WO2004043862A1 - Procede de lixiviation d'elements de valeur de beryllium au moyen d'acide fluorhydrique - Google Patents
Procede de lixiviation d'elements de valeur de beryllium au moyen d'acide fluorhydrique Download PDFInfo
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- WO2004043862A1 WO2004043862A1 PCT/IL2003/000954 IL0300954W WO2004043862A1 WO 2004043862 A1 WO2004043862 A1 WO 2004043862A1 IL 0300954 W IL0300954 W IL 0300954W WO 2004043862 A1 WO2004043862 A1 WO 2004043862A1
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- WIPO (PCT)
- Prior art keywords
- beryllium
- reacting
- fluorine
- process according
- containing compound
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- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 113
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 70
- 238000002386 leaching Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011737 fluorine Substances 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000012736 aqueous medium Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims description 60
- 229910052614 beryl Inorganic materials 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 42
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 229960002050 hydrofluoric acid Drugs 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 14
- 239000002775 capsule Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- QZVSYHUREAVHQG-UHFFFAOYSA-N diberyllium;silicate Chemical compound [Be+2].[Be+2].[O-][Si]([O-])([O-])[O-] QZVSYHUREAVHQG-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052842 phenakite Inorganic materials 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001573 beryllium compounds Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- 208000023355 Chronic beryllium disease Diseases 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 2
- 208000019693 Lung disease Diseases 0.000 description 2
- 229910004014 SiF4 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- -1 bertrandite Inorganic materials 0.000 description 2
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 2
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 2
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000001684 chronic effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 206010016256 fatigue Diseases 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- 206010001488 Aggression Diseases 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 206010008479 Chest Pain Diseases 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000004596 appetite loss Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 1
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NJJFVOQXYCEZLO-UHFFFAOYSA-N dialuminum;triberyllium;dioxido(oxo)silane Chemical compound [Be+2].[Be+2].[Be+2].[Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O NJJFVOQXYCEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 208000017574 dry cough Diseases 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 208000019017 loss of appetite Diseases 0.000 description 1
- 235000021266 loss of appetite Nutrition 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- JTDPJYXDDYUJBS-UHFFFAOYSA-N quinoline-2-carbohydrazide Chemical compound C1=CC=CC2=NC(C(=O)NN)=CC=C21 JTDPJYXDDYUJBS-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000037390 scarring Effects 0.000 description 1
- 208000013220 shortness of breath Diseases 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B35/00—Obtaining beryllium
-
- 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
- C01F3/00—Compounds of beryllium
- C01F3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method of leaching beryllium values from beryllium-containing ores using a fluorine-containing compound in an acidic aqueous medium.
- Beryllium (Be) is one of the lightest of all metals and has one of the highest melting points of any light metal.
- Beryllium metal and its alloys are used principally in aerospace and defense applications because of its stiffness, low specific gravity, and dimensional stability over a wide temperature range.
- Beryllium metal is stiffer than 1010 steel, and is also highly conductive.
- Beryllium and alloys thereof are often the preferred materials for electronic equipment.
- Beryllium-copper alloys are used in a variety of applications because of their electrical and thermal conductivity, high strength and hardness, good corrosion resistance and fatigue resistance, and nonmagnetic properties.
- Beryllium oxide is an excellent heat conductor, with high strength and hardness, and acts as an electrical insulator in some applications.
- beryllium is extracted from mineral ores, primarily from beryl, bertrandite and phenakite.
- the composition of beryl is 3BeO-Al 2 ⁇ 3 -6Si0 2 .
- Commercial Beryl contains about 12% BeO, which is close to the theoretical composition of beryl (14% BeO).
- the composition of bertrandite is 4BeO-2Si0 2 ⁇ ?0, which, according to the theoretical chemical composition, contains 42% BeO.
- Commercially-available bertrandite contains only about 0.6%-0.9% BeO.
- the commercially-available beryl is almost a pure mineral
- the commercially-available bertrandite contains only 1.0-1.5% of the pure bertrandite, admixed with additional minerals such as aluminum and iron oxides, calcium and alkali oxides or silicates and quartz.
- boiling sulfuric acid is used to dissolve the bertrandite, along with various oxide impurities (e.g., aluminum, iron) typically present in the commercial ore.
