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US3211520A - Process for the manufacture of low titanium chlorides - Google Patents

Process for the manufacture of low titanium chlorides Download PDF

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Publication number
US3211520A
US3211520A US126852A US12685261A US3211520A US 3211520 A US3211520 A US 3211520A US 126852 A US126852 A US 126852A US 12685261 A US12685261 A US 12685261A US 3211520 A US3211520 A US 3211520A
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Prior art keywords
hydrogen
titanium tetrachloride
titanium
nozzle
temperature
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US126852A
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English (en)
Inventor
Harnisch Heinz
Mehne Artur
Rodis Franz
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Knapsack AG
Knapsack Griesheim AG
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Knapsack AG
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/02Halides of titanium
    • C01G23/026Titanium trichloride
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/02Halides of titanium

Definitions

  • a mixture of hydrogen and titanium tetrachloride is reduced in an electric arc.
  • the hydrogen must be preheated to a temperature above 1000o C., advantageously above 2500 C., to obtain economical yields.
  • the hydrogen is advantageously heated electrically, for example in an electric arc, since it is very diiicult to heat hydrogen indirectly in a heat exchanger to ⁇ a temperature of l000 C. and more owing to the permeability to hydrogen of the walls of the vessel.
  • an electric arc such a high temperature is generally obtained that at least part of the hydrogen is present in the form of atoms. It is particularly advantageous to use an electric arc arrangement as described in German Utility Patent No. 1,781,880.
  • the reactants are advantageously mixed in the gaseous phase as rapidly yas possible.
  • the heated hydrogen is conducted through a channel of annular cross-section and the titanium tetrachloride which has been converted into the gaseous state by heating to above the boiling point is introduced approximately vertically to the said channel through an annular slot provided in the channel.
  • the titanium tetrachloride is evaporated under a certain pressure so that the titanium tetrachloride vapor is brought into contact with the preheated hydrogen at a relatively high speed.
  • additional hydrogen gas may be admixed.
  • the titanium tetrachloride or the mixture of titanium tetrachloride and hydrogen may be introduced tangentially into a channel of circular cross-section through which hot hydrogen flows. In any case, it is important to mix the two reactants Vas rapidly as possible.
  • reaction gases are then conducted to a moved cooled surface in order to be chilled.
  • the reaction product which has deposited on the moving cooled surface as a loose layer is removed therefrom by a cleaning device, such as a stationary knife or Ia brush, so that the reaction gases arriving at the said surface always strike a clean surface whereby, and especially also owing to the high thermal conductivity of the hydrogen used in excess, ⁇ a very intense chilling is produced.
  • chilling is generally brought about by injecting cold liquids.
  • a thermally stable liquid which does not react with the reaction products.
  • stable liquids particularly water
  • liquids that are inert with respect to the reaction product such as organic liquids (benzene, toluene, decahydronaphthalene)
  • organic liquids benzene, toluene, decahydronaphthalene
  • an apparatus using a recycled chilling agent is more complicated than the apparatus of the invention which dispenses with all accessories necessary for such chilling cycle (pump, heat exchanger, storage container).
  • the heat content absorbed by the gases to be chilled is lost, whereas in the present process the energy may, under certain circumstances, be recovered, for example, in the form of hot water or steam.
  • the moving cooled surface must be disposed within a casing which is secluded from the outer atmosphere since the desired reaction products would react even with traces of oxygen or water vapor.
  • the starting materials, titanium tetrachloride and hydrogen must also be free from oxygen, nitrogen and other impurities, in order to obtain a pure reaction product. If the temperature of the cooled surface is too low, the separated reaction products absorb unreacted titanium tetrachloride. The temperature is, therefore, advantageously kept so high that such absorption is substantially avoided.
  • the cooling agent for the moving surface for example water
