CN104894376B - Electrothermal reduction method for preparing V-Ti-Fe base hydrogen storage alloy - Google Patents
Electrothermal reduction method for preparing V-Ti-Fe base hydrogen storage alloy Download PDFInfo
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Abstract
The invention discloses an electrothermal reduction method for preparing a V-Ti-Fe base hydrogen storage alloy. The method comprises specific steps as follows: A, reaction materials are prepared and comprise aluminum powder, aluminum calcium alloy powder, vanadium oxide, titanium oxide, scrap iron, calcium oxide, calcium fluoride and potassium chlorate; B, part of the reaction materials are placed in an electric arc furnace and ignited by magnesium chips for a metal thermal reduction reaction; C, after the reaction is stabilized, the residual reaction materials are added gradually; D, the electric arc furnace adopts submerged-arc heating, and powder injection refining is performed; E, a product is discharged from the furnace. Compared with a traditional pure metal doped smelting method, the electrothermal reduction method has the advantages of low raw material cost and high production speed, is suitable for large-scale production of the V-Ti-Fe base hydrogen storage alloy and has a good application prospect.
Description
Technical field
The invention belongs to hydrogen bearing alloy preparation field, particularly to a kind of electrothermal reduction system of V-Ti-Fe base hydrogen storage alloy
Preparation Method.
Background technology
Today of environmental problem growing tension, actively develop cleaning power source and seemed increasingly important.Hydrogen Energy is as dry
Only, efficient clean energy resource, receives the extensive concern of people, and hydrogen storage material is as the key technology of hydrogen utilization, always
It is research worker focus of attention.
V-Ti-Fe base hydrogen storage alloy theory hydrogen storage content is big, and it is good, before having good application that room temperature inhales hydrogen desorption kineticses performance
Scape.Its preparation method is commonly used at present converts the method for mixing, that is, with simple metal such as vanadium, titaniums as raw material, anti-using induction furnace or electric arc furnace
Remelt refining obtains.Because pure vanadium is expensive, the melting point metal such as vanadium, titanium is too high in addition, and the preparation cost that result in alloy is too high,
Limit its large-scale application.
With the pure V of VFe alloy replacing, carry out alloy preparation although the preparation cost of V-Ti-Fe alloy can be reduced, but work
The impurity such as more Al, Si, O in industry VFe, can produce larger negative effect to the hydrogen storage property of alloy.Additionally, because industrial vanadium
Ferrum mostly is FeV50 and FeV80, and it contains Fe amount and is respectively 50wt% and 20wt%, and that is, the ratio of V and Fe is relatively fixed, this is just
Bring difficulty to the hydrogen bearing alloy preparing special component.
In the one-tenth present aspect reducing the preparation of V-Ti-Fe alloy, also carry out the trial of alloy preparation with metallothermic processes.
It is high that the method has the advantages that composition flexibly can be in harmonious proportion production efficiency, can be raw material with more cheap metal-oxide in addition,
So production cost is relatively low.But because smelting time is short, reaction is insufficient, slag gold separating effect is bad, exists certain in alloy
The slag inclusion of amount and the impurity such as aluminum, oxygen.In addition the recovery rate of metal is also quite low, the response rate nearly 80% of vanadium, and the recovery rate of titanium is only
Have 30% about.Therefore, metallothermic reduction method also needs to improve further.
Content of the invention
For overcoming the defect of metallothermic processes or deficiency in prior art, it is an object of the invention to, provide a kind of with
Metal-oxide prepares V-Ti-Fe base hydrogen storage alloy for raw material by electric reduction process, and the method can improve receiving of metal
Rate, reduces the impurity in alloy.
In order to realize above-mentioned task, the present invention takes following technical solution：
A kind of electric reduction process preparation V-Ti-Fe base hydrogen storage alloy is it is characterised in that step is as follows：
A, preparation reaction material；Described reaction material is aluminium powder, Al alloy powder, barium oxide, titanium oxide, iron filings, oxidation
Calcium, calcium fluoride and potassium chlorate；
B, partial reaction material is put in electric arc furnace, lighted using magnesium chips, carry out metallothermic reduction reaction；
After C, metallothermic reduction reacting balance, it is gradually added into remaining reaction material；
After D, reaction material add, electric arc furnace energising striking heating, and pass through dusting device, to melt bottom spray refining powder
Carry out refine, refine powder is loaded by argon, refine powder is CaO-CaF2-V2O5Slag system, refining time 10min～20min；
After E, refine terminate, come out of the stove under argon protection, obtain V-Ti-Fe base hydrogen storage alloy；
Step D refine meal component by mass percentage, CaO：50%～65%, CaF2：20%～50%, V2O5：
0.1%～15%.
