US2821468A - Production of titanium - Google Patents

Production of titanium Download PDF

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Publication number
US2821468A
US2821468A US628709A US62870956A US2821468A US 2821468 A US2821468 A US 2821468A US 628709 A US628709 A US 628709A US 62870956 A US62870956 A US 62870956A US 2821468 A US2821468 A US 2821468A
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US
United States
Prior art keywords
titanium
crystals
mass
titanium metal
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
Application number
US628709A
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English (en)
Inventor
Lester D Grady
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
New Jersey Zinc Co
Original Assignee
New Jersey Zinc Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to NL112297D priority Critical patent/NL112297C/xx
Priority to LU35440D priority patent/LU35440A1/xx
Priority to NL222106D priority patent/NL222106A/xx
Priority to BE560682D priority patent/BE560682A/xx
Priority to US628709A priority patent/US2821468A/en
Application filed by New Jersey Zinc Co filed Critical New Jersey Zinc Co
Priority to US664898A priority patent/US2875033A/en
Priority to GB25399/57A priority patent/GB806470A/en
Priority to FR1182039D priority patent/FR1182039A/fr
Priority to DEN14082A priority patent/DE1086051B/de
Application granted granted Critical
Publication of US2821468A publication Critical patent/US2821468A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C13/00—Disintegrating by mills having rotary beater elements ; Hammer mills
    • 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
    • C22B34/1295—Refining, melting, remelting, working up of titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode

