CN103147096A - Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium - Google Patents
Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium Download PDFInfo
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- CN103147096A CN103147096A CN2013101046421A CN201310104642A CN103147096A CN 103147096 A CN103147096 A CN 103147096A CN 2013101046421 A CN2013101046421 A CN 2013101046421A CN 201310104642 A CN201310104642 A CN 201310104642A CN 103147096 A CN103147096 A CN 103147096A
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Abstract
The invention provides a method for preparing molten-salt electrolyte containing low-valent titanium chloride and a method for extracting titanium. The method for preparing molten-salt electrolyte comprises the following steps: mixing alkali chloride and/or alkaline-earth metal chloride with a pre-set amount of metal chloride to form mixture, wherein the standard electrode potential of metal ions in the metal chloride is more positive than the standard electrode potential of divalent or trivalent titanium ion; with the electrode containing the metal titanium as an anode and the mixture as molten-salt electrolyte, configuring a cathode and electrolyzing so that all the metal chloride in the mixture is deposited on the cathode, wherein the obtained molten salt is the molten-salt electrolyte containing the low-valent titanium chloride. The method disclosed by the invention has the beneficial effects that the molten-salt electrolyte containing low-valent titanium chloride can be prepared under the conditions that the molten-salt electrolyte is not polluted and test devices are not corroded, the reaction rate is high, and the technical processes are continuous.
Description
Technical field
The present invention relates to the technical field of extracting titanium from electrolyzed molten salt, more particularly, relate to a kind of method for preparing the molten salt electrolyte that contains low-valence titanium chloride and a kind ofly extract the method for titanium as molten salt electrolyte with this molten salt electrolyte that contains low-valence titanium chloride.
Background technology
At present, extracting titanium from electrolyzed molten salt is compared existing magnesium reduction technique (Kroll method) and is had that technical process is short, production cost is low, advantages of environment protection, thereby studied by lot of domestic and foreign scientific research institution, thereby formed the novel process of a series of extracting titanium from electrolyzed molten salt such as titanium oxide, titanium chloride electrolysis and useless titanium electrorefining.
Usually, the molten salt system of extracting titanium from electrolyzed molten salt generally forms (being called for short female ionogen) by one or more in alkali metal chloride and/or alkaline earth metal chloride, and is different according to technique, suitably adds low-valence titanium chloride.For improving cathode product quality, controlling product pattern and size of particles, need to form Low-valent Titanium in molten salt system.At present, the method that forms Low-valent Titanium in female ionogen is: pass into titanium tetrachloride in female electrolytical fused salt and make itself and the titanium valve reaction that is added in this fused salt, thereby forming Low-valent Titanium.Yet for the method, along with the carrying out of reaction, the titanium valve particle diminishes gradually, and the fine powder disperse causes electrolyte pollution in molten salt system, and reactivity is lower; Simultaneously, TiCl at high temperature
4Have strong corrosion, easily corrosion testing apparatus, also can introduce molten salt system with foreign ion.
Summary of the invention
For the reaction that exists in present low price titanium chloride fused salt preparation process not exclusively, pollute molten salt electrolyte, TiCl
4The problems such as etching apparatus the invention provides a kind of method for preparing the molten salt electrolyte that contains low-valence titanium chloride, to overcome at least one in these problems.In addition, the present invention also provides a kind of and adopts the described molten salt electrolyte that contains low-valence titanium chloride to extract the method for titanium.
An aspect of of the present present invention provides a kind of method for preparing the molten salt electrolyte that contains low-valence titanium chloride.Described method comprises step: alkali metal chloride and/or alkaline earth metal chloride are mixed to form mixture with the metal chloride of predetermined amount, wherein, in described metal chloride the standard potential of metal ion is being than the standard potential of divalence or trivalent titanium ion just; Take the electrode that contains metal titanium as anode, take described mixture as molten salt electrolyte, the configuration negative electrode carries out electrolysis, and so that the described metal chloride in described mixture all is deposited on negative electrode, the gained fused salt is the molten salt electrolyte that contains low-valence titanium chloride.
