CN102061489A - Improved process for smelting metallic titanium by electro-deoxidation method - Google Patents
Improved process for smelting metallic titanium by electro-deoxidation method Download PDFInfo
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- CN102061489A CN102061489A CN2009102372582A CN200910237258A CN102061489A CN 102061489 A CN102061489 A CN 102061489A CN 2009102372582 A CN2009102372582 A CN 2009102372582A CN 200910237258 A CN200910237258 A CN 200910237258A CN 102061489 A CN102061489 A CN 102061489A
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Abstract
The invention provides an improved process for smelting metallic titanium by an electro-deoxidation method, which is characterized in that cathode plates used in the process are prepared by mixing titanium dioxide powder, a PVA binder with a carbon powder additive based on a certain ratio, and then sintering at a temperature of 1300 DEG C for 4-6 hours after forming in batch at a pressure of 15-20 MPa. The cathode plates are connected with cathode wires in series to form cathode bars. An anode adopts a rotating graphite anode; the graphite anode can reduce the deoxidation potential in the process of deoxidation; and a rotating electrode can weaken the anode effect on the surface and fast discharge reaction products, wherein the rotating speed is generally in the range of 60-200rpm. The improved process has the advantages of short production cycle, simple structure and low production cost of titanium sponge, and can be applied to manufacturing fields of other metals and alloy products..
Description
Technical field
The present invention relates to a kind of electrolysis deoxidation new technology that can increase substantially the current efficiency in the fused salt electricity deoxidation process.Be primarily aimed at the low current efficiency problem in the electric deoxidation titanium smelting technology, modification and deoxidation process control by counter electrode are effectively promoted oxygen ions migrate and the electrolytic condition that removes, and have improved the service efficiency of electric current when shortening the reaction times greatly.The invention belongs to fields such as metallurgy, electrochemistry.
Background technology
In the smelting technology of metal titanium, the Kroll method is the method that the world today generally adopts.The Kroll method mainly adopts metal M g reduction TiCl
4Operation-vacuum separation operation is made metal titanium, this technology can make highly purified metal titanium, but this technology owing to thermal reduction process flow length, complex procedures, can not continuous production etc. reason make the titanium production cost high, environmental pollution in the production process has in addition restricted the widespread use of titanium greatly.For this reason, low-cost, the short flow process of research and development, eco-friendly metal titanium preparation method, significant.At present, a series of electrochemistry metallurgical methods such as FFC method are regarded as the novel process that is hopeful to replace traditional method most.
Melt salt electro-deoxiedation (FFC, international monopoly PCT/GB99/01781) and all obtained certain achievement in the research aspect technology and the basic theory in recent years.This method has broken through that people thought in the past can only be TiCl
4Dissolve in thought in the ionogen as raw material, directly utilize solid phase t iO
2As negative electrode.FFC method technological process is simple, and has save energy, pollutes advantages such as few.
The inventor is devoted to metal oxide, especially titanium dioxide (TiO always
2) the research of electrochemical reduction, and in research process, finished the present invention.The inventor think present electro-deoxiedation prepare the problem that exists in the metal titanium technology be mainly reflected in the reaction times long, current efficiency is low excessively, product quality is not high.
The inventor is through a large amount of summaries, and reach a conclusion: length and the current efficiency of production time are inversely proportional to.In the early stage of electrolysis production, current efficiency generally can reach more than 60%, and the side reaction ratio is very little, the speed control link in this stage be oxygen in fused salt transfer and in anodic discharge link, the deoxidation speed of metal oxide cathode is very fast.And the electrolysis middle and later periods belongs to the deep deoxidation process, according to electric deoxidation theory, the oxygen in the cathode oxide to external diffusion, is dissolved in the fused salt under the effect of voltage, and continue anode migration under effect of electric field, oxidizing reaction finally takes place on anode discharge from system.Oxygen in this stage metal oxide cathode has dropped to certain level, is in degree of depth killing stage.The reducing of oxygen level causes the deep deoxidation resistance further to increase, and therefore effectively electrolysis is difficult to carry out, and the side reaction ratio increases gradually.Because the purity of producing metallic product has higher requirements, thereby therefore must prolong the production time causes production efficiency to descend, and the effective rate of utilization of while electric current is decline thereupon also.
Summary of the invention
The purpose of this invention is to provide a kind of technology that is intended to improve the electro-deoxiedation metal smelting titanium of electrolytic process current efficiency.