  • suflicient to keep the cooling agent for the moving surface, for example water, at a temperature of about 50 to about 300 C., advantageously about 50 to about 100 C., in order to obtain a final product containing less than about 2% of titanium tetrachloride.
  • titanium trichloride is generally obtained almost exclusively, besides unreacted titanium tetrachloride. If a higher molar ratio is used, the titanium trichloride obtained contains increasing amounts of titanium dichloride.
  • the space-time yield exceeds 0.15 kg./l. h. and the reaction product is obtained in the form of a fine pyrophoric powder which oxides in air with glowing and emission of a white fog.
  • the reaction products which have been stripped off are collected under an inert gas in a receiver disposed beneath the housing of the cooling roller.
  • the gases flowing off contain, in addition to unreacted titanium tetrachloride, reaction products in the form of dust, i.e. the gas flowing off contains a considerable portion of loW titanium halides which are removed by dry gas purification.
  • the dry gas purification it is necessary -to maintain the walls of the apparatus used lfor the removal of the dust at temperatures which prevent a condensation of unreacted titanium. tetrachloride. These temperatures depend on the partial pressure of the titanium tetrachloride in the apparatus and shall be about 5 to about 100 C. above the dew point of the titanium tetrachloride under the working conditions in a given case.
  • the dust may be separated, for example, in a cyclone, impact Crusher or quiescent vessel.
  • the unreacted titanium tetrachloride is separated from the dust-free exhaust gas in known manner by cooling and may be returned to the process. Cooling may be effected in, for example, two stages: first, in a liquid condensation stage operating at a temperature above the melting point of titanium tetrachloride (-23 C.) and then in a solid condensation stage operating at a temperature below the said melting point.
  • the hydrogen used in excess then only contains hydrogen chloride, which may be removed, for example, by absorption with the help of an appropriate device, so that the hydrogen can subsequently be dried and reused for the reduction.
  • the substances obtained by the process of the invention are very pure.
  • the reduction of titanium tetrachloride yields products which consist of more than 99.8% of titanium and chlorine. This is of particular importance when the process of the invention is carried out as a preliminary stage for the production of titanium metal.
  • FIG. l is a side elevation of an apparatus in which the moving and cooled surface is, for example, cylindrical, the elevation being taken along line I-I of FIGURE 2;
  • FIGURE 2 is an elevation of the same apparatus taken along line II-II of FIGURE 1;
  • FIGURE 3 is a longitudinal elevational of an apparatus in which ⁇ the moving and cooled surface is, yfor example, conical.
  • FIGURES 1 and 2 illustrate a technical mode of executing the reaction.
  • Hydrogen is introduced into the burner at 13 and preheated on its passage through an electric arc between cathode 4 and anode 5.
  • mixing nozzle 6 the preheated hydrogen, which is partially split into atoms, is admixed with gaseous titanium tetrachloride introduced through feed pipe 14.
  • the burner and the mixing nozzle 6 are disposed in a recess of cover 3.
  • the reaction products and the unreacted starting material strike the moved cooled roller 1.
  • a cooling agent for example water or oil, of a temperature of about 50 to about 300 C. is sprayed from the inside against that segment of roller 1 which is nearest to the burner.
  • the lower part of roller 1 is filled with the cooling agent coming from lthe upper part of roller 1.
  • the excess of cooling agent leaves roller 1 at 9 through an open cylinder.
  • Cooling roller 1 is surrounded with casing 2 provided with cooling jacket 10.
  • the solid reaction products adhering to the surface of roller 1 and the inside wall of casing 2 are removed by knife 17 secured to the casing and by a rotatable knife 16.
  • the latter can be operated by crank 15 or another mechanical drive disposed at that place.
  • the reaction products fall into receiver 19.
  • the exhaust gas leaves the apparatus through outlet 18 (FIG. 2) to be conducted through another separator, for example a cyclone or impact crusher.
  • FIG. 3 Another mode of executing the process of the invention can be realized with the apparatus shown in FIG. 3 -in which the reaction products are chilled and separated on a rotating cone.
  • the other parts of apparatus are analogous to those shown in FIGURE 1 and need not be explained here.
