US2890953A - Continuous process for the manufacture of titanium metal - Google Patents
Continuous process for the manufacture of titanium metal Download PDFInfo
- Publication number
- US2890953A US2890953A US546692A US54669255A US2890953A US 2890953 A US2890953 A US 2890953A US 546692 A US546692 A US 546692A US 54669255 A US54669255 A US 54669255A US 2890953 A US2890953 A US 2890953A
- Authority
- US
- United States
- Prior art keywords
- titanium
- sodium
- titanium tetrachloride
- reaction
- metal
- 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
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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
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S266/00—Metallurgical apparatus
- Y10S266/905—Refractory metal-extracting means
Definitions
- This invention relates to a continuous process for the manufacture of ductile titanium by reduction of titanium tetrachloride by means of sodium metal and to an apparatus for effecting this process.
- the apparatus is so designed that the products of reaction are in a free-flowing non-adherent form so that their removal from a primary reaction vessel to a subsequent process stage is a relatively straight forward matter.
- Titanium is normally produced by the reduction of titaniurn tetrachloride using a molten metal, usually sodium or magnesium, as the reducing metal.
- a major setback to the economic application of this process is the tendency of the titanium metal so produced to form a single block of metal of sponge-like form, which commonly adheres to the walls of the primary reaction vessel used to contain the reactants, thus making withdrawal of the titanium difiicult.
- a principal object of the present invention is to provide a process and apparatus whereby the reduction of titanium tetrachloride by means of sodium metal to ti tanium metal may be carried out effectively and economically without the reaction taking place adjacent to the wall of the containing vessel.
- a further object of the present invention is to produce the titanium metal, sodium chloride and excess sodium metal in a form Which facilitates the subsequent removal of the latter two components.
- a process for the manufacture of ductile titanium comprises reacting together titanium tetrachloride in liquid or vapour phase with sodium metal in atomised liquid phase in an inert atmosphere, the rate of admixture of the reactants being so adjusted that the sodium metal is present in excess over the stoichiometric equivalent.
- the process for the production of ductile titanium comprises introducing titanium tetrachloride in liquid or vapour phase into a reaction chamber within the confines of which an inert atmosphere prevails, introducing sodium metal in atomised liquid phase into said reaction chamber at a rate sufiicient to ensure that the sodium metal is present in slight excess over the stoichiometric equivalent of titanium tetrachloride, the two reactants being arranged to commingle out of physical contact with the walls of the reaction chamber, whereby to avoid localised titanium sponge deposition.
- the sodium metal shall be present in the reaction chamber in excess, albeit slight, over the stoichiometric equivalent of titanium tetrachloride. A 5% excess is particularly suitable.
- apparatus for the production of ductile titanium by reduction of titanium tetrachloride by means of sodium metal comprises a gastight reaction chamber, means for introducing titanium tetrachloride in liquid or vapour phase into said chamber, means for introducing molten sodium in an atomate ised liquid phase into said chamber, and means for withdrawing the products of reaction from said reaction chamher.
- the inert atmosphere may comprise a noble gas such as helium or argon.
- Apparatus in accordance with the invention consists of a containing chamber which shall be gas-tight and so constructed that it may be completely filled with an inert atmosphere, for example argon or helium.
- the upper portion of the reaction chamber is fitted with a liquid atomising device, through which the sodium metal, as a liquid, is fed into the apparatus.
- the atomising device used may be chosen from one of the several types available for the atomisation of liquids, for example, gas atomising nozzles of a design currently used for the spraying of paints, pressure atomising nozzles of various types such as are used for water atomisation, for the spraying of crops and similar duties, and spinning disc atomisers commonly in use in spray drying apparatus.
- the pressure atomising type operated with a liquid pressure of 25/30 lbs. per square inch has been used the most extensively.
- the upper portion of the apparatus is also fitted with a duct through which titanium tetrachloride is fed into the apparatus. It is advantageous to so design the titanium tetrachloride inlet system that the concentration of titanium tetrachloride is sensibly constant at all points on the periphery of the reaction chamber. If this is not so, there may be a tendency for a local excess of titanium tetrachloride over sodium metal, leading to the formation of lower chlorides of titanium which are undesirable.
- the atomisation of the liquid sodium metal is efiected by means of a noble gas under pressure and titanium tetrachloride in liquid or vapour phase is introduced into the reaction chamber so as to commingle with the atomised liquid spray of sodi um metal.
- titanium tetrachloride vapour may be used as the means for atomising the sodium meal.