- oxide impurities e.g., aluminum, iron
- the solution is filtered to remove any insoluble silica from the solution.
- bertrandite as a feed material is that commercially- available bertrandite contains less than 1 % BeO, i.e., only 5-8% of the BeO content of commercially-available beryl.
- alkali treatment finely ground beryl is heated until fusion or sintered- below the melting point with a sufficient quantity of alkaline flux.
- Suitable alkali compounds include hydroxides or carbonates of sodium, potassium and calcium; mixtures of these carbonates; calcium oxide; borax; lead chloride; and sodium sulfate and charcoal.
- the ratio of flux to beryl depends on the operating conditions, especially the temperature: the higher the temperature the less flux.
- gas-heated or oil-heated rotary furnaces or blast furnaces are suitable.
- Rotary kilns, muffle furnaces, or tunnel kilns are used for sintering.
- the beryl In the heat treatment, the beryl is melted, without additives, at a temperature exceeding 1650°C. and then quenched in water. After this treatment, about 50-60% of the beryl has an enhanced solubility in sulfuric acid. The rest of the beryllium oxide forms a solid solution with silicon dioxide that is not attacked by sulfuric acid. At 900°C this solid solution separates into beryllium oxide and silicon dioxide components, hence, a second heat treatment at this high temperature produces a free beryllium oxide that is soluble in sulfuric acid.
- the obtained powder After cooling and grinding to 200 mesh, the obtained powder is heated to 250°C to 300°C in concentrated sulfuric acid, reacting so as to convert the beryllium, aluminum, and any iron, to soluble sulfates.
- the silica fraction largely remains in the dehydrated, water insoluble form. This two-stage heat treatment typically renders soluble a total of about 90% of the beryl.
- the heat-treated beryl is extracted with hot concentrated sulfuric acid, whereas alkali-treated beryl is extracted with cold sulfuric acid. While in the alkali process, there are relatively low heating costs, the total consumption of acid is considerably greater because of the alkali added.
- the insoluble silicon dioxide is separated by filtration.
- the filtrate contains not only beryllium and aluminum sulfate but also considerable quantities of iron sulfate and smaller amounts of other impurities, all of which must be removed before the precipitation of beryllium hydroxide.
- Many separation processes are known, including alum separation, ammonium carbonate separation, and chelate separation.
- beryl is melted or sintered with sodium hexafluorosilicate at approximately 700°C, according to the stoichiometry of the following equation: 2 (3BeO-Al 2 O 3 -6SiO 2 ) + 6Na 2 SiF 6 ⁇ 6Na 2 BeF 4 + 2Al 2 O 3 -+ 15SiO 2 + 3SiF (1)
- A4, p.18 are hydrogen fluoride gas at 630°C, molten fluorides, other fluorosilicates, or silicon tetrafluoride.
- Rotary kilns are used for reaction with the gases (hydrogen fluoride, silicon tetrafluoride); the solid mixtures (molten fluorides, other fluorosilicates) are briquetted and sintered in muffle furnaces or tunnel kilns. All of these processes are gas-phase or molten-phase processes conducted at extremely high temperatures and requiring expensive equipment.
- U.S. Patent No. 3,375.060 to Olson, et al. discloses a method of solubilizing beryllium values in a mineral by reacting the mineral with fl ⁇ orite (CaF 2 ) and sulfuric acid. The reaction takes place at a temperature of 200°C - 300°C and atmospheric pressure. The products of the reaction are gaseous hydrogen fluoride and a salt cake containing water soluble beryllium sulfate along with calcium sulfate, aluminum sulfate, iron sulfate and various impurities. Separation of beryllium values from the solid calcium sulfate is subsequently performed by leaching with water.
- U.S. Patent No. 3,375,060 to Zimmermann teaches a method of decomposing beryl and beryl-containing minerals by reacting- powdered beryl with gaseous hydrogen fluoride at 100°C - 900°C. Preferably, the reaction is performed at 500°C - 600°C.
- the products of the reaction are SiF 4 vapor (which is condensed with water to produce Si0 2 ) and a cake containing water-soluble beryllium fluoride along with aluminum fluoride, iron fluoride and various impurities. Separation of beryllium values from the cake is subsequently performed by leaching with hot water.
