Method for preparing reduced titanium powder by multistage deep reduction

Patent metadata

Field	Value
Publication number	US-11033965-B2
Application number	US-201816319197-A
Country	US
Kind code	B2
Filing date	May 21, 2018
Priority date	May 23, 2017
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

Provided is a method for preparing a reduced titanium powder by a multistage deep reduction, including the following steps of: uniformly mixing a dried titanium dioxide powder with a magnesium powder to obtain a mixture, adding the mixture in a self-propagating reaction furnace, triggering a self-propagating reaction, obtaining an intermediate product of which low-valence titanium oxides TixO are dispersed in an MgO matrix, leaching the intermediate product with a hydrochloric acid as a leaching solution, performing filtering, washing and vacuum drying to obtain a low-valence titanium oxide TixO precursor, uniformly mixing the low-valence titanium oxide TixO precursor with a calcium powder, performing a pressing to obtain semi-finished products, placing the semi-finished products in a vacuum reduction furnace for a second-time deep reduction, and leaching a deep reduction product with a hydrochloric acid as a leaching solution so as to obtain the reduced titanium powder.

First claim

What is claimed is:

1. A method for preparing a reduced titanium powder by a multistage deep reduction, comprising the following steps:
Step 1:
placing a titanium dioxide powder in a drying oven, performing drying to obtain a dried titanium dioxide powder, uniformly mixing the dried titanium dioxide powder with a magnesium powder to obtain a mixture,
adding the mixture in a self-propagating reaction furnace, performing a self-propagating reaction and cooling to obtain an intermediate product of which low-valence titanium oxides Ti x O are dispersed in an MgO matrix, wherein TiO 2 :Mg=1:0.8-1.2 by molar ratio, and the intermediate product of which the low-valence titanium oxides Ti x O dispersed in the MgO matrix is a mixture of non-stoichiometric-ratio low-valence titanium oxides, with x being in the range of 0.6-1;
Step 2:
placing the intermediate product of which the low-valence titanium oxides Ti x O are dispersed in the MgO matrix in a sealed reaction kettle, leaching the intermediate product with a hydrochloric acid as a leaching solution to obtain a filtrate and a leached product, removing the filtrate, washing the leached product, and performing a vacuum drying to obtain a low-valence titanium oxide Ti x O precursor, wherein a molar concentration of the hydrochloric acid is 1-6 mol/L;
Step 3:
uniformly mixing the low-valence titanium oxide Ti x O precursor with a calcium powder in a molar ratio of Ti x O:Ca=1:1.5-3, and performing a pressing at 2-20 MPa to obtain block-shaped semi-finished products, placing the block-shaped semi-finished products in a vacuum reduction furnace, performing heating to raise a temperature to 700-1200° C., performing a second-time deep reduction for 1-6 h, after the second-time deep reduction, obtaining the block-shaped semi-finished products, cooling the block-shaped semi-finished products along with the furnace to obtain a deep reduction product;
Step 4:
placing the deep reduction product in the sealed reaction kettle, leaching the deep reduction product with a hydrochloric acid as a leaching solution to obtain a leaching solution and filtered residues, removing the leaching solution, washing the filtered residues, and performing a vacuum drying so as to obtain a reduced titanium powder, wherein a molar concentration of the hydrochloric acid is 1-6 mol/L,
wherein the reduced titanium powder comprises the following components in percentage by mass of 98-99.5% of Ti, 0.1-2% of O, and a balance being unavoidable impurities, with a size of 8-40 μm.

2. The method according to claim 1 , wherein in the step 1, the mixture is treated by one of the following two manners before being placed in the self-propagating reaction furnace:
Mode I: performing a pressing at 10-60 MPa to obtain a block-shaped semi-finished products, and then adding the block-shaped semi-finished products to the self-propagating reaction furnace; and
Mode II: adding the mixture to the self-propagating reaction furnace directly without a treatment.

