CN106348343B - The preparation method of High-density Niobium Oxide - Google Patents
The preparation method of High-density Niobium Oxide Download PDFInfo
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- CN106348343B CN106348343B CN201610692339.1A CN201610692339A CN106348343B CN 106348343 B CN106348343 B CN 106348343B CN 201610692339 A CN201610692339 A CN 201610692339A CN 106348343 B CN106348343 B CN 106348343B
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- niobium oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of preparation method of High-density Niobium Oxide, passes through fluorine niobic acid (H2NbF7) in solution ammonia and when use secondary neutralization, control ph and control temperature when calcining when ammonification is washed, obtain High-density Niobium Oxide.The invention also discloses the method that niobium oxide is produced with described device.The niobium pentaoxide apparent density of preparation is set to bring up to 1.8g/cm3 by the method for the present invention.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to a kind of preparation side of High-density Niobium Oxide
Method.
Background technology
Niobium is a kind of high-melting-point rare metal, is both special functional material, is excellent structural material again.Niobium and its conjunction
Gold is widely used in the fields such as electronics, metallurgy, machinery, space flight and aviation, chemistry, medical science；As niobium compound single-crystal surface ripple is filtered
Ripple device increases rapidly what the electronic applications such as colour television set, video recorder, mobile communication were applied, and the glass of special optical containing niobium is shining
Camera, video camera and other optical instrument application amounts constantly expand；With the new and high technologies such as infrared, laser and Military Application, family
Electrical appliance produces and electronics industry fast development, the demand of niobium oxide increasingly increase.
High-density Niobium Oxide is in the production of niobium bar, niobium carbide and its alloy because apparent density is greatly same
In the case of Deng mould, fill niobium oxide amount just it is more, substantially increase production efficiency, reduce cost.According to current technique side
Niobium pentaoxide apparent density prepared by method is relatively low, about 1g/cm3.
The content of the invention
In view of above mentioned problem of the prior art, it is an object of the invention to provide a kind of High-density Niobium Oxide
Preparation method.
To achieve the above object, the present invention uses following technical scheme：
1st, the preparation method of High-density Niobium Oxide, comprises the following steps：
1) tantalum niobium concentrate is provided, is ground；
2) add hydrofluoric acid and sulfuric acid is dissolved, generate fluorotantalic acid and fluorine niobic acid；
3) extract and be stripped through sec-octyl alcohol, isolate fluorine niobic acid；
4) ammonia neutralization is passed through for the first time, is neutralized to pH=5-6, controls no white precipitate to produce；
5) it is cooled to 20-40 DEG C；
6) ammonia neutralization is passed through for the second time, is neutralized to pH=9, the neutralization time is 30-150 minutes；
7) circulating filtration is washed to fluorine ion ＜ 1000ppm
8) separation of solid and liquid is carried out with filter press,
9) and then at 200 DEG C of temperature dried.
10) in the 00-900 DEG C of calcining of temperature 7, High-density Niobium Oxide is obtained.
Preferably, the flow that ammonia is passed through in step 4) is 1-15 liters/min.
Preferably, the flow that ammonia is passed through in step 6) is 1-15 liters/min.
Preferably, step 7) carries out circulating filtration washing using ceramic membrane.It is favourable to enter behavior washing using ceramic membrane filter
In production high-density niobium oxide, as shown in figure 1, ceramic membrane filter washing principle is：Under the driving of pressure effect, material liquid exists
Flow at high speed in membrane tube, the clarified permeation liquid containing small molecule component outwards passes through film along direction normal thereto, containing macromolecular components
Muddy concentrate be rejected by so that fluid reach separation, concentration, washing, purifying purpose.Because niobium hydroxide is powder
Material, it is macromolecular components, is rejected by, fluoride etc. is small molecule component, outwards through film, reaches the mesh of filtration washing
's.
The preparation method for the High-density Niobium Oxide stated, it is characterised in that forged in step 10) at 750 DEG C
Burn.
Preferably, the step 5) is cooled to 30 DEG C.
In terms of niobium pentaoxide apparent density, second of neutralization time is longer, and apparent density is bigger.Reach certain time
Change is just not much afterwards, and it is 120 minutes that step 6) the neutralization time, which is preferably,.
Higher from calcining heat in terms of niobium pentaoxide apparent density, apparent density is bigger.But 800 DEG C, 850 DEG C are calcined
It is more or less the same to niobium pentaoxide apparent density, because calciner is with the rotary furnace that nickel chromium is heating element heater, temperature
Too high, the service life of rotary furnace is with regard to short, and general control is used below at 800 DEG C in production, it is preferable that 750 in step 10)
Calcined at DEG C.
According to the present invention, there is following beneficial effect：Make the niobium pentaoxide pine dress of preparation by the method for the present invention
Density brings up to 1.8g/cm3.
Brief description of the drawings
Fig. 1 is the structural representation of ceramic membrane；
Fig. 2 is the schematic diagram of the neutralization reaction device of the present invention；
Fig. 3 is the schematic diagram of the circulation washing device of the present invention.