- the main disadvantages in the above-described process relate to the use of hydrogen fluoride in the vapor phase. Operation at elevated temperatures of 100°C - 900°C, and preferably, at 500°C - 600°C, requires extremely high pressures, tremendous superheating, or both. In the case of superheating, an extremely large reaction volume is required. Operation at elevated pressures requires special equipment. In particular, operation above about 200°C requires exotic materials of construction that render the process impractical.
- the present invention is a production process for treating a beryllium feed material, such as beryl, by reacting the beryllium feed material with a fluorine- containing compound in an acidic aqueous medium.
- a production process for dissolving beryllium in a beryllium feed source by means of a fluorine-containing compound in an aqueous medium including the steps of: (a) providing the beryllium feed source; (b) reacting the beryllium feed source with the fluorine-containing compound in a reaction stage to produce dissolved beryllium values in the aqueous medium, and (c) processing the dissolved beryllium values to produce a refined beryllium-containing product.
- the fluorine-containing compound is an active fluorine-containing compound.
- the fluorine-containing compound is a major component.
- the fluorine-containing compound includes hydrofluoric acid. According to still further features in the described preferred embodiments, the fluorine-containing compound includes hydrofluoric acid. According to still further features in the described preferred embodiments, the reacting is performed at a pressure exceeding a pressure of one atmosphere absolute ( 1 ata).
- the reacting is performed at a pressure exceeding a pressure of 1.5 atmospheres absolute (1.5 ata).
- the reacting is performed at a pressure exceeding a pressure of two atmospheres absolute (2 ata). According to still further features in the described preferred embodiments, the reacting is performed at a pressure exceeding a pressure of three atmospheres absolute (3 ata).
- the fluorine-containing compound includes silicon tetrafluoride.
- the aqueous medium is an acidic aqueous medium.
- the reaction stage yields a solid residue along with the aqueous medium
- the process further including the step of: (d) separating at least a portion of the aqueous medium from the solid residue.
- the beryllium feed source includes beryl.
- the beryl is directly introduced to the reaction stage.
- the reacting is performed at a temperature below 250°C.
- the reacting is performed at a temperature below 220°C.
- the reacting is performed at a temperature below 180°C. According to still further features in the described preferred embodiments, the reacting is performed at a temperature below 150°C.
- the process further includes the step of: (d) introducing a second beryllium source, prior to step (c). so as to dissolve additional beryllium values and to consume at least a portion of any excess acid from step (b).
- the second beryllium source includes a readily soluble beryllium feed source.
- the second beryllium source is a readily soluble beryllium feed source.
- the reacting is performed in a vessel that is fl ⁇ idly sealed from an outside environment.
- reaction stage is performed at a temperature above 120°C and below 350°C.
- Figure 1 is a block diagram of the inventive method for processing a beryllium feed source in an aqueous medium by means of a fluorine-containing acid such as hydrofluoric acid. DESCRIPTION OF THE PREFERRED EMBODIMENTS
- the present invention is a method of treating a beryllium feed material, such as beryl, by reacting the beryllium feed material with a fluorine-containing compound in an acidic aqueous medium.
- the beryllium feed source 6 largely or completely dissolves, leaving the highly soluble beryllium values (largely) in the liquid phase. Most of the other species are also dissolved in the liquid phase. If necessary, the reaction product mixture 18 produced in reaction stage 10 is subsequently subjected to a solid/liquid separation 20, to produce a residue 14 and a beryllium-rich solution 16. Residue 14 may be processed for further retrieval of beryllium values, or may be discarded. It must be emphasized that the production process of the present invention is appropriate for both batch and continuous modes of operation.
- beryllium feed source 6 is a commercially-available ore containing beryl (3BeO-Al 2 ⁇ 3 -6Si0 2 ). bertrandite (4BeO-2SiO?-H 2 0), and/or phenakite (Be 2 Si0 4 ). Often, such commercially-available ores include additional minerals containing aluminum and iron oxides, calcium and alkali oxides or silicates and quartz. In reaction stage 10, various aluminum, silica, and iron-based minerals from beryllium feed source 6 tend to dissolve.
- beryl is known to be the most difficult to dissolve.
- beryllium feed source 6 will refer specifically to beryl.
