CN101993111B - Method for preparing nanometer vanadous oxide - Google Patents
Method for preparing nanometer vanadous oxide Download PDFInfo
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- CN101993111B CN101993111B CN2010105136989A CN201010513698A CN101993111B CN 101993111 B CN101993111 B CN 101993111B CN 2010105136989 A CN2010105136989 A CN 2010105136989A CN 201010513698 A CN201010513698 A CN 201010513698A CN 101993111 B CN101993111 B CN 101993111B
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Abstract
The invention provides a method for preparing nanometer vanadous oxide, which relates to a preparation method of a chemical metallurgy material. The method comprises the following steps of: adding vanadate in a reactor; adding an organic solvent; heating the reactor to reach a temperature of 100-500 DEG C and a pressure of 0.5-20.0Mpa, and maintaining the state for 0.1-6.0h; reducing the pressure of the reactor to 0-5.0Mpa at the heating state; separating the organic solvent out; and stopping heating to cool the reactor to a room temperature so as to obtain the black nanometer vanadous oxide. The method has the advantages of low cost and simple process, and can realize industrialized production, and the raw materials are cheap and easy to be obtained. The prepared nanometer vanadous oxide can be widely applied to various fields, such as electric switches, magnetic switches, optical switches, gas sensors, storage media, resistance materials, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of chemical materials, particularly relate to a kind of preparation method of nano level vanadous oxide.
Background technology
V
2O
3Two phase transformations relevant with temperature are arranged, at about 160K the first-order phase transition of the antiferromagnetic insulation phase of low temperature (AFI) to high temperature paramagnetic metal phase (PM) takes place, change in resistance is the NTC characteristic, and the sudden change of monocrystalline resistivity reaches 7 one magnitude.Arrive the second-order phase transition of high temperature paramagnetic metal phase (PM) to the scope generation low temperature paramagnetic metal phase (PM) of 540K at about 350K.Resistivity is PTC (PTC) characteristic during phase transformation.V
2O
3Also be a kind of gunn material, susceptibility during phase transformation, optical transmittance and reflectivity also produce sudden change.
Since have excellent light, electricity, magnetic property, in the serial oxide compound of vanadium, vanadous oxide (V
2O
3) be a kind of crucial product, at electricity, magnetic, photoswitch, the multiple fields such as gas sensor, storage medium, resistive material that reach all have widely uses.
Yet, because V
2O
3In the AFI-PI phase transformation, approximately there is 1.4% or 1.5% unit cell volume variation, in the PM-PI phase transformation, has about 1.2% unit cell volume variation.Therefore in material thermal cycling process, can produce cracked problem, destroy the performance of material; To a great extent limit the application of vanadous oxide; And cracked generation and its microstructure of material has relation, when the particle of vanadous oxide reaches nano level, into the high density ceramic of sintering again; Just can improve material property significantly, avoid producing cracked problem.
The method for preparing at present nano grade vanadium trioxide mainly contains:
It is the method for feedstock production nano grade vanadium trioxide with the Vanadium Pentoxide in FLAKES that Chinese patent CN1300002C discloses a kind of.This method is earlier with V
2O
5And H
2C
2O
4Backflow 2h obtains VOC in absolute ethyl alcohol
2O
4Ethanolic soln, reduction obtains nano level V under the condition of HTHP then
2O
3This method steps is complicated, need prepare VOC in advance for obtaining nano grade vanadium trioxide
2O
4, increased preparation cost.In addition, the raw material of this method only is confined to Vanadium Pentoxide in FLAKES.
" Zhongshan University's journal " (natural science edition) (2003,42 (1): 116～118) introduced: at H
2In the atmosphere to vanadyl (IV) basic carbonate ammonium ammonium (NH
4)
5[(VO)
6(CO
3)
4(OH)
9] 10H
2O obtains the spherical pure V of the about 30nm of granularity under the condition of 900 ℃ of insulation 30min
2O
3Powder.The shortcoming of this method is: temperature of reaction is too high, and reaction raw materials vanadyl (IV) basic carbonate ammonium is difficult simultaneously obtains, and synthetic cost is high, is difficult to realize suitability for industrialized production.
" J.Photopolym.Sci.Technol. " (1997,10 (2): 211-215) introduced: utilize the method for the vanadous oxide of induced with laser method synthesis nano, used raw material is VOCl
3, through with H
2, O
2With
Mixed after, induced with laser generates V
2O
3The shortcoming of this method is: the raw material VOCl that this method is used
3Itself add the water moulding after by pentachloro-ization two vanadium and coke burden, dry back introduce chlorine gas to make reaction makes, the feedstock production cost is high, is not easy to obtain, and be liquid, is difficult for storage, receives the heat-flash decomposition can emit poisonous gas, be prone to set off an explosion.In addition, the raw material chance time of tide is corrosive to most metal, and is strict to production unit.