In one exemplary embodiment of the present invention, described metal chloride can be one or more in cupric chloride, silver chloride, nickelous chloride, cuprous chloride.
In one exemplary embodiment of the present invention, in described mixture, can to make divalence in the described molten salt electrolyte that contains low-valence titanium chloride and the muriatic total content of titanous be 1.4%～8% to the content of metal chloride.
In one exemplary embodiment of the present invention, before described method also can be included in described electrolysis step, described mixture is carried out drying and processing and carries out vacuum hydro-extraction at 280～320 ℃ and process at 100～140 ℃, to remove free-water and crystal water wherein.
In one exemplary embodiment of the present invention, the metal titanium of described anode can be titanium valve, titanium sponge or titanium rod, and described negative electrode can be carbon steel rod.
In one exemplary embodiment of the present invention, in described electrolysis step, anodic current density may be controlled to 0.1～0.5A/cm
2
Another aspect of the present invention provides a kind of method of extracting titanium from electrolyzed molten salt.Described method adopts the molten salt electrolyte that contains low-valence titanium chloride as above to come the electrowinning titanium as molten salt electrolyte.
Compared with prior art, beneficial effect of the present invention comprises: can in the situation that do not pollute molten salt electrolyte, corrosion testing apparatus does not make the molten salt electrolyte that contains low-valence titanium chloride, and reactivity is high, technological process can be continuous.
Embodiment
Hereinafter, describe preparation of the present invention in detail in connection with exemplary embodiment and contain the method for molten salt electrolyte of low-valence titanium chloride and the method for extracting titanium from electrolyzed molten salt.
The method that preparation according to an aspect of the present invention contains the molten salt electrolyte of low-valence titanium chloride comprises the following steps: alkali metal chloride and/or alkaline earth metal chloride are mixed to form mixture with the metal chloride of predetermined amount, wherein, in described metal chloride the standard potential of metal ion is being than the standard potential of divalence or trivalent titanium ion just; Take the electrode that contains metal titanium as anode, take described mixture as molten salt electrolyte, the configuration negative electrode carries out electrolysis, and so that the described metal chloride in described mixture all is deposited on negative electrode, the gained fused salt is the molten salt electrolyte that contains low-valence titanium chloride.
Wherein, the amount of allocating into of described metal chloride (content of described metal chloride in described mixture in other words) can be determined according to the content of titanium lower chloride in the required molten salt electrolyte that contains the titanium lower chloride that makes.Preferably, in described mixture the content of metal chloride can to make divalence in the described molten salt electrolyte that contains low-valence titanium chloride and the muriatic total content of titanous be 1.4%～8%.
Wherein, metal chloride can be one or more in cupric chloride, silver chloride, nickelous chloride, cuprous chloride, but is not limited to this.
Wherein, the metal titanium of anode can be titanium valve, titanium sponge or titanium rod; Negative electrode can be carbon steel rod, carbon-point etc.
Preferably, in described electrolysis step, anodic current density is controlled to be 0.1～0.5A/cm
2
In addition, before described method also can be included in described electrolysis step, described mixture is carried out drying and processing and carries out vacuum hydro-extraction at 280～320 ℃ and process at 100～140 ℃, to remove free-water and crystal water wherein.
Specifically, in one exemplary embodiment of the present invention, the method that preparation contains the molten salt electrolyte of low-valence titanium chloride also can realize in the following way:
The current potential metal chloride more positive than titanium that adds predetermined amount in alkali metal chloride and/or alkaline earth metal chloride; after ball milling mixes; under 120 ℃ of conditions, be placed in oven drying 24h, then be transferred in electrolyzer; after vacuum hydro-extraction 3h under 300 ℃ of conditions; pass into shielding gas, after continuation heats up and makes electrolyte melting, take metal titanium as anode; carbon steel rod is that negative electrode is implemented electrolysis, and the reaction that occur on electrode this moment is as follows:
Negative electrode: M
n++ ne → M
Anode: Ti → Ti
n+2≤n in+ne(anode≤3)
When the metal ion (M that wherein adds being detected
n+) be zero after, stop power transmission, and extract negative electrode, namely get the prepared molten salt electrolyte that contains low-valence titanium chloride.In the present invention, the chemical valence of metal M is not limited to the scope of above-mentioned n, also can be other scope.
