US3736132A - Method for producing refractory metals - Google Patents

Method for producing refractory metals Download PDF

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Publication number
US3736132A
US3736132A US00209094A US3736132DA US3736132A US 3736132 A US3736132 A US 3736132A US 00209094 A US00209094 A US 00209094A US 3736132D A US3736132D A US 3736132DA US 3736132 A US3736132 A US 3736132A
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United States
Prior art keywords
titanium
metal
reduction
rod
sodium
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Expired - Lifetime
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US00209094A
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English (en)
Inventor
H H Morse
C L Easterday
D E Easterday
L S Plock
F K Morgan
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United States Steel Corp
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Steel Corp
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    • 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
    • C22B34/10—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

Definitions

  • This invention relates to the manufacture of titanium or zirconium. More particularly, the invention relates to an improved process for continuously producing titanium or zirconium in which a partially reduced material corresponding to a metal tetrahalide-sodium mixture in which about 45% to 55% of the stoichiometric reduction of the metal tetrahalide to the metal has occurred is continuously mixed with an alkali metal at a temperature between 10D-200 C. to form an intermediate material corresponding to a metal tetrahalide-sodium mixture in which about 55% to 95% of the stoichiometric reduction to the metal has occurred, compacting the intermediate material at a temperature of less than C.
  • the process of this invention provides a' continuous process in which the reaction mixture has good processahility at all stages of the process and in which the intermediate material can be compacted into the continuous rod without particles sloughing off or the application of undue pressures or the use of temperatures which can cause alloying of the highly reactive metal to any of the process equipment.
  • the invention also provides a non-compacted, nonaking intermediate material which can be compacted and extruded into a unique self-supporting, continuous rod without using undue pressure and without the probability of sloughing off of particles from the reaction mass.
  • the unique self-supporting continuous rod, both sintered and non-sintered is another feature of this invention.
  • the continuous rod provides a means of achieving a continuous reduction process and thereby convert the semicontinuous, semi-batch process of the prior art into a large scale, continuous commercial process.
  • a partially reduced material a TiCl4-Na mixture in which about 45% to 55% of the stoichiometric reduction to the metal has occurred, is continuously mixed with sodium.
  • the partially reduced material is obtained in any suitable manner and preferably as described in the first step of the aforementioned Schott et al patent.
  • titanium tetrachloride is reduced with an insuicient amount of sodium for stoichiometric reduction to the metal.
  • hte sodium is employed at about 45% to 55%, preferably about 50%, of the theoretical amount required to completely convert the titanium tetrachloride to titanium.
  • the average composition of the partially reduced material principally corresponds to NagTiCh, i.e., the composition, on the average, is equivalent to Na2TiCl4 (TiCl2:2NaCl).
  • Such sodium titanium chloride complex which can, of course, be admixed with varying proportions of unreacted TiCl4 and varying proportions of other partially reduced or totally reduced materials, will hereinafter be referred ot as the reducer product because the reaction is usually accomplished in a reactor commonly called the reducer,
  • the reducer product and sodium are mixed and partially reacted in an inert atsmosphere, such as argon, at a temperature between 100-200 C., preferably about 130-160 C., to insure that complete reduction of the titanium chloride content of the Na2TiCl4 to titanium does not occur.
  • an inert atsmosphere such as argon
  • temperatures below about 100 C. either no reduction occurs or the reduction is so slow as to be impractical.
  • temperatures above about 200 C. it is too dicult to practically control the degree of reaction.
  • the sodium employed in this step is employed in an amount sucient to complete stoichiometric reduction of the reducer product to titanium metal and preferably a slight excess over the stoichiometric amount.
  • the amount of sodium employed is generally about 50% of the theoretical stoichiometric amount necessary to reduce the original amount of titanium tetrachloride to titanium and preferably, slightly in excess of 50%.
  • the mixing and further reducing is continued in the mixer until an intermediate product (mixer product) corresponding to a TiCl4-Na mixture in which about 55% to 95%, preferably about 75% of the stoichiometric reduction of the initial TiCl4 has occurred.
  • an intermediate product mixture product
  • the reacted portion of the mass has u an average composition principally corresponding to NasTiCl., and is in the presence of the remaining sodium for complete reduction.
  • the composition of the mixer product approaches 100% Na3TiCl4
  • the material approaches its lightest color and becomes extremely fluffy, with a high angle of repose, and has the appearance and consistency of dirty wet snow.
  • the concentration of the Na3TiCl4 complex approaches 100%, compaction, the next step in the preferred process, can be performed at low pressures and without particles of the mixer product sloughing off.
  • reaction of the additional sodium over and above that required to form the Na3TiCl4 is very slow at the reaction remperature employed in the mixing step. As a result, complete reduction to the metal is avoided by cooling the mixer product to 100 C. or lower when the desired amount of complex has been formed without a significant amount of the complex being converted to titanium.
  • the mixer product cooled to less than 100 C.
  • the mixer product is compacted into a continuous rod.
  • Incremental charges of the granular intermediate material are continuously compacted into a die and each charge is compacted against and into engagement with a prior compacted charge to form the continuous bar or rod.