- the diameter of the reaction chamber is a function of the size and type of atomising spray, but should be sufiiciently large to ensure that the spray atomised metal does not impinge upon the side walls, otherwise at the point of impingement a growth of titanium sponge is likely to develop. Such growths could eventually block the reaction chamber.
- the product of reaction is particulate and relatively free-flowing so that its removal from the reaction chamber is not a difficult operation.
- the removal is achieved successfully by means of a broken flight screw conveyor mounted at the lower extremity of a preferably hopper shaped bottom section of the reaction chamber. This whole lower section of the reaction chamber may conveniently be cooled in order to prevent any tendency for sodium chloride to become sticky through melting and thus binding the product together.
- the titanium produced by the reaction shall be in the form of a fairly coarse powder to facilitate collection and subsequent processing, there are grounds for believing that the particle size of the drops of sodium metal should be controlled. It is thought that the formation of very fine drops of sodium metal or of sodium vapour in the reaction chamber may give rise to a titanium powder which is too fine for practical purposes. It seems logical to presume that drops of sodium metal of different particle size differ in the time required to react with the titanium tetrachloride, and that, in order to facilitate complete reaction, the particle size should be as uniform'as possible.
- the products of reaction removed from the apparatus hereinbefore described are essentially titanium metal and sodium chloride, together with a small excess of sodium metal and the titanium may then be purified by leaching or vacuum distillation techniques.
- FIG. 1 and 2 illustrate two different embodiments of an apparatus each capable of providing operating conditions in which the process according to the invention may be carried out.
- a reaction space 1 is enclosed by a reaction or spray chamber (members 2, 3, 4 and 5), the main reaction space being that enclosed by the portion of the vessel 2 which is of such diameter that the cone of sprayed reactants does not impinge on the walls until reaction is substantially complete, and of such length that reaction is complete before the hopper bottom 4 is reached.
- the sodium metal is introduced down a duct 7 which is fed from melting and filtration means (not shown).
- the molten metal is atomised in an externally atomising spray head 6, inert gas, argon or helium, being introduced under pressure through a duct 8, to efiect the atomisation.
- the atomised sodium metal forms a well defined cone 9.
- the gaseous titanium tetrachloride under pressure is introduced via a duct 10 into a circular duct 11 from which it is expelled through a series of small holes forming cones 12 of vapour which intermingle and react with cone 9.
- the titanium tetrachloride may be added as a liquid under pressure, in which case cones 12 will be formed of small liquid droplets.
- Duct 13 is also used in conjunction with duct 8 for evacuating the apparatus and filling it with an inert atmosphere, prior. to the start of the reaction.
- the titanium metal formed in the reaction between the atomised molten sodium metal and the titanium tetrachloride vapour is in the form of discrete particles which fall through the reaction space 1 into the hopper bottom 4 from which they flow via a duct 14 to the next stage of the process.
- a screw coveyor 15 is used for removing the product metal and a vibrator mounting 17 is provided to assist the flow of the metal powder.
- Thermo-couples 16 suitably disposed in the reaction chamber indicate the operating temperature and allow control of the reaction to be maintained and similarly the absolute pressure in the reactor measured through duct 13 also gives an indication of the manner in which the reaction is proceeding.
- Suitable heating means for the upper part of the reaction chamber may be provided, if desired.
- the reaction space 18 is enclosed by vessel 19 enclosed partly in a furnace 20.
- the sodium metal pre-heated and at a pressure of 20 pounds per square inch, enters through duct 21 to the atomising nozzle 22, a well defined cone 23 of sodium metal particles being produced.
- Titanium tetrachloride vapour enters through tangentially disposed duct 24.
- Noble gas argon is also fed into the apparatus through duct 24 and any pressure build up in the apparatus is relieved through duct 25, which passes to condensing means (not shown). During the preparation of the reaction chamber ducts 24 and 25 are used for purging the apparatus of air.
- Example Titanium tetrachloride was added at a measured rate of 68.7 lbs. per hour through a tangential inlet pipe heated to 500 0.; simultaneously sodium metal, pro-'- heated to 400 C., was added at a rate equivalent to a 5% excess over the stoichiometrical equivalent.
- the sodium metal was pressurised to 25 lbs. per square inch and atomised through a pressure atomising nozzle.
- the reaction chamber Prior to the addition of reactants, the reaction chamber was heated externally to 600 C. and filled with an inert argon atmosphere. When reaction commenced, all the external heating was stopped and the temperature henceforth was maintained by the heat of reaction. The reaction chamber was operated continuously for 3 hours 50 minutes before being shut down.