- sulfuric acid 12 may be added to reaction stage 10 to promote the dissolution of beryllium feed source 6, the addition of sulfuric acid 12 has been found to be unnecessary, as the dissolution proceeds essentially to completion at atmospheric or near-atmospheric pressures and at a temperature of about 100°C.
- the temperature in the reaction stage is at least S0°C. and more preferably. above about 100°C.
- hydrofluoric acid reacts with SiO? values to produce fluosilicic acid (H 2 SiF 6 ) and water according to the following stoichiometry:
- Reaction stage 10 can be operated such that vapor stream 13, which may contain hydrofluoric acid, silicon tetrafluoride and water, is removed from reaction stage 10. Alternatively, vapor stream 13 can be refluxed back to the reaction mixture in reflux stream 15.
- the dissolution of beryllium feed source 6, and more specifically, beryl is performed in a sealed vessel, autoclave, or the like (reaction stage 10), which is hermetically sealed from the environment (i.e., there is no vapor stream 13 being discharged from reaction stage 10).
- reaction stage 10 a sealed vessel, autoclave, or the like
- substantially all of the reaction volume is filled with the reaction mixture.
- Substantially complete dissolution of the beryl can be effected using hydrofluoric acid 8. added in excess. Under such conditions, no addition of sulfuric acid 12 is needed. With increasing temperature, and for a fixed residence time, the fraction of dissolved beryllium increases. 5
- reaction stage 10 Upon completion of reaction stage 10, a mixture of (excess) hydrofluoric acid and fluosilicic acid, together with the products of dissolution, is typically obtained. This mixture can be separated, and all the acids recovered, according to various processes known in the art.
- reaction stage 10 26 is introduced to a second reaction stage 30 along with reaction product mixture 18 so as to dissolve beryllium values present in second beryllium source 26 as well as to allow additional beryllium values to be leached from any residue remaining from reaction stage 10. This is particularly advantageous in that at least a portion, and preferably substantially all of the excess acid from reaction stage 10 can be consumed,
- Second beryllium source 26 preferably includes bertrandite, which has been found by the inventors to dissolve readily (substantially 100%) in the presence of these acids at moderate temperatures as low as 60°C - 110°C.
- Other beryllium feed 0 sources that dissolve more readily than beryl may also be used in second beryllium source 26.
- beryllium feed source' refers to a raw material, or combination of raw materials, containing beryllium.
- Beryllium feed source specifically includes, but is 5 not limited to, materials containing beryl, bertrandite, and/or phenakite.
- readily soluble beryllium feed source refers to a beryllium feed source that includes, but is not limited to, bertrandite, and/or phenakite.
- readily soluble beryllium feed source is meant to specifically exclude beryl. .
- the term "directly introduced to the reaction stage” and the like, used in conjunction with “beryllium feed source” refers to a beryllium feed source that is reacted with hydrofluoric acid, without first undergoing melting or other high-temperature treatments, and particularly, without undergoing high-temperature treatment at temperatures exceeding 600°C.
- the particular operating conditions of the process of the present invention will understandably vary according to the composition of beryllium feed source 6, local process conditions, etc.
- the high toxicity of beryllium introduces various safety and ecology issues into the production process.
- the inhalation of beryllium particles or fumes can trigger acute or chronic lung disease of a serious nature.
- the inventive process obviates the need for the high-temperature, multiple-stage thermal treatment, significantly reducing thereby the health risk to plant personnel and/or reducing the costs associated with maintaining the requisite high standard of air quality for beryllium production facilities.
- the amount of beryllium dissolved is typically around 90%. In the inventive process, the amount of beryllium dissolved is typically up to 100%. under relatively mild conditions and reasonable residence times.
- the finely-ground beryl used in Examples 1-5 contained: 13.08% BeO, 17.25% A1 2 0 3 , 63.91% Si0 2 , 0.91 % Fe 2 0 3. 0.19% MgO, 0.7% Na 2 0, 1.4% ZrO, 0.35% PbO.