A kind of technology of electro-deoxiedation metal smelting titanium; in the cathode titanium oxide compound, add 200 purpose activated carbon powders; activated carbon powder was controlled at 1: 4 to 1: 10 with cathode titanium oxide mass ratio; binding agent adopts the 5%PVA aqueous solution; its cathode titanium oxide mass ratio was controlled at 1: 4 to 1: 10; compacting in flakes after the combination treatment; forming pressure 15～80Mpa; be assembled into negative electrode again behind oversintering, sintering temperature is 1000 ℃～1400 ℃, and sintering time is 4～8h; sintering atmosphere adopts hydrogen or protection of inert gas gas; cathode sheets after the moulding is in 100 ℃～130 ℃ 24h～48h that dewater down, and anode adopts the rotation graphite anode, with CaCl
2Fused salt is as ionogen, and negative electrode is converted into metal titanium after electrolysis.
Another technical scheme of the present invention is that described graphite anode speed range is 60～200rpm.
Sintered cathode chip size of the present invention is controlled at about Φ 20mm*5mm, and by being composed in series cathode bar, the anodic-cathodic spacing is controlled at about 200mm.
The invention advantage
The present invention is guaranteeing that product quality reaches on the basis of level Four national standard, a large amount of shorten the reaction times, improve current efficiency, with short production cycle, process structure is simple, the titanium sponge production cost is low, and can be applied to the preparation field of other metal and alloy product.
Description of drawings
Fig. 1 electro-deoxiedation system titanium electrode collocation sketch.
The SEM Electronic Speculum pattern collection of illustrative plates of cathode sheets behind Fig. 2 example 3 sintering of the present invention.
The spongy titanium powder X-ray diffracting spectrum that Fig. 3 example 3 of the present invention is produced.
The SEM Electronic Speculum pattern collection of illustrative plates of cathode sheets behind Fig. 4 example 6 sintering of the present invention.
The spongy titanium powder X-ray diffracting spectrum that Fig. 5 example 6 of the present invention is produced.
Fig. 6 electro-deoxiedation of the present invention is produced the process flow sheet of metal titanium.
Embodiment
Example 1:
Get the smart powder (〉=99%) of 100g titanium dioxide, add 5% polyvinyl alcohol (PVA) aqueous solution 10g, the back batch under the 15Mpa forming pressure that stirs is pressed into the wafer body of Φ 20mm*5mm, central authorities process Φ 3mm perforate, cathode sheets after the moulding is at 100 ℃ of 24h that dewater down, sintering 4h under 1300 ℃ of hydrogen atmospheres, obtaining the cathode sheets porosity is 19%.The cathode sheets that sinters is composed in series cathode bar with resistance wire, the about 100g of titanium dioxide cathode sheets total amount, cathode and anode spacing is 200mm.Protection gas argon flow amount is set at 5L/min, fused salt CaCl
2The degree of depth is 140mm, and 48h is carried out in electrolysis under 950 ℃.Product, color is grey black, and there is a small amount of grey tight zone in inside, is mainly intermediate product TiO, Ti after testing
2The O composition.Product obtains titanium sponge powder 30g after fragmentation, pickling, cleaning, titanium content is 99.09%, and production process current efficiency is 49%.Fused salt surface carbon-coating is obvious, and thickness is about 1mm.The integrated artistic flow line as shown in Figure 6.
Example 2:
Get the smart powder (〉=99%) of 100g titanium dioxide, add 10% polyvinyl alcohol (PVA) aqueous solution 25g, the back batch under the 15Mpa forming pressure that stirs is pressed into the wafer body of Φ 20mm*5mm, central authorities process Φ 3mm perforate, cathode sheets after the moulding is at 130 ℃ of 48h that dewater down, sintering 4h under 1100 ℃ of hydrogen atmospheres, obtaining the cathode sheets porosity is 25%.The cathode sheets that sinters is composed in series cathode bar with resistance wire, cathode bar external parcel stainless (steel) wire, the about 100g/ group of titanium dioxide feeding quantity.Cathode and anode spacing is 200mm, and anode bar links to each other with motor by transmission shaft, and speed setting is 120rpm, and electrode is arranged in pairs or groups as shown in Figure 1.Argon flow amount is set at 5L/min, fused salt CaCl
2Controlling depth is 140mm, and 36h is carried out in electrolysis under 950 ℃.Remove the stainless (steel) wire parcel, it is higher to obtain product appearance density, and color is grey black, obtains titanium sponge powder 32g after fragmentation, pickling, cleaning, and titanium content is 99.10, and production process current efficiency is 54%.A small amount of carbon-coating appears in the fused salt surface.The integrated artistic flow line as shown in Figure 6.