Definitions

  • This invention relates to the production of titanium metal and more particularly, to the recovery of the highest purity fraction of a mass of electrodeposited titanium metal.
  • the metal is obtained as a massive deposit on the electrolytic cell cathode.
  • the titanium deposit on the cathode contains a considerable amount of occluded salt from the bath.
  • the cathode deposit is harvested by bodily withdrawing the cathode and its deposit from the fused salt bath, a further considerable quantity of salt adheres to the surface of the deposit. Accordingly, the recovery of the titanium metal component of this cathode deposit requires separation of the entrained salt from the metal, and this is usually achieved by leaching the salt away from the metal after the massive cathode deposit has been crushed to expose the entrained salt.
  • the lattice work of titanium metal in the cathode .deposit is composed of a dendritic mass of titanium crystals having a large range of particle sizes.
  • the finer crystals, to the extent that their surfaces are exposed, have a larger ratio of surface area to volume than do the coarser crystals, and consequently there is more opportunity for surface oxidation per unit of volume in the case of the fine crystals than in the coarse crystals.
  • coalesced granules coarser than 8 mesh need to be broken down into their component individual crystals so that any entrained impure fines may be removed in later sizing operations. While this may appear to be a simple operation, many methods and apparatuses have been tried with little success.
  • the difficulty is that titanium metal of high purity is soft, and milling methods that function by impact simply compress the soft metal granules without shattering them into their individual components.
  • Prolonged ball milling for example, will produce flakes of metal in which very fine, highly impure, titanium particles are embedded. These embedded particles cannot be removed from the purer larger particles by subsequent screening or elutriation operations.
  • the method of my invention is adapted to selectively separate the relatively pure and relatively impure crystals of electrolytically deposited titanium metal from a massive cathode deposit composed essentially of a mixture of titanium crystals with adhering and entrained electrolyte salts.
  • the method comprises first crushing the cathode deposit to form a mass of coarse aggregates not substantially smaller than that which will pass through approximately one-quarter inch screen openings, leaching the crushed mass with an aqueous medium to dissolve the electrolyte salts away from the titanium metal, and disintegrating the residual mass of titanium metal predominantly into its own component crystals with a scissor-like action between cutting blades spaced apart a distance at least as great as the maximum particle size of the individual titanium crystals in the cathode deposit.
  • the blades move at sufficiently high speed so that the mass of titanium metal is disintegrated substantially exclusively by shearing impact, and a chemically inert atmosphere is maintained surrounding the mass of titanium metal while it is being disintegrated.
  • the resulting disintegrated mass is classified by screening, elutriation, centrifuging or the like, to separate a relatively pure fraction composed of the relatively coarse titanium crystals from a relatively impure fraction composed of the relatively fine ltitanium crystals.
  • the harvested cathode deposit composed of metallic titanium and entrained electrolyte salts is first broken up by any conventional crushing operation.
  • a jaw crusher is wholly satisfactory for this purpose, but regardless of the apparatus used in [this operation the cathode deposit should not be crushed fine enough to cause such compression of the mass as to result in a significant proportion of the fine, low-purity crystals being welded or embedded in the coarser, high-purity crystals.
  • the crushing operation should be merely sufiicient to break up ⁇ the cathode deposit into pieces small enough to facilitate extraction of the entrained salt, the major amount of disintegration of the titanium metal into its own component crystals being effected by the scissor-like shearing impact action to which the salt-free mass is subjected pursuant to the invention.
  • a relatively low metal-content cathode deposit composed of about 35% by weight of metallic titanium and the balance entrained salt should not be crushed finer than that required for it to pass through approximately one-quarter inch screen openings.
  • a relatively high metalcontent cathode deposit containing about 60% metallic titanium should not be crushed finer than that required for it to pass through approximately one inch screen openings.
  • the electrolyte salts are extracted by any suitable aqueous medium.
  • aqueous medium for example, plain water may be used, although the use of water acidified with about 0.5% by weight of hydrogen chloride is particularly advantageous.
  • Such a dilute hydrochloric acid solution tends to minify hydration of the salts .to relatively insoluble residues with resulting oxygen-contamination of the leached metal.
  • any other effective leaching medium may be used in practicing my invention, the only requirement of the leaching operation being that it produces a mass of titanium metal substantially free of entrained salts.
  • the resulting salt-free mass of titanium metal is then disintegrated pursuant to my invention so as to obtain the original crystals of the titanium cathode deposit substantially completely freed of one another.
  • This disintegration is efiected by subjecting the crushed and leached mass to a scissor-like action between cutting blades spaced apart a distance at least as great as the maximum particle size of the individual titanium crystals in the leached mass.
  • the spacing between the blades is significantly less than the maximum crystal particle size, the larger crystals, which are relatively pure, are broken up into smaller particles within the range of the lower-purity naturally-occurring crystals.
  • rotary cutters and knife cutters used to disintegrate plastic chips, leather and rubber scraps, asbestos, cork, paper board, and the like, are particularly suitable.
  • These rotary cutters comprise a cylindrical enclosure provided with stationary or bed knives and an inner rotary member carrying cooperating knives. The relative motion of these knives, whose spacing may be readily adjusted, provides a scissor-like cutting action by shearing impact which is wholly different from the compressive and distorting action of roller crushers, ball mills, tumbling mills, disk grinders, and the like.
  • a rotor velocity of 1200 R. P. M. was found to be particularly satisfactory. This velocity is not critical, however; the only requirement of the rotor velocity is that it should be sufficient to effect separation of the titanium crystals by scissor-like shearing impact.
  • the final product is a mass of non-oxidized individual crystals consisting of those of which the cathode deposit was composed.
  • those having a particle size range of through 8 and on 65 mesh appear to have a significantly higher degree of purity than the other larger and smaller size fractions not only with respect to their oxygen content but also with respect to the presence of nitrogen, hydrogen and the various metallic elements with which titanium is generally contaminated.
  • the crystals having a particle size range of through 14 and on 35 mesh have the highest purity.
  • the degree of ductility measured as Brinell hardness number, is commensurate with the degree of purity.
