for other:
S5. metal magnesium salts precipitates: after merging is sufficiently stirred in step S4 merging solution, taking 920ml NaF content
29g MgCl is added in the near saturated solution of 37.83g/L2, precipitating, filtering, elution, drying obtain 23.68gMgF2Product, F from
The sub- rate of recovery is 96.40%, heavy MgF2Mother liquor fluoride ion 32.3mg/L；
S6. mother liquor purification: appropriate NaOH solution tune pH to 10 is added into mother liquor described in step S5, adds 4g calcium chloride
Precipitation reaction is carried out with adding 0.4g PAC to precipitate F, is separated by filtration to obtain precipitating and tail washings；Tail washings contains F-For 4.3mg/L, it is lower than country
Discharge standard 10mg/L, can direct emission.
Embodiment 4
The present embodiment is specially a kind of method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder,
As shown in Fig. 2, the method for the useless complex salt by-product and useless wash water of tantalum powder is produced for a kind of processing sodium reduction of the present embodiment
Process flow diagram.
The present embodiment raw material, step S1~step S4 are with embodiment 1, and specific step is as follows for other:
S5. Metal aluminum salt precipitates: after merging is sufficiently stirred in step S4 merging solution, taking 920ml NaF content
40g AlCl is added in the near saturated solution of 37.83g/L3(excessive 8.46%, disregard the crystallization water), precipitating, elution, are dried at filtering
It is dry, obtain 40.01g AlF3(AlF3.3H2O content 93%) product.AlF3Sediment is colloidal state, it is extremely difficult to be filtered, this implementation
In example, the F ion rate of recovery is 97.58%, heavy AlF3Mother liquor fluoride ion 3680mg/L；
S6. mother liquor purification: toward precipitate A lF described in step S53Mother liquor 13.12g calcium chloride and 2.05gPAC is added into one
Step precipitates F ion, and it is 1.88mg/L that F ion is contained in last solution, is substantially lower than the discharge standard of country 10mg/L.
It should be understood that in 2~embodiment of embodiment 4 after step S6 mother liquor purification to the tail washings or mother liquor that can be discharged also
The reverse osmosis regeneration treatment of step S7. as described in example 1 above can be carried out, deionized water is translated into, realizes deionized water
Regeneration cycle use.
From embodiment 1 to embodiment 4 it follows that the present invention produces the useless complex salt by-product of tantalum powder using sodium reduction
The different poor solubility of each component implements the valuable recycling to main nuisance F ion, Ke Yisheng step by step away from larger feature
Output NaF CaF2Or NaF/AlF3(MgF2) product.Wherein CaF2、AlF3、MgF2Three kinds are chosen any one kind of them, from value,
AlF3>MgF2>CaF2, from operate and defluorination effect from the point of view of, using NaF CaF2Technique is best.
Claims (10)
1. a kind of method of the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder, which is characterized in that specific
The following steps are included:
S1. it removes: taking tantalum and compound salt reaction product, the complex salt by-product that gives up will be floated on above tantalum powder after cooling and picks removing；
S2. it converts: deionized water ball milling is added in the useless complex salt removed in step S1 and carries out metathesis reaction, is obtained by filtration
NaF product and composite compaction technique；
S3. dissolve: remaining tantalum and compound salt reaction product of giving up carry out ball milling and water-soluble, mistake after dissolution after removing in step S1
Filter obtains tantalum powder and composite compaction technique；
S4. aqueous solution merges: composite compaction technique obtained by step S2 and step S3 being merged, obtained mixed solution is the close of NaF
Saturated solution；
S5. metal chloride precipitates: metal chloride is added in the mixed solution after step S4 merging and is precipitated as precipitating reagent
Then reaction is filtered and is eluted, metal fluoride precipitating and fluorine-containing mother liquor are obtained；
When step S5 metal chloride is calcium chloride, mixed solution pH is first adjusted to 9~13 before carrying out precipitation reaction, then
Calcium chloride is added and carries out precipitation reaction, obtains metal fluoride precipitating and micro- fluorine mother liquor, the micro- fluorine mother liquor acid adjustment pH for 6~
It can direct emission after 9；When step S5 metal chloride is other metal chlorides, need to carry out following S6 purification to fluorine-containing mother liquor
Step；
S6. mother liquor purification: being adjusted to 9~13 for the mother liquid obtained pH of step S5, be added appropriate calcium chloride and PAC precipitate it is anti-
It answers, is separated by filtration to obtain CaF2、CaSO4Mixture precipitation and the dense degree of F ion≤5PPm tail washings, are adjusted to 6~9, Ji Kepai for tail washings pH
It puts.
2. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 1,
It is characterized in that, precipitating reagent is one of chloride of calcium metal, aluminium or magnesium or a variety of in step S5.
3. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 1,
It is characterized in that, step S2 conversion process, the useless complex salt of the removing and the volume ratio of deionized water are 1:0.9~1.2.
4. the useless complex salt by-product of processing sodium reduction production tantalum powder according to claim 1 or 3 and the side of useless wash water
Method, which is characterized in that step S2 conversion process, it is anti-that the useless complex salt of the removing carries out double decomposition during adding water polo grinding machine
It answers, the amount of water is the potassium fluoride and sodium chloride that can be completely dissolved in abraum salt.
5. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 4,
It is characterized in that, the ratio of grinding media to material of the ball milling is 1:1.1~1.5, ball milling converts the double decomposition time as 0.5~4h.
6. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 1,
It is characterized in that, step S3 course of dissolution, remaining tantalum powder and complex salt product are milled to 40~100 mesh after removing, when ball milling
Between be 0.5~1.5h.
7. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 1,
It is characterized in that, step S6 mother liquor purification process, the quantity that calcium chloride is added is the 105~110% of theoretical amount, is added PAC's
Quantity is the 5~20% of calcium chloride amount.
8. described in any item processing sodium reductions produce the useless complex salt by-product of tantalum powders and give up and wash according to claim 1~7
The method of water, which is characterized in that further include the regeneration of S7. tail washings: the tail washings that can be discharged that step S5 or S6 are obtained is with reverse osmosis
Method, recycling obtain reverse osmosis water, and the reverse osmosis water obtains deionized water by producing ion exchange water system, realizes water
Regeneration cycle uses.
9. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 8,
It is characterized in that, step S7 specifically: reduce Cl in solution using single-stage reverse osmosis-、K+、Na+、Ca2+\Mg2+\Al3+From
The content of son, obtains the raw water that can carry out ion exchange.
10. the method for the useless complex salt by-product and useless wash water of processing sodium reduction production tantalum powder according to claim 9,
It is characterized in that, the single-stage reverse osmosis process, using common commercially available single-stage reverse osmosis equipment, reverse osmosis preceding tail water TDS is
500~2000, reverse osmosis rear Wei≤100 TDS Jiang.
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| CN112358104A (en) * | 2020-09-28 | 2021-02-12 | 稀美资源(广东)有限公司 | Wastewater and waste residue recycling treatment system and method in tantalum powder smelting production |
| CN114988454A (en) * | 2022-02-22 | 2022-09-02 | 西安交通大学 | Resource utilization method and system for halogen mixed salt waste residues |
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| CN102352444A (en) * | 2011-05-30 | 2012-02-15 | 宁夏东方钽业股份有限公司 | Method for producing compound salts by tantalum metallurgy byproducts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102352444A (en) * | 2011-05-30 | 2012-02-15 | 宁夏东方钽业股份有限公司 | Method for producing compound salts by tantalum metallurgy byproducts |
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| CN112358104A (en) * | 2020-09-28 | 2021-02-12 | 稀美资源(广东)有限公司 | Wastewater and waste residue recycling treatment system and method in tantalum powder smelting production |
| CN114988454A (en) * | 2022-02-22 | 2022-09-02 | 西安交通大学 | Resource utilization method and system for halogen mixed salt waste residues |
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