Example 3:
Get the smart powder (〉=99%) of 100g titanium dioxide, mix 10g activated carbon powder (100～200 order), mix the back and add 15% polyvinyl alcohol (PVA) aqueous solution 20g, after further stirring, be pressed into the wafer body of Φ 20mm*5mm in batches under the 20Mpa forming pressure, central authorities process Φ 3mm perforate, cathode sheets after the moulding is at 120 ℃ of 36h that dewater down, sintering 4h under 1200 ℃ of hydrogen atmospheres, obtaining the cathode sheets porosity is 35%, the SEM Electronic Speculum pattern collection of illustrative plates of cathode sheets is seen Fig. 2 behind the sintering.The cathode sheets that sinters is composed in series cathode bar with resistance wire, the about 100g of titanium dioxide cathode sheets total amount, cathode and anode spacing is 200mm, and anode bar links to each other with motor by transmission shaft, and speed setting is 120rpm, and electrode is arranged in pairs or groups as shown in Figure 1.Protection gas argon flow amount is set at 5L/min, fused salt CaCl
2The degree of depth is 140mm, and 36h is carried out in electrolysis under 950 ℃.Shape of product does not have to change substantially, and density increases, and color is grey black, obtains titanium sponge powder 39g after fragmentation, pickling, cleaning, and the product titanium content is 99.27%, reaches national level Four titanium standard, and the spongy titanium powder X-ray diffracting spectrum that obtains is seen Fig. 3.Production process current efficiency is 62%.The integrated artistic flow line as shown in Figure 6.
Example 4:
Get the smart powder (〉=99%) of 100g titanium dioxide, mix 15g activated carbon powder (200～400 order), mix the back and add 10% polyvinyl alcohol (PVA) aqueous solution 20g, after further stirring, be pressed into the wafer body of Φ 20mm*5mm under the 40Mpa forming pressure in batches, central authorities process Φ 3mm perforate, and the cathode sheets after the moulding is at 120 ℃ of 36h that dewater down, sintering 5.5h under 1200 ℃ of argon gas atmosphere, obtaining the cathode sheets porosity is 41%.The cathode sheets that sinters is composed in series cathode bar with resistance wire, the about 100g of titanium dioxide electrodes sheet feeding quantity.Cathode and anode spacing is 200mm, and anode bar links to each other with motor by transmission shaft, and speed setting is 120rpm, and electrode is arranged in pairs or groups as shown in Figure 1.Argon flow amount is set at 5L/min, fused salt CaCl
2Controlling depth is 140mm, and 30h is carried out in electrolysis under 950 ℃.Shape of product slightly shrinks, and density increases, and color is grey black, obtains titanium sponge powder 40g after fragmentation, pickling, cleaning, and titanium content is 99.25%, reaches national level Four titanium standard, and production process current efficiency is 69%.The integrated artistic flow line as shown in Figure 6.
Example 5
Get the smart powder (〉=99%) of 100g titanium dioxide, mix 20g activated carbon powder (50～100 order), mix the back and add 10% polyvinyl alcohol (PVA) aqueous solution 20g, after further stirring, under the 50Mpa forming pressure, be pressed into the wafer body of Φ 20mm*5mm in batches, cathode sheets after the moulding is dehydration 36h under 120 ℃, sintering 6h under 1300 ℃ of argon gas atmosphere, and obtaining the cathode sheets porosity is 48%.The cathode sheets that sinters is composed in series cathode bar with resistance wire, cathode bar external parcel stainless (steel) wire, the about 100g of titanium dioxide electrodes sheet feeding quantity.Cathode and anode spacing is 200mm, and anode bar links to each other with motor by transmission shaft, and speed setting is 200rpm, and electrode is arranged in pairs or groups as shown in Figure 1.Argon flow amount is set at 5L/min, fused salt CaCl
2Controlling depth is 140mm, and 28h is carried out in electrolysis under 950 ℃.Obtain the product appearance and be heaped-up, density is lower, and color is grey black, obtains titanium sponge powder 44g after fragmentation, pickling, cleaning, and titanium content is 99.35%, reaches national level Four titanium standard, and production process current efficiency is 71%.The integrated artistic flow line as shown in Figure 6.
Example 6:
Get the smart powder (〉=99%) of 100g titanium dioxide, mix 25g activated carbon powder (100～200 order), mix the back and add 8% polyvinyl alcohol (PVA) aqueous solution 25g, after further stirring, be pressed into the wafer body of Φ 20mm*5mm in batches under the 80Mpa forming pressure, central authorities process Φ 3mm perforate, cathode sheets after the moulding is at 130 ℃ of 48h that dewater down, sintering 6h under 1400 ℃ of argon gas atmosphere, obtaining the cathode sheets porosity is 60%, the SEM Electronic Speculum pattern collection of illustrative plates of cathode sheets is seen Fig. 4 behind the sintering.The cathode sheets that sinters is composed in series cathode bar with resistance wire, cathode bar external parcel stainless (steel) wire, the about 100g/ group of titanium dioxide feeding quantity.Cathode and anode spacing is 200mm, and cloudy the moon/positive anode spacing is 50mm.Anode bar links to each other with motor by transmission shaft, and speed setting is 60rpm, and electrode is arranged in pairs or groups as shown in Figure 1.Argon flow amount is set at 5L/min, fused salt CaCl
2Controlling depth is 140mm, and 36h is carried out in electrolysis under 950 ℃.Remove the stainless (steel) wire parcel, obtain the product appearance and be heaped-up, density is lower, color is grey black, obtains titanium sponge powder 43g after fragmentation, pickling, cleaning, and titanium content is 99.31%, reach national level Four titanium standard, the spongy titanium powder X-ray diffracting spectrum that obtains is seen Fig. 5.Production process current efficiency is 65%.The integrated artistic flow line as shown in Figure 6.