  • the cathode deposit was crushed in a jaw crusher so as to pass completely through 1 inch diameter openings. The crushed mass was then leached for two hours with aqueous hydrochloric acid containing 0.5% by weight of hydrogen chloride and maintained at a temperature of about 25 C.
  • the leached mass was washed with water so as to obtain a coarse titanium metal substantially free of entrained salts.
  • a sample of this material was examined microscopically and was found to contain titanium metal crystals having a maximum size of through 14 mesh (just under 1 millimeter in diameter).
  • the resulting moist mass of titanium was then charged to the type of rotary cutter shown in the accompanying drawing in which the single figure is a front sectional elevation of the cutter.
  • the cutter comprises an outer cylindrical frame 1.
  • a number of bed knives 2 are mounted around the interior surface of the frame.
  • the bed knives cooperate with rotor knives 3 carried at the extremities of arms 4 mounted on a rotatable shaft 5 axially positioned within the cylindrical frame 1.
  • the feed material is charged through a hopper 6 at the top of the frame, and the disintegrated material which passes through a sizing screen 7 is discharged through a hopper 8.
  • the spacing between the rotor knives 3 and the stationary bed knives 2 was one-sixteenth inch.
  • the crushed and leached titanium metal was charged to the feed hopper 6, and the disintegrated titanium mass was discharged through the screen 7 having inch openings, thence through the discharge hopper 8.
  • the rotor shaft 5 was rotated at a speed of 1200 R. P. M. and an atmosphere of argon was maintained within the bed casing by means of a gas inlet line 9.
  • the 84.5 pounds of titanium were fed into the rotary cutter at the rate of 3 to 4 pounds per minute.
  • the discharged material had the screen and chemical analyses shown in the following table:
  • cent ness cent cent cent cent cent parts per million 4. 6 118 0.11 0. 003 0.002 about 1,000 15. 6 103 0.085 0.001 0.001 about 30 35. 2 87 0. 059 O. 001 0. 001 about 30 24. 8 102 0.077 0.001 0.001 about 40 8. 4 128 0. 14 0. 002 0.003 over 5. 0 161 0. 22 0. 003 0. 004 over 150 3. 5 189 0. 32 O. 005 0. 006 over 150 -200 +325 2. 9 215 0.43 0. 005 0.006 over 150 It can be seen from Table I that the particles having a size range of through 8 and on 65 mesh have a higher degree of purity than the largerand smaller-size fractions.
  • the larger-size fraction was composed of aggregates of crystals which had not been completely disintegrated into their component crystals, and the smaller- -size fraction was composed of the smaller-size crystals freed from the original aggregates.
  • the crystals having a size range of through 14 and .on 35 mesh had the highest degree of purity. The difference in purity and in Brinell hardness number are clear indications of the effectiveness of the method of the present invention.
  • the method of selectively separating relatively pure and relatively impure crystals of electrolytically deposited titanium metal from a massive cathode deposit composed essentially of a mixture of titanium crystals with adhering and entrained electrolyte salts which comprises crushing the cathode deposit to form a mass of coarse aggregates not substantially smaller than that which will pass through approximately one-quarter inch screen openings, leaching the crushed mass with an aqueous medium to dissolve the electrolyte salts away from the titanium metal, disintegrating the residualrnass of titanium metal predominantly into its own component crystals with a scissor-like action betveen cutting blades spaced apart a distance at least as great as the maximum particle size of the individual titanium crystals and moving at sufiiciently high speed so that the mass of titanium metal is disintegrated substantially exclusively by shearing impact, maintaining a chemically inert atmosphere surrounding the mass of titanium metal while it is being disintegrated, and classifying the resulting disintegrated mass to separate a relatively pure fraction composed of the relatively coarse titanium crystal
  • the method of selectively separating relatively pure and relatively impure crystals of electrolytically deposited titanium metal from a massive cathode deposit composed essentially of a mixture of titanium crystals with adhering and entrained electrolyte salts which comprises crushing the cathode deposit to form a mass of coarse aggregates not substantially smaller than that which will pass through approximately one-quarter inch screen openings, leaching the crushed mass with an aqueous medium to dissolve the electrolyte salts away from the titanium metal, disintegrating the residual mass of titanium metal predominantly into its own component crystals with a scissor-like action between cutting blades spaced apart a distance at least as great as the maximum particle size of the individual titanium crystals and moving at sufficiently high speed so that the mass of titanium metal is disintegrated substantially exclusively by shearing impact, maintaining a chemically inert atmosphere surrounding the mass of titanium metal while it is being disintegrated, and classifying the resulting disintegrated mass to separate a relatively pure fraction composed of titanium particles having a size range of through 8 and on 65 mesh screen from
  • the method of selectively separating relatively pure and relatively impure crystals of electrolytically deposited titanium metal from a massive cathode deposit composed essentially of a mixture of titanium crystals with adhering and entrained electrolyte salts which comprises crushing the cathode deposit to form a mass of coarse aggregates not substantially smaller than that which will pass through approximately one-quarter inch screen openings, leaching the crushed mass with an aqueous medium to dissolve the electrolyte salts away from the titanium metal, disintegrating the residual mass of titanium metal predominantly into its own component crystals with a scissor-like action between cutting blades spaced apart a distance at least as great as the maximum particle size of the individual titanium crystals and moving at sufficiently high speed so that the mass of titanium metal is disintegrated substantially exclusively by shearing impact, maintaining a chemically inert atmosphere surrounding the mass of titanium metal While it is being disintegrated, and classifying the resulting disintegrated mass to separate a relatively pure fraction composed of titanium particles having a size range of through 14 and on 35 mesh screen from
  • the method of selectively separating relatively pure and relatively impure crystals of electrolytically deposited titanium metal from a massive cathode deposit composed essentially of a mixture of titanium crystals with adhering and entrained electrolyte salts which comprises crushing the cathode deposit to form a mass of coarse aggergates not substantially smaller than that which will pass through approximately one-quarter inch screen openings, leaching the crushed mass with an aqueous medium to dissolve the electrolyte salts away from the titanium metal, disintegrating the residual mass of titanium metal predominantly into its own component crystals with a scissor-like action between cutting blades spaced apart a distance at least as great as the maximum particle size of the individual titanium crystals and moving at sufliciently high speed so that the mass of titanium metal is disintegrated substantially exclusively by shearing impact, maintaining the titanium suspended in a body of Water while it is being disintegrated, and classifying the resulting disintegrated mass to separate a relatively pure fraction composed of the relatively coarse titanium crystals from a relatively impure fraction composed of

