EP0236221B1 - Procédé de préparation par lithiothermie de poudres métalliques - Google Patents
Procédé de préparation par lithiothermie de poudres métalliques Download PDFInfo
- Publication number
- EP0236221B1 EP0236221B1 EP87400417A EP87400417A EP0236221B1 EP 0236221 B1 EP0236221 B1 EP 0236221B1 EP 87400417 A EP87400417 A EP 87400417A EP 87400417 A EP87400417 A EP 87400417A EP 0236221 B1 EP0236221 B1 EP 0236221B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- bath
- reduced
- lithium
- molten salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 5
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000000374 eutectic mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010936 titanium Substances 0.000 abstract description 16
- 229910052719 titanium Inorganic materials 0.000 abstract description 15
- 150000002739 metals Chemical class 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011872 intimate mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229910020312 KCl—KF Inorganic materials 0.000 description 1
- 229910020361 KCl—LiCl Inorganic materials 0.000 description 1
- 229910020999 NaCl—RbCl Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical class [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Inorganic materials [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
- C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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
- C22B59/00—Obtaining rare earth metals
Definitions
- the present invention relates to a method of manufacturing powdered metals by metallothermy. It relates more particularly to a process for the manufacture by lithiothermal of metals of groups IV A of the Periodic Table of the Elements or of metals of the Lanthanide class.
- This process can in particular be advantageously applied to the manufacture of high purity titanium in powder form.
- This operation takes place batchwise in a steel reactor and under an inert atmosphere (helium or argon).
- the metallic titanium is then released in the form of a sponge embedded in molten MgCl2.
- This sponge contains approximately 30% of its weight in impurities, in particular in magnesium and magnesium chloride entrained during the precipitation of the sponge.
- To obtain a very pure metal it is then necessary to carry out a very high vacuum distillation of magnesium and its chloride, a long operation, delicate and costly in energy.
- the purified sponge is then dried and then ground to obtain a titanium powder.
- liquid titanium tetrachloride is poured onto a sheet of molten lithium supernatant over a bath of molten salts.
- the titanium obtained is in the form of a sponge containing impurities, such as lithium and its chloride, entrained during the precipitation of the sponges in the bath of molten salts.
- Another object of the invention is to provide a process for the continuous manufacture of these metals, in which the yields are improved and savings are made, in particular thanks to the ease of purification of the product.
- the Applicant has developed a process for manufacturing a metal essentially in the form of a powder belonging to group IV A of the Periodic Table of the Elements or to the class of Lanthanides by reduction of a salt of this metal by lithium which is characterized in that the abovementioned salt is introduced into a liquid mixture comprising lithium maintained in dispersion by mechanical stirring in a bath of molten salts.
- this process makes it possible to obtain, with good yield, a metal directly and essentially in the form of a powder, this powder proving to be easy to purify.
- the process of the invention applies particularly well to the case of titanium.
- the metal to be obtained is therefore initially in the form of one of its salts.
- titanium it will be possible in particular to work directly with tetrachloride or tetrabromide of titanium, obtained respectively by carbochlorination and carbobromuration around 1000 ° C of the rutile TiO2.
- tetrachloride or tetrabromide of titanium obtained respectively by carbochlorination and carbobromuration around 1000 ° C of the rutile TiO2.
- neodymium it is advantageously possible to work with neodymium trichloride.
- a preferred embodiment of the invention will consist in operating with the chlorides of these metals.
- the molten salt baths used in the present invention preferably consist of mixtures of halides chosen from the group of halides of alkali metals or alkaline earth metals. They may be binary mixtures or ternary mixtures. As binary mixtures which can be used, mention may be made of LiCl and KCl, LiCl and CsCl, LiCl and RbCl, LiBr and KBr, LiBr and CsBr, LiBr and NaBr, LiBr and SrBr2, LiI and CsI.
- ternary mixtures which can be used, mention may be made of mixtures containing, in addition to lithium chloride or potassium chloride, a chloride chosen from sodium, rubidium, strontium, magnesium, calcium and barium chlorides. Finally, mention may be made of the ternaries LiCl-NaCl-CsCl, LiCl-NaCl-RbCl and LiCl-KCl-KF.
- the eutectic composition of the mixture this in order to reduce the bath melting temperature as much as possible. Even more preferably, the eutectic mixture LiCl - KCl will be taken.
- baths and operating conditions will be chosen such that the temperature of the salt bath will be between 400 and 550 ° C., preferably close to 500 ° C.
- the molten lithium necessary for the reduction of the metal salt may in particular be advantageously produced according to the process as described in French application FR 2560 221.
- This process has the advantage of continuously operating the electrolysis of lithium chloride in a mixture of molten salts, for example the binary KCl-LiCl, whereby a liquid layer of molten lithium supernatant is obtained continuously on said salt bath.
