CN103147096B - 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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- CN103147096B CN103147096B CN201310104642.1A CN201310104642A CN103147096B CN 103147096 B CN103147096 B CN 103147096B CN 201310104642 A CN201310104642 A CN 201310104642A CN 103147096 B CN103147096 B CN 103147096B
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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 prepare containing the molten salt electrolyte of low-valence titanium chloride method and a kind of using this containing molten salt electrolyte of low-valence titanium chloride as molten salt electrolyte to extract the method for titanium.
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, thus study by lot of domestic and foreign scientific research institution, thus define 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 is generally made up of (being called for short female ionogen) one or more in alkali metal chloride and/or alkaline earth metal chloride, different according to technique, suitably adds low-valence titanium chloride.For improving cathode product quality, controlling product morphology and size of particles, need to form Low-valent Titanium in molten salt system.At present, the method forming Low-valent Titanium in female ionogen is: to be passed into by titanium tetrachloride in female electrolytical fused salt and itself and the titanium valve be added in this fused salt reacts, thus formation Low-valent Titanium.But for the method, along with the carrying out of reaction, titanium valve particle diminishes gradually, and fine powder disperse, in molten salt system, causes electrolyte pollution, and reactivity is lower; Meanwhile, at high temperature TiCl
4there is aggressive, easy corrosion testing apparatus, also foreign ion can be introduced molten salt system.
Summary of the invention
, pollution molten salt electrolyte, TiCl incomplete for the reaction existed in the current preparation process of titanium chloride fused salt at a low price
4the problems such as etching apparatus, the invention provides a kind of method preparing molten salt electrolyte containing low-valence titanium chloride, to overcome at least one item in these problems.In addition, present invention also offers and a kind ofly adopt the described molten salt electrolyte containing low-valence titanium chloride to extract the method for titanium.
An aspect of of the present present invention provides a kind of method preparing molten salt electrolyte containing 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 metal ion standard potential than divalence or trivalent titanium ion standard potential just; With the electrode containing metal titanium for anode, with described mixture for molten salt electrolyte, configuration negative electrode, carry out electrolysis, so that the described metal chloride in described mixture is all deposited on negative electrode, gained fused salt is the molten salt electrolyte containing 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, the content of metal chloride can make the described muriatic total content containing the divalence in the molten salt electrolyte of low-valence titanium chloride and titanous be 1.4% ~ 8%.
In one exemplary embodiment of the present invention, before described method also can be included in described electrolysis step, described mixture is carried out to drying and processing at 100 ~ 140 DEG C and carries out vacuum hydro-extraction process at 280 ~ 320 DEG C, to remove free-water wherein and crystal water.
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 provides a kind of method of extracting titanium from electrolyzed molten salt.Described method adopts the molten salt electrolyte containing low-valence titanium chloride as above to carry out electrowinning titanium as molten salt electrolyte.
Compared with prior art, beneficial effect of the present invention comprises: can when do not pollute molten salt electrolyte, not corrosion testing apparatus the obtained molten salt electrolyte containing low-valence titanium chloride, and reactivity is high, technological process can be continuous.
Embodiment
Hereinafter, preparation of the present invention will be described in detail in conjunction with exemplary embodiment containing the method for molten salt electrolyte of low-valence titanium chloride and the method for extracting titanium from electrolyzed molten salt.
Preparation according to an aspect of the present invention comprises the following steps containing the method for the molten salt electrolyte of low-valence titanium chloride: 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 metal ion standard potential than divalence or trivalent titanium ion standard potential just; With the electrode containing metal titanium for anode, with described mixture for molten salt electrolyte, configuration negative electrode, carry out electrolysis, so that the described metal chloride in described mixture is all deposited on negative electrode, gained fused salt is the molten salt electrolyte containing low-valence titanium chloride.
Wherein, the amount of allocating into (in other words, the content of described metal chloride in described mixture) of described metal chloride can according to required obtained determining containing the content of titanium lower chloride in the molten salt electrolyte of titanium lower chloride.Preferably, in described mixture, the content of metal chloride can make the described muriatic total content containing the divalence in the molten salt electrolyte of low-valence titanium chloride and 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 thereto.
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, it is 0.1 ~ 0.5A/cm that anodic current density controls
2.
In addition, before described method also can be included in described electrolysis step, described mixture is carried out to drying and processing at 100 ~ 140 DEG C and carries out vacuum hydro-extraction process at 280 ~ 320 DEG C, to remove free-water wherein and crystal water.
Specifically, in one exemplary embodiment of the present invention, preparation also can realize in the following way containing the method for the molten salt electrolyte of low-valence titanium chloride:
The metal chloride that the current potential of predetermined amount is more positive than titanium is added in alkali metal chloride and/or alkaline earth metal chloride; after ball milling mixes; under 120 DEG C of conditions, be placed in oven drying 24h, be then transferred in electrolyzer; under 300 DEG C of conditions after vacuum hydro-extraction 3h; passing into shielding gas, after continuation intensification makes electrolyte melting, take metal titanium as anode; carbon steel rod is that negative electrode implements electrolysis, and the reaction now electrode occurred is as follows:
Negative electrode: M
n++ ne → M
Anode: Ti → Ti
n+2≤n≤3 in+ne(anode)
When the metal ion (M wherein added being detected
n+) be after zero, stop power transmission, and extract negative electrode, obtain the prepared molten salt electrolyte containing 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.
