CN103305875A - Preparation method for preparing anode of metallic titanium by molten salt electrolysis - Google Patents
Preparation method for preparing anode of metallic titanium by molten salt electrolysis Download PDFInfo
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- CN103305875A CN103305875A CN2013102611931A CN201310261193A CN103305875A CN 103305875 A CN103305875 A CN 103305875A CN 2013102611931 A CN2013102611931 A CN 2013102611931A CN 201310261193 A CN201310261193 A CN 201310261193A CN 103305875 A CN103305875 A CN 103305875A
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- titanium
- salt electrolysis
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Abstract
The invention discloses a preparation method for preparing an anode of metallic titanium by molten salt electrolysis, and relates to a preparation method for preparing a TiOxCy compound anode of metallic titanium by molten salt electrolysis. The method is characterized in that the preparation process comprises the following steps: 1) by using TiOxCy as a basic raw material and using paraffin and PVA (Polyvinyl Acetate) as diluters, preparing slurry; 2) injecting the slurry into an extruder to prepare an anode blank in required shape by way of extrusion and die forming; and 3) sintering to blank to mould at high temperature to prepare the anode required for electrolysis of titanium. The method provided by the invention is an integral molding method, wherein a TiOxCy soluble solid solution is used as the anode raw material which is directly electrolyzed in an alkaline earth molten salt electrolyte to prepare the TiOxCy compound anode of metallic titanium by direct electrolysis. The method provided by the invention realizes industrial production of anodes by electrolysis of titanium, and promotes industrial progress of preparing metallic titanium by electrolysis.
Description
Technical field
A kind of fused salt electrolysis prepares the preparation method of the anode of metal titanium, relates to the TiO that a kind of fused salt electrolysis prepares metal titanium
xC
yThe preparation method of composite anode.
Background technology
Titanium is one of important Rare Metals Materials, little because of its density, specific tenacity is high, heat-resisting, without magnetic, the many merits such as can weld.Be widely used in fields such as Aeronautics and Astronautics, oil, chemical industry, metallurgy, medical treatment, aerospace field especially, titanium metal becomes very important material.The titanium resource of China is very abundant, and reserves rank first in the world.Although titanium resource is very abundant, the throughput of titanium sponge only accounts for the demand that 2%～3%. of the world can not satisfy the national economic development far away.Therefore, improve the titanium sponge industrial capacity and become the task of top priority.
At present, the unique method of commercial production of metals titanium is the magnesium reduction process preparation, also claims the Kroll method.This technique is discrete, must feed to reaction in process of production, the operation such as heat and discharging.The shortcoming of Kroll method maximum be long flow path, operation many, can not produce continuously so that the cost of titanium sponge is high, the environmental pollution in the production process is large, has affected the application of titanium.
Direct electrolysis method is the method that people imagine employing always, and scholars have also carried out multiple trial, wherein TiO
xC
yThe method that composite anode direct electrolysis method (claiming again MER technique) prepares metal titanium has that cost is low, efficient is high, pollution-free all advantages have been subject to paying close attention to widely.The main flow process of this technique mainly is with TiO
2With carbon dust or related substances as basic raw material, the mode by thermal reduction is reduced into TiO
xC
y, then with TiO
xC
yCarry out electrolysis as anode, the pure titanium of preparation metal.Withers(US Patent No. 2005/0166706 A1, US7410562, US7794580) studied and passed through TiO
2Prepare composite anode materials with carbon dust, and then the electrowinning metal titanium; The people such as Zhu Hongmin (Chinese patent CN1712571A, CN101187042A) have studied with titanium complex ore, TiO
2With carbon dust and TiO
2With titanium carbide be raw material, the preparation composite anode, then carry out the electrowinning titanium; Also have in addition other scholar this also to be carried out a large amount of research work (Chinese patent CN1664173A).But above research all is the technical process for the general overview of preparing metallic titanium by electrolyzing, and for concrete each step process process, especially can satisfy the efficient feasible TiO of suitability for industrialized production
xC
yThe composite anode integral forming process is not also carried out relevant research work.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists for above-mentioned prior art, provides a kind of flow process simple, and yield rate is high, and the fused salt electrolysis that forming efficiency is high prepares the preparation method of the anode of metal titanium.
The objective of the invention is to be achieved through the following technical solutions.
A kind of fused salt electrolysis prepares the preparation method of the anode of metal titanium, it is characterized in that the step of its preparation process comprises:
1) with TiO
xC
yBe basic raw material, as thinner, make slurry with paraffin, PVA;
2) slurry is injected into the anode blank that the mode that adopts the extrusion die pressing formation in the extrusion machine is prepared desired shape;
3) the blank high temperature sintering is shaped, prepares the required anode of electrolytic titanium.