Embodiment
The main chemical reactions equation that Nb-Ta mineral decomposes is as follows：
Fe(TaO3) 2+16HF=2H2TaF7+FeF2+6H2O
Fe(NbO3) 2+16HF=2H2NbF7+FeF2+6H2O
Fe2O3+ 12HF=2H3FeF6+3H2O
SiO2+ 6HF=H2SiF6+2H2O
H2NbF7+7NH3.H2O=Nb (OH) 5 ↓+7NH4F+2H2O
The present invention will be further described with preferred embodiment below in conjunction with the accompanying drawings.
In this manual, unless otherwise expressly noted, unit ppm refers to " hundred a ten thousandths " represented with mass ratio.
Hydrofluoric acid is added after tantalum niobium concentrate is ground and sulfuric acid is dissolved, and fluorotantalic acid and fluorine niobic acid is generated, through Zhong Xin
Alcohol extracts and back extraction, and it is standby to isolate fluorine niobic acid, and fluorine niobic acid concentration is 105 g/l.
Embodiment 1
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 4 with pump
In reactor 6, ammonia, 1 liter/min of control ammonification flow are added from ammonia inlet pipe 5, while starts agitating device 2, is neutralized to pH=
5, and control no white precipitate to produce (can be observed by observation panel 1).Be cooled to 20 DEG C, then from second of ammonia inlet pipe 5 plus
Enter ammonia, 1 liter/min of control ammonification flow, be neutralized to pH=9, the time is 120 minutes.Waste gas is discharged from Waste gas outlet 3.So
The feed liquid become reconciled afterwards from floss hole 7 by is put into the circulation barrel 8 of circulation washing device 14 (inside setting ceramic membrane) as shown in Figure 3
In, stirring 9 is started, feed liquid is squeezed into ceramic membrane charging aperture 11 with feed liquid booster pump 10, under the driving of pressure effect, fluoride
Discharged Deng for the outside permeation ceramic membrane of small molecule component from outlet 12, niobium hydroxide is that macromolecular components are rejected by.Pass through
Discharging opening 13 enters in circulation barrel 8, and the ammoniacal liquor for adding pH=9 by ammonification water pipe 15 protects circulation barrel 8 into circulation barrel 8
It is constant to hold liquid level, carries out circulating filtration washing, washs to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid
Material niobium hydroxide is dried at 200 DEG C of temperature, then in 700 DEG C of calcinings of temperature, obtains the oxidation of high apparent density five two
Niobium.Analysis niobium oxide apparent density, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Embodiment 2
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 4 with pump
In reactor 6, ammonia, 15 liters/min of control ammonification flow are added from ammonia inlet pipe 5, while starts stirring, is neutralized to pH=6, and
No white precipitate is controlled to produce.It is cooled to 40 DEG C.Again from second of ammonia inlet pipe 5 addition ammonia, 15 liters of control ammonification flow/
Point, pH=9 is neutralized to, the time is 150 minutes.
Then the feed liquid become reconciled from floss hole 7 by is put into the circulation barrel 8 of device as shown in Figure 3, starts agitating paddle
9, feed liquid is squeezed into ceramic membrane charging aperture 11 by feed liquid booster pump 10, and under the driving of pressure effect, fluoride etc. is small molecule group
Divide and outwards discharged through film from outlet 12, niobium hydroxide is that macromolecular components are rejected by.Entered by discharging opening 13 and circulated
In bucket 8, and the ammoniacal liquor for adding pH=9 by ammonification water pipe 15 makes circulation barrel 8 keep liquid level constant, followed into circulation barrel 8
Ring filtration washing, wash to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid matter niobium hydroxide is in temperature
Dried at 200 DEG C of degree, then in 900 DEG C of calcinings of temperature, obtain High-density Niobium Oxide.Analyze niobium oxide pine dress
Density, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Embodiment 3
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 3 with pump
In reactor 6, ammonia, 8 liters/min of control ammonification flow are added from ammonia inlet pipe 2, while starts stirring, is neutralized to pH=5.5,
And no white precipitate is controlled to produce.It is cooled to 30 DEG C.Again from second of the addition ammonia of ammonia inlet pipe 2, control ammonification flow 8
Liter/min, pH=9 is neutralized to, the time is 90 minutes.Then the feed liquid become reconciled from floss hole 7 by is put into ceramic membrane equipment (as schemed
3) in circulation barrel 8, agitating paddle 9 is started, feed liquid is squeezed into what ceramic membrane charging aperture 11 acted in pressure with feed liquid booster pump 10
Under driving, fluoride etc. is that small molecule component is outwards discharged through film from outlet 12, and niobium hydroxide is macromolecular components envelope
Retain by discharging opening 13 to enter in circulation barrel 8, ammoniacal liquor to the circulation barrel 8 for adding pH=9 keeps liquid level constant, is circulated
Filtration washing, wash to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid matter niobium hydroxide is in temperature
Dried at 200 DEG C, then in 750 DEG C of calcinings of temperature, obtain High-density Niobium Oxide.Analysis niobium oxide pine fills close
Degree, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Embodiment 4
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 3 with pump
In reactor 6, ammonia, 9 liters/min of control ammonification flow are added from ammonia inlet pipe 2, while starts stirring, is neutralized to pH=5.2,
And no white precipitate is controlled to produce.It is cooled to 30 DEG C.Again from second of the addition ammonia of ammonia inlet pipe 2, control ammonification flow 10
Liter/min, pH=9 is neutralized to, the time is 100 minutes.Then the feed liquid become reconciled from floss hole 7 by is put into ceramic membrane equipment (such as
In circulation barrel 8 Fig. 3), agitating paddle 9 is started, feed liquid is squeezed into ceramic membrane charging aperture 11 with feed liquid booster pump 10 acts in pressure
Driving under, fluoride etc. be small molecule component outwards discharged through film from outlet 12, niobium hydroxide is macromolecular components quilt
Film retains.Entered by discharging opening 13 in circulation barrel 8, and liquid is kept by adding hot pure water or circulation washings, circulation barrel 8
Invariant position, circulating filtration washing is carried out, is washed to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid matter
Niobium hydroxide is dried at 200 DEG C of temperature, then in 7 50 DEG C of calcinings of temperature, obtains High-density Niobium Oxide.