- any mechanical means providing sufficiently high agitation may be suitable, in particular a paddle stirrer, for example with straight and inclined paddles and a system of counterpales fixed to the reactor vessel.
- the counterpales will have a width equal to approximately one tenth of the diameter of the reactor vessel.
- the stirring speed will obviously vary depending on the size of said tank.
- peripheral rotation speeds of the paddle stirrer greater than 1.3 m / s and more particularly greater than 1.9 m / s may be mentioned.
- the metal salt can be introduced in solid, liquid or gaseous form.
- contacting it can be done on the surface or even inside the intimate mixture of lithium and molten salts.
- the quantity of lithium present in the mixture must correspond at least to stoichiometric equality with respect to the metal salt to be reduced.
- the reaction which is then brought into play can be generally written: MCl n + n Li ⁇ M + n LiCl
- the metal thus obtained is essentially in the form of powder.
- the yield of the lithiothermal reduction is also improved, since generally at least 70% of the metal to be reduced introduced in the form of salt is found after the reaction in the metallic state.
- the metal thus produced being solid in this temperature zone, it can be easily separated from the reaction medium, enriched in dissolved lithium chloride originating from the reaction, which remains in the molten state.
- the reduced metal can be separated from the bath by any known means, in particular by filtration, whereby the desired metal extracted on the one hand is obtained in the form of fine particles and on the other hand the mixture of molten salts, LiCl-KCl for example.
- At least 70% of the particles have a size of between 100 ⁇ m and 1 mm.
- the LiCl-KCl mixture can then be recycled at the top at the electrolysis which regenerates the lithium in the metallic state.
- the lithium thus regenerated is reused to reduce the salt of the metal that it is desired to obtain.
- the completion of this operation allows obviously to reduce the costs due to the reducer; indeed, to the nearest loss, the quantity of lithium contained in Li or LiCl form is constant, which in part reduces the problems of supplying lithium salts.
- the collected metallic particles can then undergo a purification operation. But unlike the other conventional methods for manufacturing these metals described above, which require a long and costly distillation purification, a simple purification by acid washing suffices here.
- the advantage is a low energy consuming process.
- This acid washing can be done with nitric acid or hydrochloric acid.
- acidulated water at a pH of at least 1.5.
- This powder generally has a metal content of at least 80% and in the case of titanium generally at least 99%.
- a 316 L stainless steel crucible with an internal diameter of 70 mm is used.
- a 24 mm diameter turbine with 6 straight blades is used as the stirring system.
- the crucible is fitted with 4 5 mm counter blades.
- the bath is a LiCl-KCl mixture.
- Test 1 concerns the preparation of neodymium.
- Tests 2 and 3 relate to the preparation of titanium. They are driven with different stirring speeds.
- titanium 100% in the form of powder.
- the titanium is in the form of powder and sponge in the respective proportions by weight of 64% and 36%.
- the titanium powder has the following particle size: 83% of the particles have a size of between 100 ⁇ m and 1 mm, 14% are of size less than 100 ⁇ m and 3% have a size greater than 1 mm.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87400417T ATE64627T1 (de) | 1986-02-28 | 1987-02-25 | Verfahren zum lithiothermischen herstellen von metallischen pulvern. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8602792A FR2595101A1 (fr) | 1986-02-28 | 1986-02-28 | Procede de preparation par lithiothermie de poudres metalliques |
| FR8602792 | 1986-02-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0236221A1 EP0236221A1 (fr) | 1987-09-09 |
| EP0236221B1 true EP0236221B1 (fr) | 1991-06-19 |
Family
ID=9332628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87400417A Expired - Lifetime EP0236221B1 (fr) | 1986-02-28 | 1987-02-25 | Procédé de préparation par lithiothermie de poudres métalliques |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4725312A (enrdf_load_stackoverflow) |
| EP (1) | EP0236221B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS62240704A (enrdf_load_stackoverflow) |