- the product which was in the form of a free-flowing black powder, was heated to 0 C. which had the efiect of distilling off the excess sodium which had been added and the resulting mass was then crushed and leached, firstly in hydrochloric acid to which ferric chloride had been added, followed by water washing.
- the product after arc melting, was analysed, and shown to contain 99.5% titanium. Based on the titanium content of the titanium tetrachloride used in the experiment, the yield of leached metal product was 72%.
- Titanium metal prepared in accordance with the process and in the apparatus described hereinbefore has a surface area so large that if it were exposed to .the
- the present invention provides a process which may be carried out continuously thus permitting maximum utilisation of the apparatus employed.
- Continuous reduction means that any accidental residual impurities on the walls of, or in the atmosphere in the reaction chamher will be gettered in the initial working of the process and thereafter the product titanium of the continuous process will attain a higher degree of purity than is normally possible in batch work where each batch runs the risk of contamination.
- a process for the production of ductile titanium in solid, particulate, relatively free-flowing form from titanium tetrachloride which consists of introducing a conical spray of atomized liquid sodium under pressure into a chamber containing an atmosphere inert to said sodium and titanium tetrachloride, circumferentially intersecting the periphery of said conical spray at a point spaced from the entry of said spray into said atmosphere and spaced from the walls of said chamber with titanium tetrachloride and substantially completely reacting said atomized liquid sodium with said titanium tetrachloride at substantially the points of the intersection to form solid particulate titanium, lower chlorides of titanium, and sodium chloride, the rate of admixture of the reactants being so adjusted that the sodium metal is present in from 1 to excess over the stoichiometric equivalent of titanium tetrachloride.
- a process for the production of ductile titanium in solid, particulate, relatively free-flowing form from titanium tetrachloride by means of liquid sodium which consists of separately preheating said ingredients to temperature above the boiling point of titanium tetrachloride but below the boiling point of sodium metal, atomizing said preheated sodium at a pressure within the range of 10 to pounds per square inch, introducing a continuous conical spray of said preheated atomized liquid sodium into a chamber containing an atmosphere inert to said sodium and titanium tetrachloride, circumferentially intersecting the periphery of said spray at a point spaced from the entry of said spray into said atmosphere and spaced from the Walls of said chamber with vaporous titanium tetrachloride and substantially completely reacting said liquid sodium with said titanium tetrachloride at substantially the points of intersection to form solid, particulate titanium, lower chlorides of titanium and sodium chloride, the rate of admixture of the reactants being so adjusted that the sodium metal is present in from 1 to
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- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB33087/54A GB821817A (en) | 1954-11-16 | 1954-11-16 | Continuous process for the manufacture of titanium metal |
Publications (1)
Publication Number | Publication Date |
---|---|
US2890953A true US2890953A (en) | 1959-06-16 |
Family
ID=10348395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US546692A Expired - Lifetime US2890953A (en) | 1954-11-16 | 1955-11-14 | Continuous process for the manufacture of titanium metal |
Country Status (3)
Country | Link |
---|---|
US (1) | US2890953A (fr) |
FR (1) | FR1138925A (fr) |
GB (1) | GB821817A (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2995440A (en) * | 1958-04-23 | 1961-08-08 | Union Carbide Corp | Process for producing reactive metals |
US3069255A (en) * | 1957-11-25 | 1962-12-18 | Jr Don H Baker | Production of high purity titanium by metallic sodium reduction of titanic halide |
US3535109A (en) * | 1967-06-22 | 1970-10-20 | Dal Y Ingersoll | Method for producing titanium and other reactive metals |
US3554521A (en) * | 1966-05-23 | 1971-01-12 | British Iron Steel Research | The treating or refining of metal |
WO1984002516A1 (fr) * | 1982-12-27 | 1984-07-05 | Stanford Res Inst Int | Procede et appareil pour obtenir du silicium a partir d'acide fluosilicique |