The method that a kind of thermolysis oxalate prepares the nanometer vanadous oxide has been introduced in " Materials Letters " (2005,59:2729～2731).The Vanadium Pentoxide in FLAKES and the vitriol oil are joined in the zero(ppm) water, after vigorous stirring obtains suspension-s, be heated to 90 ℃, in suspension-s, feed SO then
2Gas, and stir constantly simultaneously and know that solution becomes blueness.Adding 5% ammoniacal liquor, to regulate pH be 6～7, obtains gray precipitate, vacuum-drying and with distilled water wash 5 times; Gray precipitate is dissolved in the 0.1M oxalic acid aqueous solution, obtains black-and-blue crystal after concentrating, after letting with crystal 90 ℃ of dry 5h under vacuum condition; Place silica tube then; Under the argon shield,, obtain the black powder that particle diameter is 25～50nm after being cooled to room temperature at 400～500 ℃ of following heating 6h.The shortcoming of this method is: technology very complicated, raw materials used kind many (Vanadium Pentoxide in FLAKES, the vitriol oil, SO
2, ammoniacal liquor, oxalic acid, argon gas), the time long (＞11h), production cost is high.
" Anhui chemical industry " (2003,29 (6): 20～21) introduced and use YLENE to be that solvent adopts the poroid V of solvent-thermal method synthesis of nano
2O
3Powder.With V
2O
5Put into autoclave with KI, adding YLENE to compactedness is 80%, sealing autoclave; Autoclave is maintained under 200 ℃, be incubated 24 hours, slowly cool to room temperature again; Suction filtration, solid-liquid separation, collecting precipitation; Respectively wash three times with sig water, deionized water, Hydrogen chloride, deionized water, absolute ethyl alcohol,, obtain the poroid V of nanometer at last with 80 ℃ of dryings of product vacuum 4 hours
2O
3Black powder.The shortcoming of this method is: route time length (＞28h), the product aftertreatment is too complicated.
Chinese patent CN1347856A discloses a kind of V
2O
3The preparation method of base nano-powder.At first with V
2O
5At reductive agent H
2C
2O
42H
2O, xitix, N
2H
4Be prepared into VOCl under the effects such as 2HCl, water hydrazine or oxammonium hydrochloride
2Solution is then at CO
2, N
2Or under the Ar atmosphere, with VOCl
2Generate vanadyl basic carbonate ammonium presoma with volatile salt or the reaction of bicarbonate of ammonia supersaturated solution; And in absolute ethyl alcohol, presoma is crushed to≤granularity of 2 μ m with UW; At last under hydrogen atmosphere with the presoma thermal degradation; Temperature is 500～1000 ℃, and the time is 0.5～3h, can obtain the V of granularity less than 100nm
2O
3Powder.The shortcoming of this method is: need pass through V
2O
5Preparation VOCl
2Intermediate, technological process are too complicated, and intermediate reduction simultaneously generates V
2O
3Required reduction temperature is higher.
As stated, produce the used raw material of nano grade vanadium trioxide and be mostly V
2O
5, (NH
4)
5[(VO)
6(CO
3)
4(OH)
9] 10H
2O and VOCl
3As use Vanadium Pentoxide in FLAKES to be raw material; Because it is to be decomposed to produce by ammonium meta-vanadate or many (gathering) ammonium vanadate heated oxide to obtain that Vanadium Pentoxide in FLAKES is gone up in industry, just there is very high cost in itself, and the process environment of suitability for industrialized production Vanadium Pentoxide in FLAKES pollutes bigger simultaneously; When using Vanadium Pentoxide in FLAKES as feedstock production nanometer vanadous oxide, just meaning has increased extra preparation raw materials cost and Environmental costs.At present the method for synthesis of nano vanadous oxide all exists some drawback or weak point, and for example: synthesis temperature is higher, complex technical process, raw material are not easy to obtain, cost is high.Also do not utilize ammonium meta-vanadate or many (gathering) ammonium vanadate to prepare the report of nano grade vanadium trioxide.