| KR (1) | KR910006946B1 (enrdf_load_stackoverflow) |
| AT (1) | ATE64627T1 (enrdf_load_stackoverflow) |
| CA (1) | CA1286507C (enrdf_load_stackoverflow) |
| DE (1) | DE3770834D1 (enrdf_load_stackoverflow) |
| FR (1) | FR2595101A1 (enrdf_load_stackoverflow) |
Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4865644A (en) * | 1987-07-23 | 1989-09-12 | Westinghouse Electric Corporation | Superconducting niobium alloys |
| US4897116A (en) * | 1988-05-25 | 1990-01-30 | Teledyne Industries, Inc. | High purity Zr and Hf metals and their manufacture |
| US5259862A (en) * | 1992-10-05 | 1993-11-09 | The United States Of America As Represented By The Secretary Of The Interior | Continuous production of granular or powder Ti, Zr and Hf or their alloy products |
| US5442978A (en) * | 1994-05-19 | 1995-08-22 | H. C. Starck, Inc. | Tantalum production via a reduction of K2TAF7, with diluent salt, with reducing agent provided in a fast series of slug additions |
| US7445658B2 (en) | 1994-08-01 | 2008-11-04 | Uchicago Argonne, Llc | Titanium and titanium alloys |
| US20030145682A1 (en) * | 1994-08-01 | 2003-08-07 | Kroftt-Brakston International, Inc. | Gel of elemental material or alloy and liquid metal and salt |
| US20030061907A1 (en) * | 1994-08-01 | 2003-04-03 | Kroftt-Brakston International, Inc. | Gel of elemental material or alloy and liquid metal and salt |
| US7435282B2 (en) | 1994-08-01 | 2008-10-14 | International Titanium Powder, Llc | Elemental material and alloy |
| DE69521432T2 (de) * | 1994-08-01 | 2002-05-29 | International Titanium Powder L.L.C., Willowbrook | Verfahren zur herstellung von metallen und anderen elementen |
| WO2004033736A1 (en) * | 2002-10-07 | 2004-04-22 | International Titanium Powder, Llc. | System and method of producing metals and alloys |
| US7416697B2 (en) | 2002-06-14 | 2008-08-26 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
| AU2003252040A1 (en) * | 2002-07-17 | 2004-02-02 | Liquidmetal Technologies | Method of making dense composites of bulk-solidifying amorphous alloys and articles thereof |
| UA79310C2 (en) * | 2002-09-07 | 2007-06-11 | Int Titanium Powder Llc | Methods for production of alloys or ceramics with the use of armstrong method and device for their realization |
| US20050284824A1 (en) * | 2002-09-07 | 2005-12-29 | International Titanium Powder, Llc | Filter cake treatment apparatus and method |
| EA006616B1 (ru) * | 2002-09-07 | 2006-02-24 | Интернэшнл Тайтейнием Паудер, Ллк | Способ отделения титана от содержащей титан суспензии |
| WO2004033737A1 (en) * | 2002-10-07 | 2004-04-22 | International Titanium Powder, Llc. | System and method of producing metals and alloys |
| BR0204587A (pt) | 2002-11-04 | 2004-06-29 | Cbmm Sa | Processo de produção de pó de nióbio e/ou de tântalo de elevada área superficial |
| US6968990B2 (en) * | 2003-01-23 | 2005-11-29 | General Electric Company | Fabrication and utilization of metallic powder prepared without melting |
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| WO2006098055A1 (ja) * | 2005-03-15 | 2006-09-21 | Sumitomo Titanium Corporation | 高融点金属の分離回収方法 |
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| JP2009511739A (ja) | 2005-10-06 | 2009-03-19 | インターナショナル・タイテイニアム・パウダー・リミテッド・ライアビリティ・カンパニー | ホウ化チタン |
| US20080031766A1 (en) * | 2006-06-16 | 2008-02-07 | International Titanium Powder, Llc | Attrited titanium powder |
| US20100288649A1 (en) * | 2006-10-11 | 2010-11-18 | Pal Uday B | Magnesiothermic som process for production of metals |
| US7753989B2 (en) * | 2006-12-22 | 2010-07-13 | Cristal Us, Inc. | Direct passivation of metal powder |
| US9127333B2 (en) * | 2007-04-25 | 2015-09-08 | Lance Jacobsen | Liquid injection of VCL4 into superheated TiCL4 for the production of Ti-V alloy powder |
| RU2353686C1 (ru) * | 2007-11-09 | 2009-04-27 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Способ переработки титановой губки |
| CN102470443B (zh) * | 2009-07-17 | 2014-10-15 | 波士顿电子材料有限公司 | 金属粉末和合金的制造和应用 |
| RU2466198C1 (ru) * | 2011-06-14 | 2012-11-10 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Способ получения губчатого титана |
| AU2012358205B2 (en) | 2011-12-22 | 2017-10-12 | Universal Achemetal Titanium, Llc | A system and method for extraction and refining of titanium |
| CN103305876B (zh) * | 2013-06-05 | 2015-08-12 | 哈尔滨工程大学 | 熔盐电解和还原萃取连用提取镨并制得铝锂镨合金的方法 |