US4584181A (en) * | 1982-12-27 | 1986-04-22 | Sri International | Process and apparatus for obtaining silicon from fluosilicic acid |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE505801A (fr) * | ||||
DE296867C (fr) * | ||||
US2205854A (en) * | 1937-07-10 | 1940-06-25 | Kroll Wilhelm | Method for manufacturing titanium and alloys thereof |
US2277067A (en) * | 1940-02-16 | 1942-03-24 | Minerals And Metals Corp | Manufacture of metal products |
US2530077A (en) * | 1948-02-11 | 1950-11-14 | Frederick C Ramsing | Metallurgical furnace |
US2559419A (en) * | 1948-03-01 | 1951-07-03 | Fouquet Robert | Continuous production of volatilizable metals |
US2564337A (en) * | 1948-11-02 | 1951-08-14 | Battelle Development Corp | Production of refractory metals |
US2618549A (en) * | 1949-05-02 | 1952-11-18 | Kennecott Copper Corp | Method for the production of titanium |
USRE23825E (en) * | 1954-05-11 | Rotary drum apparatus and means | ||
FR1074024A (fr) * | 1952-01-02 | 1954-09-30 | Crane Co | Appareil pour la production de métaux par réduction de leurs sels |
GB717930A (en) * | 1951-11-01 | 1954-11-03 | Ici Ltd | Improvements in or relating to the extraction of titanium from its halides |
FR1088006A (fr) * | 1953-09-18 | 1955-03-02 | Nat Res Corp | Procédé pour la fabrication de titane pur et autres métaux |
US2708158A (en) * | 1950-09-27 | 1955-05-10 | Eugene M Smith | Production of titanium |
US2782118A (en) * | 1952-02-19 | 1957-02-19 | Monsanto Chemicals | Production of refractory metals |
US2828199A (en) * | 1950-12-13 | 1958-03-25 | Nat Res Corp | Method for producing metals |
-
1954
- 1954-11-16 GB GB33087/54A patent/GB821817A/en not_active Expired
-
1955
- 1955-11-14 US US546692A patent/US2890953A/en not_active Expired - Lifetime
- 1955-11-16 FR FR1138925D patent/FR1138925A/fr not_active Expired
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE23825E (en) * | 1954-05-11 | Rotary drum apparatus and means | ||
DE296867C (fr) * | ||||
BE505801A (fr) * | ||||
US2205854A (en) * | 1937-07-10 | 1940-06-25 | Kroll Wilhelm | Method for manufacturing titanium and alloys thereof |
US2277067A (en) * | 1940-02-16 | 1942-03-24 | Minerals And Metals Corp | Manufacture of metal products |
US2530077A (en) * | 1948-02-11 | 1950-11-14 | Frederick C Ramsing | Metallurgical furnace |
US2559419A (en) * | 1948-03-01 | 1951-07-03 | Fouquet Robert | Continuous production of volatilizable metals |
US2564337A (en) * | 1948-11-02 | 1951-08-14 | Battelle Development Corp | Production of refractory metals |
US2618549A (en) * | 1949-05-02 | 1952-11-18 | Kennecott Copper Corp | Method for the production of titanium |
US2708158A (en) * | 1950-09-27 | 1955-05-10 | Eugene M Smith | Production of titanium |
US2828199A (en) * | 1950-12-13 | 1958-03-25 | Nat Res Corp | Method for producing metals |
GB717930A (en) * | 1951-11-01 | 1954-11-03 | Ici Ltd | Improvements in or relating to the extraction of titanium from its halides |
FR1074024A (fr) * | 1952-01-02 | 1954-09-30 | Crane Co | Appareil pour la production de métaux par réduction de leurs sels |
US2782118A (en) * | 1952-02-19 | 1957-02-19 | Monsanto Chemicals | Production of refractory metals |
FR1088006A (fr) * | 1953-09-18 | 1955-03-02 | Nat Res Corp | Procédé pour la fabrication de titane pur et autres métaux |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3069255A (en) * | 1957-11-25 | 1962-12-18 | Jr Don H Baker | Production of high purity titanium by metallic sodium reduction of titanic halide |
US2995440A (en) * | 1958-04-23 | 1961-08-08 | Union Carbide Corp | Process for producing reactive metals |
US3554521A (en) * | 1966-05-23 | 1971-01-12 | British Iron Steel Research | The treating or refining of metal |
US3535109A (en) * | 1967-06-22 | 1970-10-20 | Dal Y Ingersoll | Method for producing titanium and other reactive metals |
WO1984002516A1 (fr) * | 1982-12-27 | 1984-07-05 | Stanford Res Inst Int | Procede et appareil pour obtenir du silicium a partir d'acide fluosilicique |
US4529576A (en) * | 1982-12-27 | 1985-07-16 | Sri International | Process and apparatus for obtaining silicon from fluosilicic acid |
US4584181A (en) * | 1982-12-27 | 1986-04-22 | Sri International | Process and apparatus for obtaining silicon from fluosilicic acid |
Also Published As
Publication number | Publication date |
---|---|
FR1138925A (fr) | 1957-06-21 |
GB821817A (en) | 1959-10-14 |
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