  • the compacting is preferably accomplished under an inert atmosphere such as argon, and ambient temperature is generally ernployed. At this temperature, no substantial amount of further reduction of the titanium chloride content of the mixer product by the non-reacted sodium in the material occurs.
  • the average composition of the mixer product does not correspond to at least 15 weight percent Na3TiCl4, it is necessary to use pressure in excess of 4000 p.s.i. and even with such pressures, a substantial amount of the material will not compact into a continuous rod or will flake off the rod formed.
  • the temperature is not below 100 C., further reduction will occur resulting in the production of titanium in a highly reactive state while still in the compactor which may alloy with the steel of the apparatus.
  • the temperature and composition of the mixer product no more than about 4000 p.s.i., and preferably about 1000 to 3000 p.s.i. is needed to compact the granular mixer product into the continuous rod.
  • any appropriate compacting device known in the art could be employed in this step such as, for example, the compacting devices described in ⁇ U.S. Pats. 2,651,952, 2,656,743 and 3,014,238.
  • the continuous rod thus produced is unique, and can only be produced when the foregoing procedures are employed. lt is self-supporting, and can be fed wherever desired for subsequent processing. It is relatively unreactive and stable under aimbient conditions.
  • the compacted rod or bar is thereafter heated to a temperature of at least about 800 C. and preferably about 900-1500 C.
  • the heating accomplishes three things: the remaining titanium chloride is reduced to titanium metal; the metallic sponge formed is sintered; and simultaneously, the salt (NaCl) by-product is melted which facilitates separation and removal of the salt from the rod-shaped, sintered titanium metal product. Any temperature above the melting point of salt will serve to complete the reaction and provide some sintering of the bar. Since salt can be removed during the heating, it is desirable to ha-ve the temperature as high as is practical considering the equipment and materials of construction in order to remove the maximum amount of salt and to secure the densest sintering.
  • the heating step is preferably accomplished under an inert atmosphere such as argon and the rod is maintained at the sintering temperature for about 1-10 minutes or more, preferably about 3-5 minutes.
  • an inert atmosphere such as argon
  • the salt left in the titanium can be reduced to less than 0.1% and subsequent purification can, if desired, be omitted.
  • the sintered rod so produced is unique-it is very flexible when hot and, with proper guides, can be fed wherever desired for subsequent processing.
  • the rodshaped, sintered titanium metal product generally contains at least about 50% titanium, usually at least 60% and the remainder is salt.
  • the titanium thus produced is sufficiently inert so that when cooled, it can easily be handled and does not react with air or water. Any salt remaining with the titanium can be further removed by any of the several continuous processes known to those skilled in the art such as leaching, drip melting, plasma arc melting, and the like.
  • the figure shows the sequence of steps of the process.
  • Sodium via line l, at a rate of 1210 parts per hour, and titanium tetrachloride via line 2, at the rate of 5000 parts per hour, are continuously introduced into a stirred reducer 3 maintained under an argon blanket and controlled at a temperature of about -175 C.
  • the resulting partially reduced material (reducer product), which is substantially all Na2TiCl4 is withdrawn via line 4 from the reducer at a rate of 6210 parts per hour and introduced into a mixer S.
  • Additional sodium is introduced via line 6 into mixer 5 at a rate of 1210 parts per hour.
  • the particular mixer employed is described in copending application Ser. No. 209,104, entitled Mixer For Preparing An Easily Compactable Material, filed of e-ven date herewith, which is hereby incorporated by reference.
  • the temperature within mixer S is controlled at about 150 C. at the reaction zone thereof and decreased to about 90 C. at the outlet.
  • the mixer product is continuously withdrawn from the apparatus via line 7 at the rate of 7420 parts per hour.
  • the mixer product thus formed contains about 92% Na3TiCl4 and about 8% free sodium.
  • the mixer product is compacted at the rate of 7420 parts per hour at room temperature in compactor 8.
  • the material enters a compacting section and is subjected to a pressure of 2000 p.s.i. by means of a hydraulically operated ram. Continuous self-supporting rods of the compacted mixer product are prepared by the interlocking action of pressing one compact against the preceding compact due to the irregular face of the piston head.
  • the resulting compacted rod is continuously withdrawn from compactor 8 via conduit 9 and introduced into a tube 10 heated to 1100 C. by an induction coil at the rate of 7420 parts per hour.
  • Tube 10 can also be heated by resistance heat, or by a gas tired furnace, and the like.
  • the rod is maintained in sintering tube 10 for about 3 minutes when operating at atmospheric pressure.
  • the tube 10 has provision 11 for drainage of liquid salt and 5210 parts per hour of sodium chloride, i.e., about 85% of the salt produced per hour, is removed.
  • the sintered rod is removed from the hot tube 10 via conduit 12 at a rate of 2210 parts per hour.
  • the thus formed sintered titanium metal rod contains about 57% titanium and about 43% salt.
  • the rm, sintered titanium sponge is continuously fed vertically downward into a vertical tube furnace 13 and the lower end melted.
  • the titanium metal, free from salt impurity, is thereafter recovered at 14.
  • step (a) is about -160 C.
  • step (a) wherein the feed rates of the respective reactants in step (a) are regulated such that an intermediate material is formed corresponding to a titanium tetrachloride-sodium mixture in which about 75% of the total stoichiometric reduction of the titanium tetrachloride to titanium metal has occurred and wherein the intermediate material is compacted in step (b) at a maximum pressure of 4000 p.s.i.
  • step (c) is heated to about 900-1500 C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)
US00209094A 1971-12-17 1971-12-17 Method for producing refractory metals Expired - Lifetime US3736132A (en)