  • the aforesaid hydrogen which is used in an amount about 1.2 to about 20 times, advantageously 10 to 15 times, in excess of the theoretical amount, is rapidly mixed intimately in the gaseous phase with a higher titanium chloride, with the help of a mixing device, such as a nozzle, which is kept at a low temperature.
  • the reaction products are chilled, with the exclusion of the atmosphere, on a moving cooled surface from which the reaction products depositing thereon are continuously removed by a cleaning device and the reaction products are then collected under an inert gas in a receiver.
  • the hydrogen is advantageously heated by means of an electric arc arrangement to a temperature advantageously above 2500 C.
  • the process may also be carried out in a manner such that additional hydrogen is added to the titanium tetrachloride before the latter enters the mixing device.
  • the heated hydrogen is conducted through a channel 20 of, for example, circular cross-section and the titanium tetrachloride or the mixture of titanium tetrachloride and hydrogen is brought into contact with the hydrogen about vertically to the direction of ow of the hydrogen through an annular slot 21 which opens into channel 20 or it may be introduced tangentially into channel 20.
  • titanium tetrachloride and hydrogen may be separated from the exhaust gases which have been freed in known manner from hydrogen chloride and reaction product present in the form of dust, and returned to the reaction process after they have been separated from each other in known manner.
  • cooling surface 1 has the shape of a cone whose apex faces the atomized jet (see FIG. 3).
  • Example I 4750 parts titanium tetrachloride were evaporated, the liquid titanium tetrachloride flowing into the evaporator at an average rate of 9.5 kg./h., and then reacted in the gaseous state according to the following Equation 1 with 2.25 cubic meters (measured at N.T.P.) of hydrogen heated in the electric arc. According to Equation 1, this corresponded to an excess of hydrogen of 8 times the theoretical amount.
  • the rate of flow of the hydrogen was 4.5 cubic meters/h. (measured at N.T.P.).
  • the mixing nozzle was kept at 150 C., by cooling with air.
  • the amount of energy supplied to the electric arc for heating the hydrogen amounted to 22 kwh. (135 amperes, 325 volts). 2320 parts of pure titanium trichloride were obtained. Yield: 60%, calculated on the titanium tetrachloride used as the starting material.
  • Example 2 3340 parts titanium tetrachloride were evaporated, the liquid substance flowing into the evaporator at a rate of 6.68 kg./h., and then reacted with 2.25 cubic meters (measured at N.T.P.) of hydrogen heated in the electric arc. According to Equation 1, this corresponded to an excess of hydrogen of 11.4 times the theoretical amount. The rate of ow of the hydrogen amounted to 4.5 cubic meters/h. (measured at N.T.P.). The amount of energy supplied to the electric arc for heating the hydrogen amounted to 25 kwh. (145 amperes, 345 volts). A mixture of 1810 parts of low titanium halides was obtained (6% titanium dichloride
  • Example 3 5900 parts titanium tetrachloride flowed at a rate of 5.9 kg./h. into the evaporator and were reacted in the gaseous state with 4.5 cubic meters (measured at N.T.P.) of hydrogen. The rate of flow of the hydrogen amounted to 4.5 cubic meters/h. (measured at N.T.P.). According to Equation 1 this corresponded to an excess of hydrogen of 13 times the theoretical amount. The amount of energy supplied to the electric arc for heating the hydrogen amounted to 48 kwh. (150 amperes, 320 volts). A mixture of 3020 parts of low titanium halides was obtained (7% titanium dichloride+93% titanium trichloride). Yield: 64.5%.
  • a process for continuously manufacturing hydrogen free, low titanium chlorides by reducing titanium tetrachloride with hydrogen comprising separately preheating hydrogen to a temperature above 1000 C. to split the hydrogen at least partially into atoms, supplying a stream of the preheated hydrogen continuously to a nozzle in a stoichiometric excess amount, continuously supplying a substance selected from the group consisting of vaporous titanium tetrachloride and a mixture of vaporous titanium tetrachloride and hydrogen to said nozzle substantially perpendicularly to the stream of hydrogen, maintaining the nozzle at a temperature between the boiling point of titanium tetrachloride and about 500 C., mixing the hydrogen and the substance selected from the group consisting of vaporous titanium tetrachloride and a mixture of vaporous titanium tetrachloride and hydrogen rapidly and intimately in the nozzle, discharging the resulting reaction products from said nozzle onto a moving, cooled surface to continuously chill the reaction products and continuously collecting the chilled reaction products from the