Wherein, barium oxide is V2O5Piece vanadium or one kind of powder vanadium, Al alloy powder is Al-Mg alloy powder or kalzium metal powder
A kind of.
Al alloy powder is Al-Mg alloy powder or kalzium metal powder.
Aluminium powder add total amount be reduction barium oxide and titanium oxide institute must theoretical value 70%～95%.
The addition of Al-Mg alloy powder or kalzium metal powder is the 10%～40% of aluminium powder gross mass.
The chemical composition of Al-Mg alloy powder is by mass percentage：Mg：45%～50%, Al：50%～55%, described
The chemical composition of kalzium metal powder be by mass percentage：Ca：65%～80%, Al：20%～35%.
Compared with the prior art, the present invention has advantage as is evident below：
V-Ti-Fe base hydrogen storage alloy preparation is carried out for raw material using more cheap metal-oxide, contributes to reducing alloy
Preparation cost, easily realize large-scale production.
Specific embodiment
The present invention is described in further detail by the following examples, it should be noted that the invention is not restricted to
Under embodiment.
Embodiment 1：
5kg is contained the powder vanadium of vanadic anhydride 99%, high titanium slag that 5kg is 96% containing titanium dioxide, 3.15kg aluminium powder,
0.95kg kalzium metal, 1.5kg potassium chlorate, 3.0kg calcium oxide, 1kg calcium fluoride and 0.45kg iron filings mix homogeneously.
The compound taking 1/3 is bed material, is put in electric arc furnace, and surface adds magnesium chips igniting, carries out metallothermic reduction reaction, instead
After answering steadily, it is gradually added into leftover materials, after reaction material adds, electric arc furnace energising submerged arc heating, and start to spray refine powder refine,
Refine meal component is CaO (60wt%)-CaF2(35wt%)-V2O5(5wt%), consumption 0.8kg, refining slag is blown by argon load
Enter molten bath bottom, after refine 15min, standing, come out of the stove under argon protection.
Come out of the stove and obtain V50.0Ti42.1Fe7.9The recovery rate of alloy 5.2kg, vanadium and titanium is respectively 92.1% and 71.3%, alloy
In 1.1wt% containing aluminum, oxygen 0.6wt%.
Embodiment 2：
5kg is contained the powder vanadium of vanadic anhydride 99%, high titanium slag that 5kg is 96% containing titanium dioxide, 3.15kg aluminium powder,
0.95kg kalzium metal, 1.5kg potassium chlorate, 3.0kg calcium oxide, 1kg calcium fluoride and 0.45kg iron filings mix homogeneously.
Melting is substantially the same manner as Example 1 with refinery practice, except that refining slag is CaO (55wt%)-CaF2
(43wt%)-V2O5(2wt%).
After coming out of the stove, obtain V48.9Ti42.5Fe8.6The recovery rate of alloy 5.2kg, vanadium and titanium is respectively 88.9% and 70.9%,
2.3wt% containing aluminum in alloy, oxygen 0.7wt%.
Embodiment 3：
5kg is contained the powder vanadium of vanadic anhydride 99%, titanium dioxide that 5kg is 98% containing titanium dioxide, 3.15kg aluminium powder,
0.95kg kalzium metal, 1.5kg potassium chlorate, 3.0kg calcium oxide, 1kg calcium fluoride and 0.45kg iron filings mix homogeneously.
Melting is same as Example 1 with refinery practice.
After coming out of the stove, obtain V52.6Ti39.8Fe7.6The recovery rate of alloy 5.0kg, vanadium and titanium is respectively 92.6% and 64.1%,
1.3wt% containing aluminum in alloy, oxygen 0.8wt%.
Comparative example：
Alloy preparation is carried out using traditional metallothermic processes.
Stove built by magnesia brick, as the metallothermic reduction reacting furnace of alloy preparation.Reaction raw materials are：5kg contains vanadic anhydride
High titanium slag that 99% powder vanadium, 5kg are 96% containing titanium dioxide, 3.15kg aluminium powder, 0.95kg kalzium metal, 1.5kg potassium chlorate,
3.0kg calcium oxide, 1kg calcium fluoride and 0.45kg iron filings.
By reaction raw materials mix homogeneously, put in thermit reaction stove, then add magnesium chips igniting on raw material surface, reaction completes
After 3h, remove body of heater, the V obtaining64.3Ti24.9Fe10.8The recovery rate of alloy 3.9kg, vanadium and titanium is respectively 85.1% He
30.4%, 3.4wt% containing aluminum in alloy, oxygen 1.1wt%.