3. The method according to claim 1 , wherein in the step 1, the drying is performed at 100-150° C. for 24 h or above.

4. The method according to claim 1 , wherein in the step 1, methods for triggering the self-propagating reaction comprises a method selected from the group consisting of a local ignition method and a whole heating method, wherein the local ignition method means that electric heating wires are used to heat a part of the mixture in the self-propagating reaction furnace to trigger the self-propagating reaction; and the whole heating method means that a temperature of the mixture is wholly raised in the self-propagating reaction furnace until the self-propagating reaction occurs, wherein the temperature is controlled to be 500-750° C. during the self-propagating reaction.

5. The method according to claim 1 , wherein in the step 2, when the hydrochloric acid is used as the leaching solution for leaching the intermediate product, an additional amount of a diluted hydrochloric acid and an additional amount of the intermediate product are in a compounding ratio with a 10-40% excess proportion of the hydrochloric acid over the stoichiometric amount required to perform a chemical reaction MgO+2H + =Mg 2+ +H 2 0; and
in the step 2, a leaching temperature of the leached intermediate product is 20-30° C. and a leaching time is 60-180 min.

6. The method according to claim 1 , wherein in the step 2, the resultant low-valence titanium oxide Ti x O precursor consists of the following components in percentage by mass: 75-88% of Ti, 12-25% of O, and unavoidable impurities being smaller than or equal to 0.5%, wherein a sum of the percentage by mass of all components are 100%, with a size of 0.8-15 μm.

7. The method according to claim 1 , wherein in the step 2, the specific steps of the washing and the vacuum drying comprise: washing the leached product without the filtrate, with a water until a washing liquid is neutral, and then performing the drying in a vacuum drying oven at a drying temperature of 20-30° C. for at least 24 h; and
wherein the washing is performed with the water, specifically a dynamic washing is adopted, wherein a constant level of the washing liquid is maintained in a washing tank in the washing process by supplementing a same amount of a fresh water as the washing liquid which is drained, and the washing is performed until the washing liquid is neutral.

8. The method according to claim 1 , wherein in the step 3, the second-time deep reduction reaction specifically comprises: raising the temperature in the vacuum reduction furnace while the furnace is at a vacuum degree of smaller than or equal to 10 Pa.

9. The method according to claim 1 , wherein in the step 4, when the deep reduction product is leached, an additional amount of a diluted hydrochloric acid and an additional amount of the deep reduction product are in a compounding ratio with a 5-30% excess proportion of the hydrochloric acid over the stoichiometric amount required to perform a chemical reaction CaO+2H + =Ca 2+ +H 2 0; and
in the step 4, a leaching temperature of the leached deep reduction product is 20-30° C. and a leaching time is 15-90 min.

10. The method according to claim 1 , wherein in the step 4, the specific steps of the washing and the vacuum drying comprise: washing the leached product without the leaching solution, with a water until a washing liquid is neutral, and then performing the drying in a vacuum drying oven at a drying temperature of 20-30° C. for at least 24 h; and
wherein the washing is performed with the water, specifically a dynamic washing is adopted, wherein a constant level of the washing liquid is maintained in a washing tank in the washing process by supplementing a same amount of a fresh water as the washing liquid which is drained, and the washing is performed until the washing liquid is neutral.

Assignees

• Univ Northeastern

Inventors

• Zhang Ting An
• Dou Zhi He
• Liu Yan
• Lv Guo Zhi
• Zhao Qiu Yue
• Niu Li Ping
• Fu Da Xue
• Zhang Wei Guang

Classifications

• B22F2301/205

  Titanium, zirconium or hafnium · CPC title

• C22B34/1268

  using alkali or alkaline-earth metals or amalgams · CPC title

• B22F9/20 Primary

  starting from solid metal compounds · CPC title

• Y02P10/20

  Recycling · CPC title

• C22B5/18

  Reducing step-by-step · CPC title