The molten salt electrolyte that contains low-valence titanium chloride of the present invention is to prepare by electrolysis mode, can effectively avoid using TiCl
4The problems such as the titanium valve reaction that exists in preparation low price titanium chloride process is incomplete, burn into pollution.Simultaneously, the appliance arrangement that the present invention uses is simple, preparation process is easy to control, only need to detect the metal chloride content that adds in ionogen and just can judge the degree of electrolytic reaction, and just can calculate prepared low price titanium chloride content according to the metal chloride content that adds, thereby prepared Low-valent Titanium concentration adopts TiCl
4Preparation is wanted accurately.When the interpolation metal chloride content in electrolyte system is zero; stop power transmission; and extract cathode product under protective atmosphere; namely complete required electrolytical preparation, at this moment, if continue energising; the metal titanium that anode dissolves in and negative electrode titanium valve are separated out and still are in equilibrium state; thereby can guarantee the system balance of titanium chloride at a low price, therefore, the present invention can realize the serialization production of whole technique.
Below, in connection with concrete example, the present invention is described in further detail.Need to prove, following example is only for the purpose of illustrating property, for being not in order to limit the present invention.
Example 1
550g Repone K and 440g sodium-chlor (mol ratio is 1:1) are mixed; after adding massfraction to be 5% cupric chloride mixing; put into reactor after 120 ℃ of dryings; after assembling anode and cathode, carry out vacuum hydro-extraction 5h under 300 ℃ of conditions, then pour into argon gas; and be warming up under argon shield atmosphere 750 ℃ make electrolyte melting after; connect the anode and cathode power supply, strength of current is 20A, and anodic current density is pressed 0.1A/cm
2Implement electrolysis, and detect content of copper ion in molten salt system, when its concentration is zero, stop power transmission, extract anode and cathode, the full titanium concentration of mensuration system is 1.8%, and valence state is+2.
Example 2
550g lithium chloride and 440g sodium-chlor (mol ratio is 1:1) are mixed, and adding massfraction is 8% NiCl
2After mixing; put into reactor after 120 ℃ of dryings; after assembling anode and cathode; carry out vacuum hydro-extraction 5h under 300 ℃ of conditions; then pour into argon gas, and be warming up under argon shield atmosphere 450 ℃ make electrolyte melting after, connect the anode and cathode power supply; strength of current is 20A, and anodic current density is pressed 0.5A/cm
2Implement electrolysis, and detect nickel ion content in molten salt system, when its concentration is zero, stop power transmission, extract anode and cathode, the full titanium concentration of mensuration system is 2%, and valence state is+3.
Example 3
With 1000g calcium chloride; adding massfraction is after 5% cupric chloride mixing; put into reactor after 120 ℃ of dryings; after assembling anode and cathode, carry out vacuum hydro-extraction 5h under 300 ℃ of conditions, then pour into argon gas; and be warming up under argon shield atmosphere 850 ℃ make electrolyte melting after; connect the anode and cathode power supply, strength of current is 20A, and anodic current density is pressed 0.3A/cm
2Implement electrolysis, and detect content of copper ion in molten salt system, when its concentration is zero, stop power transmission, extract anode and cathode, the full titanium concentration of mensuration system is 1.4%, and valence state is+2.5.
In addition, the present invention also provides a kind of method of extracting titanium from electrolyzed molten salt, and the method adopts the molten salt electrolyte that contains low-valence titanium chloride as above to come the electrowinning titanium as molten salt electrolyte.
In sum, the invention provides a kind of method for preparing the Low-valent Titanium molten salt electrolyte, the method is added a certain amount of current potential metal chloride more positive than titanium in original female ionogen, take titanium metal as anode, carbon steel rod is that negative electrode is implemented electrolysis, and the metal ion of the interpolation in fused salt is deposited on negative electrode, simultaneously, the titanium of anode enters in fused salt and to form titanium chloride at a low price, the metal ion that adds in ionogen is all removed and is made the fused salt that contains low-valence titanium chloride.The method has been avoided use TiCl
4The problem that exists in the preparation Low-valent Titanium, simultaneously, technological operation is simple, and is low to the appliance arrangement requirement, can realize serialization production.