| WO2014209173A1 (ru) * | 2013-06-28 | 2014-12-31 | Общество с ограниченной ответственностью "Современные химические и металлургические технологии" | Способ получения титана восстановлением из тетрахлорида титана |
| RU2549795C2 (ru) * | 2013-06-28 | 2015-04-27 | Общество с ограниченной ответственностью "Современные химические и металлургические технологии" (ООО "СХИМТ") | Способ получения титана и устройство для его осуществления |
| RU2559075C2 (ru) * | 2013-11-26 | 2015-08-10 | ООО "Современные химические и металлургические технологии" (ООО "СХИМТ") | Способ алюмотермического получения титана |
| US10245642B2 (en) * | 2015-02-23 | 2019-04-02 | Nanoscale Powders LLC | Methods for producing metal powders |
| CA3047102C (en) | 2016-09-14 | 2023-12-05 | Universal Achemetal Titanium, Llc | A method for producing titanium-aluminum-vanadium alloy |
| AU2018249909B2 (en) | 2017-01-13 | 2023-04-06 | Universal Achemetal Titanium, Llc | Titanium master alloy for titanium-aluminum based alloys |
| JP7388651B2 (ja) * | 2019-10-31 | 2023-11-29 | 東邦チタニウム株式会社 | 粉末金属の製造方法 |
| CN113500204A (zh) * | 2021-07-08 | 2021-10-15 | 安徽理工大学 | 一种氯化钙熔盐中钙热还原氯化铌制备细微铌粉的方法 |
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| US2839385A (en) * | 1954-12-08 | 1958-06-17 | Du Pont | Method of producing titanium metal |
| US2913332A (en) * | 1957-04-05 | 1959-11-17 | Dow Chemical Co | Production of titanium metal |
| US4105440A (en) * | 1969-09-05 | 1978-08-08 | Battelle Memorial Institute | Process for reducing metal halides by reaction with calcium carbide |
| US3966458A (en) * | 1974-09-06 | 1976-06-29 | Amax Speciality Metal Corporation | Separation of zirconium and hafnium |
| US4032328A (en) * | 1975-10-23 | 1977-06-28 | University Of Minnesota, Inc. | Metal reduction process |
| US4149876A (en) * | 1978-06-06 | 1979-04-17 | Fansteel Inc. | Process for producing tantalum and columbium powder |
| FR2432553A1 (fr) * | 1978-07-31 | 1980-02-29 | Pechiney Aluminium | Procede et dispositif de traitement d'un metal ou alliage liquide au moyen de flux liquide et solide |
| US4252564A (en) * | 1979-08-21 | 1981-02-24 | The United States Of America As Represented By The United States Department Of Energy | Method for cleaning bomb-reduced uranium derbies |
| US4468248A (en) * | 1980-12-22 | 1984-08-28 | Occidental Research Corporation | Process for making titanium metal from titanium ore |
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| US4556420A (en) * | 1982-04-30 | 1985-12-03 | Westinghouse Electric Corp. | Process for combination metal reduction and distillation |
| US4578242A (en) * | 1984-07-03 | 1986-03-25 | General Motors Corporation | Metallothermic reduction of rare earth oxides |
| US4602947A (en) * | 1984-11-01 | 1986-07-29 | Alti Corporation | Process for producing titanium metal and titanium metal alloys |
| FR2582019B1 (fr) * | 1985-05-17 | 1987-06-26 | Extramet Sa | Procede pour la production de metaux par reduction de sels metalliques, metaux ainsi obtenus et dispositif pour sa mise en oeuvre |
| US4668287A (en) * | 1985-09-26 | 1987-05-26 | Westinghouse Electric Corp. | Process for producing high purity zirconium and hafnium |
| US4680055A (en) * | 1986-03-18 | 1987-07-14 | General Motors Corporation | Metallothermic reduction of rare earth chlorides |
-
1986
- 1986-02-28 FR FR8602792A patent/FR2595101A1/fr not_active Withdrawn
-
1987
- 1987-02-13 JP JP62029961A patent/JPS62240704A/ja active Granted
- 1987-02-25 DE DE8787400417T patent/DE3770834D1/de not_active Expired - Fee Related
- 1987-02-25 AT AT87400417T patent/ATE64627T1/de not_active IP Right Cessation
- 1987-02-25 EP EP87400417A patent/EP0236221B1/fr not_active Expired - Lifetime
- 1987-02-27 CA CA000530833A patent/CA1286507C/fr not_active Expired - Lifetime
- 1987-02-27 KR KR1019870001741A patent/KR910006946B1/ko not_active Expired
- 1987-03-02 US US07/020,362 patent/US4725312A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| IUPAC, Nomenclature of Inorganic Chemistry, 2nd edition, 1971, Pergamon Press * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3770834D1 (de) | 1991-07-25 |
| KR910006946B1 (ko) | 1991-09-14 |
| US4725312A (en) | 1988-02-16 |
| JPS6365723B2 (enrdf_load_stackoverflow) | 1988-12-16 |
| FR2595101A1 (fr) | 1987-09-04 |
| EP0236221A1 (fr) | 1987-09-09 |
| CA1286507C (fr) | 1991-07-23 |
| ATE64627T1 (de) | 1991-07-15 |
| KR870007743A (ko) | 1987-09-21 |
| JPS62240704A (ja) | 1987-10-21 |
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