Compared with embodiment 1,2 and 3, only has the fusion process from heat release for the metallothermic reduction reaction in comparative example, after not having
The recovery rate of the heating melting of phase and refining process, vanadium and titanium is relatively low, and the impurity of aluminum and oxygen is also higher.
Claims (7)
1. a kind of electric reduction process preparation V-Ti-Fe base hydrogen storage alloy is it is characterised in that step is as follows：
A, preparation reaction material；Described reaction material is aluminium powder, Al alloy powder, barium oxide, titanium oxide, iron filings, calcium oxide, fluorine
Change calcium and potassium chlorate；
B, partial reaction material is put in electric arc furnace, lighted using magnesium chips, carry out metallothermic reduction reaction；
After C, metallothermic reduction reacting balance, it is gradually added into remaining reaction material；
After D, reaction material add, electric arc furnace energising striking heating, and pass through dusting device, carry out to melt bottom spray refining powder
Refine, refine powder is loaded by argon, and described refine powder is CaO-CaF2-V2O5Slag system, refining time 10min～20min；
After E, refine terminate, come out of the stove under argon protection, obtain V-Ti-Fe base hydrogen storage alloy；
The composition of described refine powder by mass percentage, CaO：50%～65%, CaF2：20%～50%, V2O5：0.1%～
15%.
2. electric reduction process as claimed in claim 1 prepares V-Ti-Fe base hydrogen storage alloy it is characterised in that described vanadium oxygen
Compound is V2O5Piece vanadium or powder vanadium, described titanium oxide is high titanium slag or titanium dioxide.
3. electric reduction process as claimed in claim 1 prepares V-Ti-Fe base hydrogen storage alloy it is characterised in that described aluminum closes
Bronze is Al-Mg alloy powder or kalzium metal powder.
4. electric reduction process preparation V-Ti-Fe base hydrogen storage alloy as claimed in claim 1 is it is characterised in that described aluminium powder adds
Enter total amount be reduction barium oxide and titanium oxide institute must theoretical value 70%～95%.
5. electric reduction process as claimed in claim 3 prepares V-Ti-Fe base hydrogen storage alloy it is characterised in that described magnalium
The addition of alloyed powder or kalzium metal powder is the 10%～40% of aluminium powder gross mass.
6. electric reduction process as claimed in claim 3 preparation V-Ti-Fe base hydrogen storage alloy it is characterised in that：Described magnalium
The chemical composition of alloyed powder is by mass percentage：Mg：45%～50%, Al：50%～55%, described kalzium metal powder
Chemical composition be by mass percentage：Ca：65%～80%, Al：20%～35%.
7. electric reduction process as claimed in claim 1 prepares V-Ti-Fe base hydrogen storage alloy it is characterised in that described V-Ti-
Fe base hydrogen storage alloy, by mole containing V：45%～65%, Ti：25%～45%, Fe：5%～15%.
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| CN106756050B (en) * | 2016-12-26 | 2018-07-27 | 北京国电龙源环保工程有限公司 | The method that conbustion synthesis recycles waste denitration catalyst |
| CN107350485B (en) * | 2017-06-19 | 2019-08-02 | 西安建筑科技大学 | A kind of gas phase reaction preparation method of V-Ti-Fe hydrogen storing alloy powder |
| CN108913972B (en) * | 2018-07-04 | 2019-10-01 | 南理工泰兴智能制造研究院有限公司 | A kind of vanadium base complex phase environmental protection hydrogen storage material |
| CN110699561B (en) * | 2019-11-12 | 2020-12-25 | 四川大学 | Method for producing high-purity metal vanadium by adopting directional solidification |
| CN115612903B (en) * | 2022-12-12 | 2023-03-17 | 四川大学 | High-vanadium solid solution type hydrogen storage alloy and preparation method thereof |
| CN117286378A (en) * | 2023-09-27 | 2023-12-26 | 承德天大钒业有限责任公司 | TiMnV-based hydrogen storage alloy and preparation method and application thereof |
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| JPH0949034A (en) * | 1995-08-10 | 1997-02-18 | Matsushita Electric Ind Co Ltd | Production of hydrogen storage alloy |
| WO2002042507A1 (en) * | 2000-11-27 | 2002-05-30 | Santoku Corporation | Hydrogen-occluding alloy and method for production thereof |
| CN1245527C (en) * | 2001-04-27 | 2006-03-15 | 株式会社三德 | Method for producing Cr-Ti-V hydrogen storage alloys |
| JP5527768B2 (en) * | 2010-08-18 | 2014-06-25 | 株式会社日本製鋼所 | High capacity hydrogen storage alloy |
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