Therefore, the production of nanometer vanadous oxide needs a kind of novel method that overcomes above drawback, simplifies production technique, reduces production costs.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nano level vanadous oxide.To be raw material with the vannadate prepare vanadous oxide to this method in nearly critical or supercritical medium system, and the whole process reaction time is short, temperature of reaction is low, raw materials used and reagent is cheap, be easy to get, and the vanadous oxide of acquisition is the uniform nano level of size.
The objective of the invention is to realize through following technical scheme:
A kind of preparation method of nano grade vanadium trioxide comprises the steps:
(a) vannadate is joined in the reactor drum, add organic solvent;
(b) air in the reactor drum is got rid of after, to the reactor drum heating, make temperature of reactor reach 100～500 ℃, reaction pressure and reach 0.5～20.0Mpa, and under this state maintenance 0.1～6.0h;
(c) keeping reducing reactor pressure to 0～5.0Mpa under the heating condition, isolate organic solvent, and the condensation and collection distillate;
(d) stop heating, when temperature is reduced to room temperature in the question response device, obtain black nano level vanadous oxide.
The preparation method of described a kind of nano grade vanadium trioxide, the described vannadate of its step (a) comprises one or both mixtures of ammonium meta-vanadate and many (gathering) ammonium vanadate (APV).
The preparation method of described a kind of nano grade vanadium trioxide; The described organic solvent of its step (a) comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sulfur alcohol, propylmercaptan, formic acid, acetate, n-caproic acid, acetone, 2-butanone, pimelinketone, N, one or both in the dinethylformamide or multiple mixed solvent.
The preparation method of described a kind of nano grade vanadium trioxide, the described air eliminating of its step (b) is meant and utilizes vacuum pump that reactor drum is vacuumized, to eliminate the air in the reactor drum; The described temperature of reaction of step (b) is 200～400 ℃; The described reaction times of step (b) is 1.0～6.0h; The described reaction pressure of step (b) is 2.0～15.0Mpa.
The preparation method of described a kind of nano grade vanadium trioxide, the described reduction reactor pressure to 0 of its step (c)～5.0Mpa is meant that the used step-down time is 0.5～3.0h.
The preparation method of described a kind of nano grade vanadium trioxide, the described reactor temperature of its step (d) is reduced to room temperature and is referred to through naturally cooling or force the refrigerative method that reactor drum is lowered the temperature.
Obtain the sphere that is shaped as of black nano level vanadous oxide powder, the about 60nm of particle diameter.
The present invention vacuumizes reactor drum through vacuum pump, to eliminate the air in the reactor drum.In the present invention, used temperature of reaction is to be advisable between 200～400 ℃; Pressure-controlling is better between 2.0～15.0Mpa; Reaction times is better between 1.0～6.0 hours.
The pressure terminal point of step-down process reactor of the present invention is 0～5.0Mpa, and the step-down time was controlled at 0.5～3.0 hour.
Reactor temperature of the present invention is reduced to room temperature can or force the type of cooling to be carried out through naturally cooling.
The used raw material of the present invention is easy to get (ammonium meta-vanadate and many (gathering) ammonium vanadate), and cost is low.
The temperature low (100 ℃～500 ℃) that the present invention is used has reduced energy consumption.
The present invention is under temperature of reaction and pressure condition; Solvent for use has reached nearly critical (Near-Critical) or overcritical (Super-Critical) state; Make reduction reaction in nearly critical or postcritical medium, carry out; Improved speed of reaction widely, also made product particulate homogeneous nucleation, the nano level V2O3 narrow diameter distribution of preparing, surperficial rounding.
Advantage of the present invention and effect are:
The present invention prepares vanadous oxide in closely critical or supercritical medium system, the reaction times is short, temperature of reaction is low; Whole process operation is simple; Raw materials used and reagent is cheap, be easy to get; The vanadous oxide that obtains is the uniform nano level of size.
Description of drawings
The nano level V that Fig. 1 makes for ammonium meta-vanadate and many (gathering) ammonium vanadate raw material
2O
3XRD contrast spectrogram;
The nano level V that Fig. 2 makes for many (gathering) ammonium vanadate
2O
3ESEM (SEM) photo.
Annotate: Fig. 1 of the present invention, Fig. 2 are the analysis synoptic diagram or the photo of product state, figure Chinese words or the unintelligible understanding that does not influence technical scheme of the present invention of shade.
Embodiment
Below through instance the present invention is done further elaboration.
At first the powder vannadate is joined in the voltage-resistant reactor, in reactor drum, add organic solvent then, reactor drum is heated; Make temperature of reactor reach 100～500 ℃, pressure and reach 0.5～20.0Mpa, and under this condition, continue 0.1～6.0h, keeping under 100～500 ℃ the state then; In 0.5～3.0h, releasing reactor pressure to 0～5.0Mpa, then; During with reactor cooling to room temperature, just can obtain the vanadous oxide of black nano level.