A kind of fused salt electrolysis of the present invention prepares the preparation method of the anode of metal titanium, it is characterized in that its raw material TiO
xC
yParticle diameter less than 100 microns.
A kind of fused salt electrolysis of the present invention prepares the preparation method of the anode of metal titanium, it is characterized in that pulping process selects any one or two kinds of mixing among paraffin and the PVA as thinner, and the weight percent of thinner in slurry is 1%-70%.
A kind of fused salt electrolysis of the present invention prepares the preparation method of the anode of metal titanium, it is characterized in that the kinematic viscosity of the slurry that the pulping process system gets is greater than 10
-6m
2/ S is less than 0.1 m
2/ S.
A kind of fused salt electrolysis of the present invention prepares the preparation method of the anode of metal titanium, and the sintering temperature that it is characterized in that blank high temperature sintering forming process is 600-2000 ℃, and sintering condition is in vacuum or the inert gas atmosphere.
A kind of fused salt electrolysis of the present invention prepares the preparation method of the anode of metal titanium, it is characterized in that its TiO
xC
yIn 0＜X＜2,0＜Y≤1.
The preparation method that a kind of fused salt electrolysis of the present invention prepares the anode of metal titanium has finished the forming process of electrolytic titanium composite anode by simple technical process, accelerated the process of industrialization of Direct Electrolysis titanium.
Embodiment
A kind of fused salt electrolysis prepares the preparation method of the anode of metal titanium, and the step of its preparation process comprises: 1) with TiO
xC
yBe basic raw material, as thinner, make slurry with paraffin, PVA; 2) slurry is injected into the anode blank that the mode that adopts the extrusion die pressing formation in the extrusion machine is prepared desired shape; 3) the blank high temperature sintering is shaped, prepares the required anode of electrolytic titanium.
Embodiment 1
Prepare oval TiO
xC
y(X=0.5 y=0.5) composite anode: select TiO
xC
yBe basic raw material, take by weighing TiO
xC
y1 ton of raw material, adopting jaw crusher to carry out Mechanical Crushing to particle diameter is 50 microns.Add the paraffin thinner of anode material gross weight 25%, then adopt automation kneading pot to carry out stir mixing 10 hours, make slurry.Then slurry is directly injected in the mechanical presses machine by pipeline, installs oval mould additional, carry out extrusion operation, form oval blank.Blank is put into argon gas atmosphere thermal response stove, under 1800 ℃ of conditions, carry out high temperature sintering.10 as a child with the Reaktionsofen cooling, has finished the shaping of material.
Embodiment 2
Prepare square TiO
xC
y(X=1 y=1) composite anode: select TiO
xC
yBe basic raw material, adopting planetary ball mill to carry out Mechanical Crushing to particle diameter is 80 microns.Add the paraffin thinner of anode material gross weight 70%, then adopt automation kneading pot to carry out stir mixing 10 hours, make slurry.Then slurry is directly injected in the mechanical presses machine by pipeline, installs square dies additional, carry out extrusion operation, form stock of square.Blank is put into argon gas atmosphere thermal response stove, under 1500 ℃ of conditions, carry out high temperature sintering.6 as a child with the Reaktionsofen cooling, finishes the shaping of material.
Embodiment 3
The middle cylindrical TiO with through hole of preparation
xC
y(X=0.2 y=0.8) composite anode: select TiO
xC
yBe basic raw material, take by weighing quantitative raw material, adopting planetary ball mill to carry out Mechanical Crushing to particle diameter is 30 microns.Add the PVA solution dilution agent of anode material gross weight 20%, then adopt automation kneading pot to carry out stir mixing 2 hours, make slurry.Then slurry is directly injected in the mechanical presses machine by pipeline, installs hollow mould additional, carry out extrusion operation, form middle stock of square with through hole.Blank is put into the vacuum reaction stove, under 1300 ℃ of conditions, carry out high temperature sintering.3 as a child with the Reaktionsofen cooling, finishes the shaping of material.
Claims (6)
1. a fused salt electrolysis prepares the preparation method of the anode of metal titanium, it is characterized in that the step of its preparation process comprises:
(1) with TiO
xC
yBe basic raw material, as thinner, make slurry with paraffin, PVA;
(2) slurry is injected into the anode blank that the mode that adopts the extrusion die pressing formation in the extrusion machine is prepared desired shape;
(3) the blank high temperature sintering is shaped, prepares the required anode of electrolytic titanium.
