# US 2010/0166643 A1 · Semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder

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- Number: US 2010/0166643 A1
- Document ID: US20100166643A1
- Status: Published application
- Kind: A1
- Application number: 12/317,791
- Filed: 2008-12-29
- Published: 2010-07-01
- Earliest claimed: 2008-12-29
- Assignees: ADMA Products, Inc.
- Inventors: Sergey A. Kasparov; Andrey G. Klevtsov; Aleksandr I Cheprasov; Vladimir S. Moxson; Volodymyr A. Duz
- Web page: https://patentgrep.com/patent/US20100166643A1

## CPC

- C01G 23/00: Compounds of titanium {(preparation of Ti-compounds from ores or scraps C22B34/12)}
- C01G 23/022: {Titanium tetrachloride}
- C01G 23/024: {Purification of tetrachloride}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)

## Abstract

The cost-effective hydrogenated, purified titanium powder is manufactured by the semi-continuous process including: (a) magnesium-thermic reduction of titanium chlorides at 830-880° C. in the hydrogen atmosphere characterized by the formation of a hollow porous block of the reaction mass having an open cavity in the center of the block, (b) full thermal-vacuum separation of the hollow block from excessive Mg and MgCl2 at 850-980° C. and residual pressure of 26-266 Pa using a multi-step cycle including: (i) purging hydrogen at 800-950° C. into the reactor at the pressure 10 kPa to 24.5 kPa, (ii) directive squeezing-out of a separated liquid phase containing magnesium and magnesium chloride into an additional vessel, and (iii) application of alternate pressure to small portions of the liquid phase in porous titanium compound from different sides which provides removal of the liquid from small pores of the titanium compound and fast evaporation of said liquid, (c) simultaneous hydrogenation and cooling of the titanium sponge down to 600° C. by purging cold hydrogen using multiple recirculation of hydrogen, (d) holding the hydrogenated porous titanium compound in the hydrogen atmosphere at 450-600° C. for 20-70 minutes, (e) removing the hydrogenated porous titanium compound from the reactor, and (f) crushing and grinding the crushed hydrogenated porous titanium pieces into the powder having a predetermined particle size.

## Claims

### Claim 1

A semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder including the steps of:
(a) magnesium-thermic reduction of titanium chlorides in a reactor in the temperature range of 830-880° C. in a hydrogen atmosphere at a pressure of 5-10 kPa resulting in a formation of a hollow block of a reaction mass having an open cavity in a center of the block,
(b) heating hydrogen in a input pipe connected to a gas compressor using an electric heater and purging hot hydrogen into the reactor for heating of the reaction mass to the temperature in a range of 980-1020° C. which is optimal for a followed up vacuum separation and for maintaining a uniform temperature along the reactor sufficient to keep magnesium and magnesium chloride in a molten state,
(c) full thermal-vacuum separation of a porous titanium compound in the reaction mass from excessive magnesium and magnesium chloride at 850-980° C. and residual pressure of 26-266 Pa (10−2-10−3 mm Hg), using a multi-step cycle including: (i) purging hydrogen at 800-950° C. into the reactor at a pressure 10 kPa to 24.5 kPa, (ii) directive squeezing-out of a separated liquid phase containing magnesium and magnesium chloride into an additional vessel, and (iii) application of alternate pressure to small portions of the liquid phase in pores of the porous titanium compound from different sides of the liquid phase which provides removal of the liquid phase from small pores of the titanium compound and fast evaporation of said liquid,
(d) simultaneous controlled hydrogenation and cooling of the porous titanium compound down to 600° C. or lower temperature by purging cold hydrogen having temperature 25-35° C. into the reactor for a speedy cooling of the block of reaction mass using multiple recirculation of hydrogen in and out of the reactor, whereby a control of temperature of the block of reaction mass is carried out by adjusting the amount of purged hydrogen,
(e) holding the hydrogenated porous titanium compound in a hydrogen atmosphere at 450-600° C. for 20-70 minutes using multiple recirculation of hydrogen that has a stable temperature,
(f) directing hydrogen in a gas refrigerator and cooling the reactor down to 150-200° C. using this cold gas,
(g) removing the hydrogenated porous titanium compound from the reactor,
(h) crushing the hydrogenated porous titanium block, and
(i) grinding the crushed hydrogenated titanium pieces into the powder having a predetermined particle size.

### Claim 2 (depends on 1)

The semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder according to claim 1, wherein the step of full thermal-vacuum separation of the porous titanium compound in the reaction mass from liquid magnesium and magnesium chloride includes following steps:
(a) degassing of the reactor down to a pressure 0.1 Pa at a rate not less than 1000 Pa/min and at 980-1020° C. in order to provide a first cycle of vacuum separation,
(b) performing the separation cycles “purge in the hydrogen-degassing-purge in the hydrogen-degassing” accompanied by alternative directing the hydrogen flow from a top and from a bottom of the reactor in order to provide a repetitive removal of liquid magnesium and magnesium chloride out of small pores of the titanium compound, as well as to keep the reaction mass uniformly heated during the separation process,
(c) a pressure ratio between hydrogen flows directed from the top and from the bottom of the reactor is 1:2, and the hydrogen used in the cycles “purge-in the hydrogen-degassing-purge-in the hydrogen-degassing” is recycled without an addition of fresh portions of the gas, and
(d) continuing said “purge in the hydrogen-degassing-purge in the hydrogen-degassing” cycles until an average magnesium content in the porous titanium compound is from 0.015 to 0.020 wt. % and an average chlorine content in the porous titanium compound is from 0.070 to 0.086 wt. %.

### Claim 3 (depends on 1)

The semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder according to claim 1, wherein the hydrogenation of the porous titanium compound is carried out at the amount of hydrogen that is significantly bigger than necessary stoichiometric ratio for this reaction.

### Claim 4 (depends on 1)

The semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder according to claim 1, wherein the hydrogen-contained atmosphere is a gaseous mixture of hydrogen with argon and/or helium.

### Claim 5 (depends on 1)

The semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder according to claim 1, wherein the magnesium-thermic reduction of titanium tetrachloride is carried out in the reactor immersed into a three-zone electric furnace; a gas-input pipe is equipped with an electric heater for heating re-circulated hydrogen and with a chlorine trap for cleaning re-circulating hydrogen; the liquid magnesium with magnesium chloride are squeezed out from the reactor into a separated vessel where they are cooled to room temperature before utilization, and after this, vapors of magnesium with magnesium chloride from the reactor after several hydrogen purging cycles are accumulated in a condenser.

### Claim 6 (depends on 5)

The semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder according to claim 5, wherein the electric heater for heating re-circulated hydrogen comprises closely packed carbon or graphite rods in order to provide effective convective heating of the gas.