Wherein, vannadate adopts a kind of or mixture in ammonium meta-vanadate, many (gathering) ammonium vanadate; Organic solvent adopts methyl alcohol, ethanol, methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sulfur alcohol, propylmercaptan, organic acid formic acid, acetate, n-caproic acid, acetone, 2-butanone, pimelinketone, N, one or both in the dinethylformamide or multiple mixed solvent; Temperature of reaction is controlled at 200～400 ℃; Reaction pressure is controlled at 2.0～15.0Mpa; Reaction times is controlled at 0.1～6.0h; The time of releasing reactor internal pressure is controlled at 0.5～3.0h; The cooling of reactor drum is adopted the nature cooling or is forced the refrigerative method.It below is embodiment.
Embodiment 1:
Take by weighing the 10.0g ammonium meta-vanadate and place 1L volumetrical reactor drum, add the 345mL absolute ethyl alcohol, after the reactor drum sealing, vacuumize with water pump; Heating at 250 ℃, is reacted 2.5h under the condition of 7.1Mpa, under the situation that keeps temperature; With the slow pressure release of reactor drum, collect distillate, after two hours, pressure becomes 0.7Mpa; Temperature is 260 ℃, and powered-down lets the reactor drum naturally cooling.Obtaining the 6.0g product is black powder.
Embodiment 2:
20.0g many (gathering) ammonium vanadate is placed reactor drum, and reactor volume is 1L, adds the mixed solvent (volume ratio is 2: 1) of 350mL ethanol and Virahol, after the reactor drum sealing; Be heated to 240 ℃, reactor pressure is 5.9Mpa, and under this condition, reacts 0.2h; Under the situation of 240 ℃ of maintenances, behind reactor drum pressure release 1.6h, pressure becomes 0.4Mpa; Distillate is collected in pressure release simultaneously, stops heating, lets reactor drum naturally cool to room temperature.In reactor drum, obtain the vanadous oxide black powder, quality is 11.4g.
Embodiment 3:
20.0g many (gathering) ammonium vanadate is placed reactor drum, add 340mL ethanol, after the reactor drum sealing; Be heated to 248 ℃, reactor pressure is 7.0Mpa, and under this condition, reacts 0.5h; Under the situation of 248 ℃ of maintenances, behind reactor drum pressure release 0.5h, pressure becomes 3.0Mpa; Distillate is collected in pressure release simultaneously, stops heating, lets reactor drum naturally cool to room temperature.In reactor drum, obtain the vanadous oxide black powder, quality is 10.6g.
Embodiment 4:
54.0g many (gathering) ammonium vanadate places reactor drum, the adding solvent is the mixed solvent of acetate, ethanol, acetone, and add-on is respectively 100,130,120mL, after mixing; Reactor drum is heated to 258 ℃, and pressure is 5.2Mpa, and under this condition, reacts 4.6h; After reaction finishes,, collect distillate with the slow pressure release 2.4h of reactor drum; When reactor pressure became 4.5Mpa, powered-down cooled off reactor drum with water of condensation fast.Obtaining the 31.6g product is black powder.
Embodiment 5:
Take by weighing the mixture of 36.7g many (gathering) ammonium vanadate and ammonium meta-vanadate, be scattered in the 343mL acetone, join in the 1L volumetrical reactor drum; Heating at 230 ℃, is reacted 0.3h under the condition of 4.5Mpa; Under the situation that keeps temperature, the solvent in the reactor drum is slowly released, and collect distillate simultaneously; When reactor pressure became 1.4Mpa, powered-down let the reactor drum naturally cooling.Collection obtains the 20.0g product.
Embodiment 6:
Take by weighing the mixture of 30.0g many (gathering) ammonium vanadate and ammonium meta-vanadate, be scattered in the 348mL acetate, join in the 1L volumetrical reactor drum; Be heated to 300 ℃, react 5.0h under the condition of 5.5Mpa, under the situation that keeps temperature; Solvent in the reactor drum is slowly released, and collect distillate simultaneously, when reactor pressure becomes 2.5Mpa; Powered-down lets the reactor drum naturally cooling.Collection obtains the 17.4g product.