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US20909471A 1971-12-17 1971-12-17

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JP (1) JPS5536694B2 (enExample)
CA (1) CA986719A (enExample)
DE (1) DE2261968A1 (enExample)
FR (1) FR2163708B3 (enExample)
GB (1) GB1364998A (enExample)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032329A (en) * 1976-02-20 1977-06-28 University Of Minnesota, Inc. Metal reduction process employing metal sub-halides
US4231790A (en) * 1975-04-18 1980-11-04 Hermann C. Starck Berlin Process for the preparation of tantalum and niobium powders of improved efficiency
US20030075011A1 (en) * 2001-10-09 2003-04-24 Washington University Tightly agglomerated non-oxide particles and method for producing the same
US20030230170A1 (en) * 2002-06-14 2003-12-18 Woodfield Andrew Philip Method for fabricating a metallic article without any melting
EP1433555A1 (en) * 2002-12-23 2004-06-30 General Electric Company Method for meltless manufacturing of rod, and its use as a welding rod
US20040208773A1 (en) * 2002-06-14 2004-10-21 General Electric Comapny Method for preparing a metallic article having an other additive constituent, without any melting
US20050223849A1 (en) * 2002-12-23 2005-10-13 General Electric Company Method for making and using a rod assembly
US20060057017A1 (en) * 2002-06-14 2006-03-16 General Electric Company Method for producing a titanium metallic composition having titanium boride particles dispersed therein
US20060102255A1 (en) * 2004-11-12 2006-05-18 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US10066308B2 (en) 2011-12-22 2018-09-04 Universal Technical Resource Services, Inc. System and method for extraction and refining of titanium
US10400305B2 (en) 2016-09-14 2019-09-03 Universal Achemetal Titanium, Llc Method for producing titanium-aluminum-vanadium alloy
US11959185B2 (en) 2017-01-13 2024-04-16 Universal Achemetal Titanium, Llc Titanium master alloy for titanium-aluminum based alloys