Although the above has described the present invention in conjunction with exemplary embodiment, those of ordinary skills should be clear, in the situation that do not break away from the spirit and scope of claim, can carry out various modifications to above-described embodiment.
Claims (8)
1. a method for preparing the molten salt electrolyte that contains low-valence titanium chloride, is characterized in that, said method comprising the steps of:
Alkali metal chloride and/or alkaline earth metal chloride are mixed to form mixture with the metal chloride of predetermined amount, and wherein, in described metal chloride, the standard potential of metal ion than the standard potential of divalence or trivalent titanium ion just;
Take the electrode that contains metal titanium as anode, take described mixture as molten salt electrolyte, the configuration negative electrode carries out electrolysis, and so that the described metal chloride in described mixture all is deposited on negative electrode, the gained fused salt is the molten salt electrolyte that contains low-valence titanium chloride.
2. preparation according to claim 1 contains the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, described metal chloride is one or more in cupric chloride, silver chloride, nickelous chloride, cuprous chloride.
3. preparation according to claim 1 contains the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, in described mixture, can to make divalence in the described molten salt electrolyte that contains low-valence titanium chloride and the muriatic total content of titanous be 1.4%～8% to the content of metal chloride.
4. preparation according to claim 1 contains the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, before described method also is included in described electrolysis step, described mixture is carried out drying and processing and carries out vacuum hydro-extraction at 280～320 ℃ and process at 100～140 ℃, to remove free-water and crystal water wherein.
5. preparation according to claim 1 contains the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, the metal titanium of described anode is titanium valve, titanium sponge or titanium rod.
6. preparation according to claim 1 contains the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, described negative electrode is carbon steel rod.
7. preparation according to claim 1 contains the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, in described electrolysis step, anodic current density is controlled to be 0.1～0.5A/cm
2
8. the method for an extracting titanium from electrolyzed molten salt, is characterized in that, described method adopts the molten salt electrolyte that contains low-valence titanium chloride as described in any one in claim 1 to 7 to come the electrowinning titanium as molten salt electrolyte.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611727A (en) * | 2013-11-01 | 2015-05-13 | 北京有色金属研究总院 | Preparation method of chloride composite electrolyte used for molten salt electrolysis |
| CN104928721A (en) * | 2015-06-12 | 2015-09-23 | 中南大学 | Preparation and refining device for low-valent titanium chloride molten salt electrolyte |
| CN105088283A (en) * | 2015-09-29 | 2015-11-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting metallic titanium |
| CN106591888A (en) * | 2016-12-26 | 2017-04-26 | 宝纳资源控股(集团)有限公司 | Preparation method and device of low-valence titanium ion molten salt electrolyte |
| CN107587169A (en) * | 2017-10-30 | 2018-01-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Ti in one kind regulation fused electrolyte2+And Ti3+The method of ratio |
| CN110184628A (en) * | 2019-06-19 | 2019-08-30 | 北京科技大学 | A method of the high-purity titanium valve of hypoxemia is prepared using Industry Waste titanium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104611727A (en) * | 2013-11-01 | 2015-05-13 | 北京有色金属研究总院 | Preparation method of chloride composite electrolyte used for molten salt electrolysis |
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| CN104928721A (en) * | 2015-06-12 | 2015-09-23 | 中南大学 | Preparation and refining device for low-valent titanium chloride molten salt electrolyte |
| CN105088283A (en) * | 2015-09-29 | 2015-11-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting metallic titanium |
| CN105088283B (en) * | 2015-09-29 | 2018-05-11 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for extracting Titanium |
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| CN107587169A (en) * | 2017-10-30 | 2018-01-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Ti in one kind regulation fused electrolyte2+And Ti3+The method of ratio |
| CN110184628A (en) * | 2019-06-19 | 2019-08-30 | 北京科技大学 | A method of the high-purity titanium valve of hypoxemia is prepared using Industry Waste titanium |
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