Molten salt electrolyte containing low-valence titanium chloride of the present invention is prepared by electrolysis mode, can effectively avoid using TiCl
4the problems such as the titanium valve reaction existed 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 detect the degree that the metal chloride content added in ionogen just can judge electrolytic reaction, and just can calculate prepared low price titanium chloride content according to the metal chloride content added, thus obtained Low-valent Titanium concentration comparatively adopts TiCl
4preparation is wanted accurately.When the interpolation metal chloride content in electrolyte system is zero; stop power transmission; and cathode product is extracted under protective atmosphere; namely required electrolytical preparation is completed, now, if continue energising; the metal titanium that anode dissolves in and negative electrode titanium valve are separated out and are still in equilibrium state; thus the balance of system low price titanium chloride can be guaranteed, therefore, the present invention can realize the continuous prodution of whole technique.
Below, will be described in further detail the present invention in conjunction with concrete example.It should be noted that, example below only for the object of illustrating property, for be not intended to limit the present invention.
Example 1
By 550g Repone K and 440g sodium-chlor (mol ratio is 1:1) mixing; adding massfraction is after 5% cupric chloride mixing; reactor is put into after 120 DEG C of dryings; after assembling anode and cathode, under 300 DEG C of conditions, carry out vacuum hydro-extraction 5h, then pour into argon gas; and be warming up under argon atmosphere 750 DEG C make electrolyte melting after; connect anode and cathode power supply, strength of current is 20A, and anodic current density presses 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
By 550g lithium chloride and 440g sodium-chlor (mol ratio is 1:1) mixing, add the NiCl that massfraction is 8%
2after mixing; reactor is put into after 120 DEG C of dryings; after assembling anode and cathode; vacuum hydro-extraction 5h is carried out under 300 DEG C of conditions; then pour into argon gas, and be warming up under argon atmosphere 450 DEG C make electrolyte melting after, connect anode and cathode power supply; strength of current is 20A, and anodic current density presses 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
By 1000g calcium chloride; adding massfraction is after the cupric chloride mixing of 5%; reactor is put into after 120 DEG C of dryings; after assembling anode and cathode, under 300 DEG C of conditions, carry out vacuum hydro-extraction 5h, then pour into argon gas; and be warming up under argon atmosphere 850 DEG C make electrolyte melting after; connect anode and cathode power supply, strength of current is 20A, and anodic current density presses 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, present invention also offers a kind of method of extracting titanium from electrolyzed molten salt, the method adopts the molten salt electrolyte containing low-valence titanium chloride as above to carry out electrowinning titanium as molten salt electrolyte.
In sum, the invention provides a kind of method preparing Low-valent Titanium molten salt electrolyte, the method adds 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 implements electrolysis, by the metal ion deposition of the interpolation in fused salt on negative electrode, simultaneously, the titanium of anode enters in fused salt and forms titanium chloride at a low price, is all removed by the metal ion added and the obtained fused salt containing low-valence titanium chloride in ionogen.This method avoid and use TiCl
4prepare Problems existing in Low-valent Titanium, meanwhile, technological operation is simple, requires low, can realize continuous prodution to appliance arrangement.
Although describe the present invention in conjunction with exemplary embodiment above, those of ordinary skill in the art should be clear, when not departing from the spirit and scope of claim, can carry out various amendment to above-described embodiment.
Claims (8)
1. prepare a method for the molten salt electrolyte containing low-valence titanium chloride, it 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, wherein, in described metal chloride metal ion standard potential than divalence or trivalent titanium ion standard potential just;
With the electrode containing metal titanium for anode, with described mixture for molten salt electrolyte, configuration negative electrode, carry out electrolysis, so that the described metal chloride in described mixture is all deposited on negative electrode, gained fused salt is the molten salt electrolyte containing low-valence titanium chloride.
2. preparation according to claim 1 is containing the method for 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 is containing the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, in described mixture, the content of metal chloride can make the described muriatic total content containing the divalence in the molten salt electrolyte of low-valence titanium chloride and titanous be 1.4% ~ 8%.
4. preparation according to claim 1 is containing the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, before described method is also included in described electrolysis step, described mixture is carried out to drying and processing at 100 ~ 140 DEG C and carries out vacuum hydro-extraction process at 280 ~ 320 DEG C, to remove free-water wherein and crystal water.
5. preparation according to claim 1 is containing 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 is containing the method for the molten salt electrolyte of low-valence titanium chloride, and it is characterized in that, described negative electrode is carbon steel rod.
7. preparation according to claim 1 is containing the method for the molten salt electrolyte of low-valence titanium chloride, it is characterized in that, in described electrolysis step, it is 0.1 ~ 0.5A/cm that anodic current density controls
2.
8. a method for extracting titanium from electrolyzed molten salt, is characterized in that, described method comprises:
Method as claimed in any of claims 1 to 7 in one of claims is adopted to obtain molten salt electrolyte containing low-valence titanium chloride; Electrowinning titanium is carried out as molten salt electrolyte using this molten salt electrolyte containing low-valence titanium chloride.
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| CN104611727B (en) * | 2013-11-01 | 2017-03-15 | 北京有色金属研究总院 | A kind of preparation method of molten-salt electrolysis with chloride composite electrolyte |
| CN104928721B (en) * | 2015-06-12 | 2017-09-22 | 中南大学 | A kind of preparation of low-valence titanium chloride molten salt electrolyte and purifier |
| 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 |
| CN106591888B (en) * | 2016-12-26 | 2019-01-15 | 宝纳资源控股(集团)有限公司 | A kind of preparation method and device of low chemical 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 |
| CN115747889B (en) * | 2022-12-01 | 2024-09-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing electrolyte for electrolytic refining of titanium and method for electrolytic extraction of titanium |
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