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4231790A (en) * 1975-04-18 1980-11-04 Hermann C. Starck Berlin Process for the preparation of tantalum and niobium powders of improved efficiency
US4347084A (en) * 1975-04-18 1982-08-31 Hermann C. Starck Berlin Electrodes of sintered tantalum powder of fine grain size and process of production
US4032329A (en) * 1976-02-20 1977-06-28 University Of Minnesota, Inc. Metal reduction process employing metal sub-halides
US20030075011A1 (en) * 2001-10-09 2003-04-24 Washington University Tightly agglomerated non-oxide particles and method for producing the same
US7442227B2 (en) 2001-10-09 2008-10-28 Washington Unniversity Tightly agglomerated non-oxide particles and method for producing the same
US20060057017A1 (en) * 2002-06-14 2006-03-16 General Electric Company Method for producing a titanium metallic composition having titanium boride particles dispersed therein
US20040208773A1 (en) * 2002-06-14 2004-10-21 General Electric Comapny Method for preparing a metallic article having an other additive constituent, without any melting
US10100386B2 (en) 2002-06-14 2018-10-16 General Electric Company Method for preparing a metallic article having an other additive constituent, without any melting
US7655182B2 (en) 2002-06-14 2010-02-02 General Electric Company Method for fabricating a metallic article without any melting
US7842231B2 (en) 2002-06-14 2010-11-30 General Electric Company Method for producing a titanium metallic composition having titanium boride particles dispersed therein
US20070269333A1 (en) * 2002-06-14 2007-11-22 General Electric Company Method for fabricating a metallic article without any melting
US7329381B2 (en) 2002-06-14 2008-02-12 General Electric Company Method for fabricating a metallic article without any melting
US7410610B2 (en) 2002-06-14 2008-08-12 General Electric Company Method for producing a titanium metallic composition having titanium boride particles dispersed therein
US20080193319A1 (en) * 2002-06-14 2008-08-14 General Electric Company Method for producing a titanium metallic composition having titanium boride particles dispersed therein
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
US20030230170A1 (en) * 2002-06-14 2003-12-18 Woodfield Andrew Philip Method for fabricating a metallic article without any melting
US20050223849A1 (en) * 2002-12-23 2005-10-13 General Electric Company Method for making and using a rod assembly
EP1433555A1 (en) * 2002-12-23 2004-06-30 General Electric Company Method for meltless manufacturing of rod, and its use as a welding rod
US7727462B2 (en) 2002-12-23 2010-06-01 General Electric Company Method for meltless manufacturing of rod, and its use as a welding rod
US7897103B2 (en) 2002-12-23 2011-03-01 General Electric Company Method for making and using a rod assembly
US7531021B2 (en) 2004-11-12 2009-05-12 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US20060102255A1 (en) * 2004-11-12 2006-05-18 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US8562714B2 (en) 2004-11-12 2013-10-22 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US20090229411A1 (en) * 2004-11-12 2009-09-17 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US10604452B2 (en) 2004-11-12 2020-03-31 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
EP2298473A3 (en) * 2005-05-27 2013-12-25 General Electric Company Method for making and using a rod assembly as feedstock material in a smelting process
US10066308B2 (en) 2011-12-22 2018-09-04 Universal Technical Resource Services, Inc. System and method for extraction and refining of titanium
US10731264B2 (en) 2011-12-22 2020-08-04 Universal Achemetal Titanium, Llc System and method for extraction and refining of titanium
US11280013B2 (en) 2011-12-22 2022-03-22 Universal Achemetal Titanium, Llc System and method for extraction and refining of titanium
US10400305B2 (en) 2016-09-14 2019-09-03 Universal Achemetal Titanium, Llc Method for producing titanium-aluminum-vanadium alloy
US11959185B2 (en) 2017-01-13 2024-04-16 Universal Achemetal Titanium, Llc Titanium master alloy for titanium-aluminum based alloys

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Publication number Publication date
DE2261968A1 (de) 1973-06-20
JPS4876713A (enExample) 1973-10-16
GB1364998A (en) 1974-08-29
JPS5536694B2 (enExample) 1980-09-22
FR2163708B3 (enExample) 1976-01-09
CA986719A (en) 1976-04-06
FR2163708A1 (enExample) 1973-07-27

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