2. a kind of fused salt electrolysis according to claim 1 prepares the preparation method of the anode of metal titanium, it is characterized in that its raw material TiO
xC
yParticle diameter less than 100 microns.
3. a kind of fused salt electrolysis according to claim 1 prepares the preparation method of the anode of metal titanium, it is characterized in that pulping process selects any one or two kinds of mixing among paraffin and the PVA as thinner, the weight percent of thinner in slurry is 1%-70%.
4. a kind of fused salt electrolysis according to claim 1 prepares the preparation method of the anode of metal titanium, it is characterized in that the kinematic viscosity of the slurry that the pulping process system gets is greater than 10
-6m
2/ S is less than 0.1 m
2/ S.
5. a kind of fused salt electrolysis according to claim 1 prepares the preparation method of the anode of metal titanium, and the sintering temperature that it is characterized in that blank high temperature sintering forming process is 600-2000 ℃, and sintering condition is in vacuum or the inert gas atmosphere.
6. require 1 described a kind of fused salt electrolysis to prepare the preparation method of the anode of metal titanium according to the authority profit, it is characterized in that its TiO
xC
yIn 0＜X＜2,0＜Y≤1.
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|---|---|---|---|
| CN2013102611931A CN103305875A (en) | 2013-06-27 | 2013-06-27 | Preparation method for preparing anode of metallic titanium by molten salt electrolysis |
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| CN2013102611931A CN103305875A (en) | 2013-06-27 | 2013-06-27 | Preparation method for preparing anode of metallic titanium by molten salt electrolysis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451781A (en) * | 2014-12-08 | 2015-03-25 | 中国铝业股份有限公司 | Preparation method of anode for producing metallic titanium by electrolysis |
| CN109650893A (en) * | 2019-01-14 | 2019-04-19 | 浙江海虹控股集团有限公司 | A kind of method of low temperature preparation titaniferous composite anode |
| CN109763148A (en) * | 2019-01-14 | 2019-05-17 | 浙江海虹控股集团有限公司 | A kind of device and method that continuous electrolysis prepares high pure metal titanium valve |
| CN110042433A (en) * | 2019-05-08 | 2019-07-23 | 北京科技大学 | A kind of industrialized preparing process of titaniferous solubility solid solution anode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712571A (en) * | 2005-05-08 | 2005-12-28 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
| CN101187042A (en) * | 2007-09-12 | 2008-05-28 | 北京科技大学 | Method for preparing TiC mTiO sosoloid using titanium complex ore as material |
| CN102061489A (en) * | 2009-11-11 | 2011-05-18 | 北京科技大学 | Improved process for smelting metallic titanium by electro-deoxidation method |
| US20120043220A1 (en) * | 2010-08-23 | 2012-02-23 | Massachusetts Institute Of Technology | Extraction of liquid elements by electrolysis of oxides |
-
2013
- 2013-06-27 CN CN2013102611931A patent/CN103305875A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712571A (en) * | 2005-05-08 | 2005-12-28 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
| CN101187042A (en) * | 2007-09-12 | 2008-05-28 | 北京科技大学 | Method for preparing TiC mTiO sosoloid using titanium complex ore as material |
| CN102061489A (en) * | 2009-11-11 | 2011-05-18 | 北京科技大学 | Improved process for smelting metallic titanium by electro-deoxidation method |
| US20120043220A1 (en) * | 2010-08-23 | 2012-02-23 | Massachusetts Institute Of Technology | Extraction of liquid elements by electrolysis of oxides |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451781A (en) * | 2014-12-08 | 2015-03-25 | 中国铝业股份有限公司 | Preparation method of anode for producing metallic titanium by electrolysis |
| CN109650893A (en) * | 2019-01-14 | 2019-04-19 | 浙江海虹控股集团有限公司 | A kind of method of low temperature preparation titaniferous composite anode |
| CN109763148A (en) * | 2019-01-14 | 2019-05-17 | 浙江海虹控股集团有限公司 | A kind of device and method that continuous electrolysis prepares high pure metal titanium valve |
| CN109763148B (en) * | 2019-01-14 | 2020-11-03 | 浙江海虹控股集团有限公司 | Device and method for preparing high-purity metal titanium powder through continuous electrolysis |
| US11821096B2 (en) | 2019-01-14 | 2023-11-21 | Zhejiang Haihong Holding Group Co., Ltd. | Device and method for preparing high-purity titanium powder by continuous electrolysis |
| CN110042433A (en) * | 2019-05-08 | 2019-07-23 | 北京科技大学 | A kind of industrialized preparing process of titaniferous solubility solid solution anode |
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Application publication date: 20130918 |