- the evaporate was completely refluxed (see stream 15 of
- EXAMPLE 6 The beryl used in Example 6 contained 13.08% BeO, 17.25% A1 2 0 3: and 0.91 % Fe 2 0 3. To a Teflon® (polytetrafluoroethylene)-lined capsule having a reaction volume of 60 ml were added 12.2 grams of beryl and 58 ml of hydrofluoric acid (38% HF), such that the entire volume o ⁇ the capsule was filled with the reaction mixture. The non-agitated capsule was hermetically sealed and placed in an oven that was heated to 125°C for 20 hours ' . The capsule was then cooled and opened. The content of the capsule was filtered, and the solid residue was washed, dried and weighed.
- Teflon® polytetrafluoroethylene
- the beryl used in Example 7 contained 12.25% BeO. and 17.5% AI9O 3.
- Example 7 The results of Example 7 are provided in Table 2.
- Example 7 the only difference being that 20.0 grams of beryl were added to the capsule.
- the results of Example 8 are provided in Table 2.
- Example 9 The beryl used in Example 9 contained 12.25% BeO, 17.5 % A1 2 0 3 , and 1.0%? Fe 2 0 3 _ The beryl particles were ground to a size of -325 mesh (44 microns). To a stirred and heated reaction vessel were added 17.5 grams of beryl and 140ml of hydro fluoric acid (507o HF). The evaporate from the reaction vessel was completely refluxed (see stream 15 of Figure 1) to the reaction mixture. After three hours, the reaction mixture - which contained a small quantity of solids - was filtered. The solid residue was washed with distilled water, dried and weighed. From the results, solute material balances were calculated, wet residue weight: 1.64g dry residue weight: 1.06g filtrate and washing liquor weight: 263.7 g filtrate and washing liquor specific gravity: 1.163
- the liquor was then boiled in an Erlenmeyer flask fluidly connected to a condenser. Solids precipitated in the reaction mixture. Fine solids (silica) were also deposited on the walls of the condenser. After 30 minutes, the reaction mixture was filtered. The wet solid residue, weighing 13.59 g, was dried. The dry residue, which largely consisted of A1F 3 -3H 2 0, weighed 9.33 g.
- the concentration of Be in the solution was 15.41 g/1. From the solute material balances, it is evident that all the beryllium values remained in the aqueous phase.
- the liquor remaining after sampling weighed 62.22 g.
- the concentration of Be in the solution was 14.2 g/1, corresponding to a substantially
- the solution produced can then be further processed [e.g., using processes known in the art, as outlined in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 4a, Wiley-VCH Verlag GmbH & Co. (1985)] to produce various refined beryllium products, including, but not limited to, beryllium hydroxide and beryllium metal.
- active used with respect to "fluorine-containing compound” and the like, is meant to include any material containing fluorine that is effective by itself, or in combination with another material (e.g., a concentrated acid), in the dissolution of a beryllium-containing mineral such as beryl, bertrandite. and/or phenakite.
- active fluorine-containing compounds include hydrogen fluoride, silicon tetrafluoride (typically in concentrated acidic media), and fl ⁇ orosilicic acid.
- major component used with respect to "fluorine-containing compound” and the like, refers to a fluorine-containing compound containing at least 3 wt.-% fluorine and/or resulting in a fluorine concentration in the reaction mixture of at least 2 wt.-% fluorine.
- the fluorine-containing compound contains at least 10 wt.-% fluorine, more preferably, at least 15 wt.-% fluorine, and most preferably, at least 20 wt.-7o fluorine.