Example 7:
Get the smart powder (〉=99%) of 100g titanium dioxide, mix 25g activated carbon powder (300～400 order), mix the back and add 15% polyvinyl alcohol (PVA) aqueous solution 25g, after further stirring, be pressed into the wafer body of Φ 20mm*5mm under the 60Mpa forming pressure in batches, central authorities process Φ 3mm perforate, and the cathode sheets after the moulding is at 130 ℃ of 48h that dewater down, sintering 8h under 1300 ℃ of argon gas atmosphere, obtaining the cathode sheets porosity is 60%.The cathode sheets that sinters is composed in series cathode bar with resistance wire, cathode bar external parcel stainless (steel) wire, the about 100g/ group of titanium dioxide feeding quantity.Cathode and anode spacing is 200mm, and cloudy the moon/positive anode spacing is 50mm.Anode bar links to each other with motor by transmission shaft, and speed setting is 120rpm, and electrode is arranged in pairs or groups as shown in Figure 1.Argon flow amount is set at 5L/min, fused salt CaCl
2Controlling depth is 140mm, and 36h is carried out in electrolysis under 950 ℃.Remove the stainless (steel) wire parcel, obtain the product appearance and be heaped-up, density is lower, and color is grey black, obtains titanium sponge powder 45g after fragmentation, pickling, cleaning, and titanium content is 99.30%, reaches national level Four titanium standard, and production process current efficiency is 70%.The integrated artistic flow line as shown in Figure 6.
Claims (2)
1. the technology of an electro-deoxiedation metal smelting titanium; it is characterized in that in the cathode titanium oxide compound, adding 40～400 purpose activated carbon powders; activated carbon powder and cathode titanium oxide mass ratio are controlled between 1: 4 to 1: 10; binding agent adopts 5%～15%PVA aqueous solution; itself and cathode titanium oxide mass ratio are controlled between 1: 4 to 1: 10; compacting in flakes after the combination treatment; forming pressure 15～80Mpa; cathode sheets after the moulding is in 100～130 ℃ of 24h～48h that dewater down; behind oversintering, be assembled into negative electrode again; sintering temperature is 1000 ℃～1400 ℃; sintering time is 4～8h; sintering atmosphere adopts hydrogen or protection of inert gas gas, and anode adopts rotation graphite active anode, with CaCl
2Fused salt is as ionogen, and negative electrode is converted into metal titanium after electrolysis.
2. the technology of a kind of electro-deoxiedation metal smelting titanium as claimed in claim 1 is characterized in that described rotation graphite active anode speed range is 60～200rpm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586809A (en) * | 2012-03-22 | 2012-07-18 | 北京科技大学 | Method for improving TiO2 cathode deoxidizing process by utilizing carbonaceous additive |
| CN103305875A (en) * | 2013-06-27 | 2013-09-18 | 中国铝业股份有限公司 | Preparation method for preparing anode of metallic titanium by molten salt electrolysis |
| TWI503453B (en) * | 2011-07-15 | 2015-10-11 | ||
| CN107587168A (en) * | 2017-10-31 | 2018-01-16 | 成都先进金属材料产业技术研究院有限公司 | The method that molten-salt electrolysis prepares Titanium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101086073A (en) * | 2006-06-09 | 2007-12-12 | 攀枝花学院 | Technology for direct electrolysis for preparing TiO2 under vacuum condition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI503453B (en) * | 2011-07-15 | 2015-10-11 | ||
| CN102586809A (en) * | 2012-03-22 | 2012-07-18 | 北京科技大学 | Method for improving TiO2 cathode deoxidizing process by utilizing carbonaceous additive |
| CN103305875A (en) * | 2013-06-27 | 2013-09-18 | 中国铝业股份有限公司 | Preparation method for preparing anode of metallic titanium by molten salt electrolysis |
| CN107587168A (en) * | 2017-10-31 | 2018-01-16 | 成都先进金属材料产业技术研究院有限公司 | The method that molten-salt electrolysis prepares Titanium |
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Granted publication date: 20120606 Termination date: 20181111 |