Embodiment 7:
The 41.8g ammonium meta-vanadate is placed reactor drum, to wherein adding the 358mL sulfur alcohol, with reactor drum with water pump vacuumize eliminate air after; Begin heating, it is 1.7h that temperature of reactor and pressure are respectively 220 ℃, 5.4Mpa reaction times, under the situation of maintenance temperature; In 2.4h, leak out solvent, collect distillate, temperature rises to 228 ℃; Powered-down forces to make reactor cooling with water of condensation.In reactor drum, collect V
2O
3
Embodiment 8:
Take by weighing 35.0g many (gathering) ammonium vanadate and 17.4g ammonium meta-vanadate respectively, both are scattered in 250mL acetone and 100mL N, in the mixed solvent of dinethylformamide, above-mentioned aaerosol solution is placed in the reactor drum; Be heated to 280 ℃, react 3.0h under the condition of 5.6Mpa, under the situation that keeps temperature, the slow pressure release of reactor drum; Collect distillate, after two hours, pressure becomes 0; Temperature is 290 ℃, and powered-down lets the reactor drum naturally cooling.Obtaining the 30.3g product is black powder.
Embodiment 9:
Take by weighing the 38.5g ammonium meta-vanadate and place 1L volumetrical reactor drum, add the mixed solvent (volume ratio is 1: 1) of 340mL propyl carbinol and 2-butanone, after the reactor drum sealing, be heated to 270 ℃; Pressure is 4.3Mpa, and under this condition, reacts 0.1h, under the situation that keeps temperature; With the slow pressure release of reactor drum, collect distillate, behind the 1.0h; Pressure becomes 0, and powered-down cools off reactor drum with water of condensation fast.Obtain product 22.6g.
Claims (3)
1. the preparation method of a nano grade vanadium trioxide is characterized in that comprising the steps:
(a) vannadate is joined in the reactor drum, add organic solvent;
(b) air in the reactor drum is got rid of after, to the reactor drum heating, make temperature of reactor reach 100～500 ℃, reaction pressure and reach 0.5～20.0MPa, and under this state maintenance 0.1～6.0h;
(c) keeping reducing reactor pressure to 0～5.0MPa under the heating condition, isolate organic solvent, and the condensation and collection distillate;
(d) stop heating, when temperature is reduced to room temperature in the question response device, obtain black nano level vanadous oxide;
The described vannadate of step (a) adopts one or both mixtures of ammonium meta-vanadate and poly ammonium vanadate; The described organic solvent of step (a) adopts methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sulfur alcohol, propylmercaptan, formic acid, acetate, n-caproic acid, acetone, 2-butanone, pimelinketone, N, one or both in the dinethylformamide or multiple mixed solvent; The described reduction reactor pressure to 0 of step (c)～5.0MPa is meant that the used step-down time is 0.5～3.0h.
2. the preparation method of a kind of nano grade vanadium trioxide according to claim 1 is characterized in that the described air of step (b) is got rid of to be meant and to utilize vacuum pump that reactor drum is vacuumized, to eliminate the air in the reactor drum; The described temperature of reaction of step (b) is 200～400 ℃; The described reaction times of step (b) is 1.0～6.0h; The described reaction pressure of step (b) is 2.0～15.0MPa.
3. the preparation method of a kind of nano grade vanadium trioxide according to claim 1 is characterized in that the described reactor temperature of step (d) reduces to room temperature and refer to through naturally cooling or force the refrigerative method that reactor drum is lowered the temperature.
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|---|---|---|---|
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| CN102133646B (en) * | 2011-03-23 | 2012-11-28 | 沈阳化工大学 | Preparation method of dispersed iron nanoparticles |
| CN102560635A (en) * | 2012-03-21 | 2012-07-11 | 电子科技大学 | Preparation method of vanadium trioxide film |
| CN103633309A (en) * | 2013-12-13 | 2014-03-12 | 黑龙江大学 | Preparation method of core-shell structure vanadium trioxide microspheres |
| CN105923654B (en) * | 2016-04-27 | 2017-09-01 | 东北大学 | A kind of vanadium trioxide micro-nano particle and preparation method thereof |
| JP7001052B2 (en) * | 2016-05-30 | 2022-01-19 | コニカミノルタ株式会社 | Method for Producing Vanadium Dioxide-Containing Particles |
| CN108314083B (en) * | 2018-04-04 | 2020-11-03 | 河钢股份有限公司承德分公司 | Method for preparing vanadium trioxide from vanadium-containing solution |
| CN110021746A (en) * | 2019-04-24 | 2019-07-16 | 青海民族大学 | A kind of preparation method and lithium ion battery of carbon coating vanadium trioxide |
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