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)
US126852A 1960-07-27 1961-07-19 Process for the manufacture of low titanium chlorides Expired - Lifetime US3211520A (en)

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Application Number Priority Date Filing Date Title
DEK41302A DE1142159B (de) 1960-07-27 1960-07-27 Verfahren und Vorrichtung zur Herstellung niederer Titanchloride

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299026A (en) * 1961-08-28 1967-01-17 John L Lang Process for producing and using a metalloid material as a polymerization catalyst

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* Cited by examiner, † Cited by third party
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US7576296B2 (en) 1995-03-14 2009-08-18 Battelle Energy Alliance, Llc Thermal synthesis apparatus
US6821500B2 (en) 1995-03-14 2004-11-23 Bechtel Bwxt Idaho, Llc Thermal synthesis apparatus and process
WO2001046067A1 (en) 1999-12-21 2001-06-28 Bechtel Bwxt Idaho, Llc Hydrogen and elemental carbon production from natural gas and other hydrocarbons
US7354561B2 (en) 2004-11-17 2008-04-08 Battelle Energy Alliance, Llc Chemical reactor and method for chemically converting a first material into a second material
US8591821B2 (en) 2009-04-23 2013-11-26 Battelle Energy Alliance, Llc Combustion flame-plasma hybrid reactor systems, and chemical reactant sources

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US296765A (en) * 1884-04-15 Xwltnesses
US1343833A (en) * 1918-11-14 1920-06-15 Leitch John Walker Apparatus for solidifying or concentrating materials
US1530493A (en) * 1920-03-15 1925-03-24 Texas Co Apparatus for producing aluminum chloride
US2768061A (en) * 1953-02-26 1956-10-23 Gen Electric Hydrogen reduction method and apparatus
US2783142A (en) * 1952-08-14 1957-02-26 Nat Res Corp Method of producing titanium
US2860094A (en) * 1954-03-18 1958-11-11 Ishizuka Kojiro Process for the recovery of metallic titanium
US2904486A (en) * 1957-07-19 1959-09-15 Exxon Research Engineering Co Electrical reduction process
FR1205462A (fr) * 1957-04-16 1960-02-03 Montedison Spa Appareil et procédé pour préparer le trichlorure de titane
US2946668A (en) * 1954-05-28 1960-07-26 Metal Chlorides Corp Continuous high-temperature reaction apparatus
US3063798A (en) * 1956-12-20 1962-11-13 Exxon Research Engineering Co Alpha olefin polymerization catalysts
US3078144A (en) * 1959-03-09 1963-02-19 Exxon Research Engineering Co Method for preparing purified titanium trichloride

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1072975B (de) * 1960-01-14 Montecatini, Societä Generale per rindustria Mineraria e Chimica, Mailand (Italien) Vorrichtung zur kontinuierlichen Herstellung von Titantrichlorid
US859750A (en) * 1907-02-08 1907-07-09 William H Davis Lampblack-machine.
DE886446C (de) * 1943-11-02 1953-08-13 Degussa Verfahren zur Herstellung von hochdispersen Oxyden
DE1008266B (de) * 1955-07-20 1957-05-16 Bayer Ag Verfahren zur Herstellung von Titandichlorid

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US296765A (en) * 1884-04-15 Xwltnesses
US1343833A (en) * 1918-11-14 1920-06-15 Leitch John Walker Apparatus for solidifying or concentrating materials
US1530493A (en) * 1920-03-15 1925-03-24 Texas Co Apparatus for producing aluminum chloride
US2783142A (en) * 1952-08-14 1957-02-26 Nat Res Corp Method of producing titanium
US2768061A (en) * 1953-02-26 1956-10-23 Gen Electric Hydrogen reduction method and apparatus
US2860094A (en) * 1954-03-18 1958-11-11 Ishizuka Kojiro Process for the recovery of metallic titanium
US2946668A (en) * 1954-05-28 1960-07-26 Metal Chlorides Corp Continuous high-temperature reaction apparatus
US3063798A (en) * 1956-12-20 1962-11-13 Exxon Research Engineering Co Alpha olefin polymerization catalysts
FR1205462A (fr) * 1957-04-16 1960-02-03 Montedison Spa Appareil et procédé pour préparer le trichlorure de titane
US2904486A (en) * 1957-07-19 1959-09-15 Exxon Research Engineering Co Electrical reduction process
US3078144A (en) * 1959-03-09 1963-02-19 Exxon Research Engineering Co Method for preparing purified titanium trichloride

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299026A (en) * 1961-08-28 1967-01-17 John L Lang Process for producing and using a metalloid material as a polymerization catalyst

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GB929929A (en) 1963-06-26
DE1142159B (de) 1963-01-10

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