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Food Science & Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US628709A 1956-12-17 1956-12-17 Production of titanium Expired - Lifetime US2821468A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NL222106D NL222106A (fr) 1956-12-17
BE560682D BE560682A (fr) 1956-12-17
NL112297D NL112297C (fr) 1956-12-17
LU35440D LU35440A1 (fr) 1956-12-17
US628709A US2821468A (en) 1956-12-17 1956-12-17 Production of titanium
US664898A US2875033A (en) 1956-12-17 1957-06-11 Method of separating titanium crystals
GB25399/57A GB806470A (en) 1956-12-17 1957-08-12 Improvements in production of titanium
FR1182039D FR1182039A (fr) 1956-12-17 1957-09-05 Production du titane
DEN14082A DE1086051B (de) 1956-12-17 1957-09-09 Verfahren und Vorrichtung zur Gewinnung von Titan hoher Reinheit

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US628709A US2821468A (en) 1956-12-17 1956-12-17 Production of titanium

Publications (1)

Publication Number Publication Date
US2821468A true US2821468A (en) 1958-01-28

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US628709A Expired - Lifetime US2821468A (en) 1956-12-17 1956-12-17 Production of titanium

Country Status (7)

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US (1) US2821468A (fr)
BE (1) BE560682A (fr)
DE (1) DE1086051B (fr)
FR (1) FR1182039A (fr)
GB (1) GB806470A (fr)
LU (1) LU35440A1 (fr)
NL (2) NL112297C (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2984560A (en) * 1960-02-08 1961-05-16 Du Pont Production of high-purity, ductile titanium powder
US20100127105A1 (en) * 2008-11-26 2010-05-27 Roland Nied Pulverizer And Operating Method Therefor
CN103111354A (zh) * 2013-01-31 2013-05-22 攀钢集团攀枝花钢铁研究院有限公司 熔盐电解精炼的阴极析出物的预处理方法
CN103878379A (zh) * 2014-04-08 2014-06-25 江苏巨鑫磁业有限公司 一种钕铁硼磁性材料破碎仓

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3921481A (en) * 1973-07-10 1975-11-25 Leesona Corp Method and apparatus for noise suppression

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB678807A (en) * 1950-05-12 1952-09-10 Shawinigan Water & Power Co Process for the production of titanium metal
GB728523A (en) * 1951-10-18 1955-04-20 Titan Co Inc A new or improved method for refining titanium metal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2984560A (en) * 1960-02-08 1961-05-16 Du Pont Production of high-purity, ductile titanium powder
US20100127105A1 (en) * 2008-11-26 2010-05-27 Roland Nied Pulverizer And Operating Method Therefor
US8800901B2 (en) * 2008-11-26 2014-08-12 Roland Nied Pulverizer and operating method therefor
CN101733181B (zh) * 2008-11-26 2015-07-15 罗兰·尼德 粉碎机和粉碎机的操作方法
CN103111354A (zh) * 2013-01-31 2013-05-22 攀钢集团攀枝花钢铁研究院有限公司 熔盐电解精炼的阴极析出物的预处理方法
CN103111354B (zh) * 2013-01-31 2014-12-24 攀钢集团攀枝花钢铁研究院有限公司 熔盐电解精炼的阴极析出物的预处理方法
CN103878379A (zh) * 2014-04-08 2014-06-25 江苏巨鑫磁业有限公司 一种钕铁硼磁性材料破碎仓

Also Published As

Publication number Publication date
FR1182039A (fr) 1959-06-22
BE560682A (fr)
LU35440A1 (fr)
NL222106A (fr)
GB806470A (en) 1958-12-23
DE1086051B (de) 1960-07-28
NL112297C (fr)

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