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Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU2003282349A AU2003282349A1 (en) | 2002-11-12 | 2003-11-12 | Method of leaching beryllium values using hydrofluoric acid |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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IL15280202A IL152802A0 (en) | 2002-11-12 | 2002-11-12 | A method for leaching beryllium oxide from its ores |
IL152802 | 2002-11-12 | ||
IL157764 | 2003-09-04 | ||
IL15776403A IL157764A0 (en) | 2003-09-04 | 2003-09-04 | Method of leaching beryllium values using hydrofluoric acid |
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WO2004043862A1 true WO2004043862A1 (fr) | 2004-05-27 |
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PCT/IL2003/000954 WO2004043862A1 (fr) | 2002-11-12 | 2003-11-12 | Procede de lixiviation d'elements de valeur de beryllium au moyen d'acide fluorhydrique |
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AU (1) | AU2003282349A1 (fr) |
WO (1) | WO2004043862A1 (fr) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2309121C2 (ru) * | 2006-02-20 | 2007-10-27 | Акционерное общество "Ульбинский металлургический завод" | Способ переработки бериллиевых концентратов |
RU2309122C2 (ru) * | 2006-02-20 | 2007-10-27 | Акционерное общество "Ульбинский металлургический завод" | Способ переработки бериллийсодержащих концентратов |
RU2324653C2 (ru) * | 2006-02-14 | 2008-05-20 | Республиканское государственное казенное предприятие "Восточно-Казахстанский государственный технический Университет им. Д. Серикбаева Министерства образования и науки Республики Казахстан" | Способ переработки бертрандит-фенакит-флюоритовых концентратов |
RU2350562C2 (ru) * | 2008-02-05 | 2009-03-27 | Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ имени первого Президента России Б.Н. Ельцина" | Способ извлечения бериллия из бериллийсодержащих концентратов |
RU2351540C2 (ru) * | 2007-12-14 | 2009-04-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ) | Способ извлечения бериллия из бериллиевых концентратов |
RU2351539C2 (ru) * | 2007-12-14 | 2009-04-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ) | Способ извлечения бериллия из бериллиевых концентратов |
RU2494964C1 (ru) * | 2012-05-03 | 2013-10-10 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Способ получения фторида бериллия |
RU2547060C1 (ru) * | 2013-12-11 | 2015-04-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина | Способ совместной переработки бериллиевых концентратов |
RU2546945C1 (ru) * | 2013-12-03 | 2015-04-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина | Способ переработки смеси бериллиевых концентратов |
CN106676285A (zh) * | 2016-12-23 | 2017-05-17 | 江西合纵锂业科技有限公司 | 一种用于锂云母分解的混合酸及其浸出方法 |
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US3879520A (en) * | 1963-01-31 | 1975-04-22 | Atomic Energy Commission | Method for dissolving ceramic beryllia |
US4729881A (en) * | 1986-12-16 | 1988-03-08 | Fmc Corporation | Hydrometallurgical process for the production of beryllium |
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- 2003-11-12 WO PCT/IL2003/000954 patent/WO2004043862A1/fr not_active Application Discontinuation
- 2003-11-12 AU AU2003282349A patent/AU2003282349A1/en not_active Abandoned
Patent Citations (2)
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US3879520A (en) * | 1963-01-31 | 1975-04-22 | Atomic Energy Commission | Method for dissolving ceramic beryllia |
US4729881A (en) * | 1986-12-16 | 1988-03-08 | Fmc Corporation | Hydrometallurgical process for the production of beryllium |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2324653C2 (ru) * | 2006-02-14 | 2008-05-20 | Республиканское государственное казенное предприятие "Восточно-Казахстанский государственный технический Университет им. Д. Серикбаева Министерства образования и науки Республики Казахстан" | Способ переработки бертрандит-фенакит-флюоритовых концентратов |
RU2309121C2 (ru) * | 2006-02-20 | 2007-10-27 | Акционерное общество "Ульбинский металлургический завод" | Способ переработки бериллиевых концентратов |
RU2309122C2 (ru) * | 2006-02-20 | 2007-10-27 | Акционерное общество "Ульбинский металлургический завод" | Способ переработки бериллийсодержащих концентратов |
RU2351540C2 (ru) * | 2007-12-14 | 2009-04-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ) | Способ извлечения бериллия из бериллиевых концентратов |
RU2351539C2 (ru) * | 2007-12-14 | 2009-04-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ) | Способ извлечения бериллия из бериллиевых концентратов |
RU2350562C2 (ru) * | 2008-02-05 | 2009-03-27 | Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ имени первого Президента России Б.Н. Ельцина" | Способ извлечения бериллия из бериллийсодержащих концентратов |
RU2494964C1 (ru) * | 2012-05-03 | 2013-10-10 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Способ получения фторида бериллия |
RU2546945C1 (ru) * | 2013-12-03 | 2015-04-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина | Способ переработки смеси бериллиевых концентратов |
RU2547060C1 (ru) * | 2013-12-11 | 2015-04-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина | Способ совместной переработки бериллиевых концентратов |
CN106676285A (zh) * | 2016-12-23 | 2017-05-17 | 江西合纵锂业科技有限公司 | 一种用于锂云母分解的混合酸及其浸出方法 |
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