Analysis niobium oxide apparent density, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Embodiment 5
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 3 with pump
In reactor 6, ammonia, 11 liters/min of control ammonification flow are added from ammonia inlet pipe 2, while starts stirring, is neutralized to pH=5.6,
And no white precipitate is controlled to produce.It is cooled to 35 DEG C.Again from second of the addition ammonia of ammonia inlet pipe 2, control ammonification flow 12
Liter/min, pH=9 is neutralized to, the time is 120 minutes.Then the feed liquid become reconciled from floss hole 7 by is put into the circulation of (such as Fig. 3)
In bucket 8, stirring is started, feed liquid is squeezed into ceramic membrane charging aperture 11 under the driving that pressure acts on feed liquid booster pump 10, be fluorinated
Thing etc. is that small molecule component is outwards discharged through film from outlet 12, and niobium hydroxide is that macromolecular components are rejected by.By going out
Material mouth 13 enters in circulation barrel 8, and by adding hot pure water or circulation washings, circulation barrel 8 keeps liquid level constant, followed
Ring filtration washing, wash to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid matter niobium hydroxide is in temperature
Dried at 200 DEG C of degree, then in 7 50 DEG C of calcinings of temperature, obtain High-density Niobium Oxide.Analyze niobium oxide pine
Dress density, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Embodiment 6
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 3 with pump
In reactor 6, ammonia, 8 liters/min of control ammonification flow are added from ammonia inlet pipe 2, while starts stirring, is neutralized to pH=5.8,
And no white precipitate is controlled to produce.It is cooled to 30 DEG C.Again from second of the addition ammonia of ammonia inlet pipe 2, control ammonification flow 10
Liter/min, pH=9 is neutralized to, the time is 120 minutes.Then the feed liquid become reconciled from floss hole 7 by is put into ceramic membrane equipment (such as
In circulation barrel 8 Fig. 3), agitating paddle 9 is started, feed liquid is squeezed into ceramic membrane charging aperture 11 with feed liquid booster pump 10 acts in pressure
Driving under, fluoride etc. be small molecule component outwards discharged through film from outlet 12, niobium hydroxide is macromolecular components quilt
Film retains.Entered by discharging opening 13 in circulation barrel 8, and liquid is kept by adding hot pure water or circulation washings, circulation barrel 8
Invariant position, circulating filtration washing is carried out, is washed to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid matter
Niobium hydroxide is dried at 200 DEG C of temperature, then in 800 DEG C of calcinings of temperature, obtains High-density Niobium Oxide.Point
Analysis niobium oxide apparent density, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Embodiment 7
Using device as shown in Figure 2,2000 liters of fluorine niobic acid (H2NbF7) solution are squeezed into neutralization by charging aperture 3 with pump
In reactor 6, ammonia, 10 liters/min of control ammonification flow are added from ammonia inlet pipe 2, while starts stirring, is neutralized to pH=5.6,
And no white precipitate is controlled to produce.It is cooled to 30 DEG C.Again from second of the addition ammonia of ammonia inlet pipe 2, control ammonification flow 12
Liter/min, pH=9 is neutralized to, the time is 110 minutes.Then the feed liquid become reconciled from floss hole 7 by is put into the circulation of (such as Fig. 3)
In bucket 8, agitating paddle 9 is started, feed liquid is squeezed into ceramic membrane charging aperture 11 under the driving that pressure acts on feed liquid booster pump 10, fluorine
Compound etc. is that small molecule component is outwards discharged through film from outlet 12, and niobium hydroxide is that macromolecular components are rejected by.Pass through
Discharging opening 13 enters in circulation barrel 8, and heat is pure or circulation washings, circulation barrel 8 keep liquid level constant, circulated by adding
Filtration washing, wash to fluorine ion ＜ 1000ppm.It is put into filter press and carries out separation of solid and liquid, solid matter niobium hydroxide is in temperature
Dried at 200 DEG C, then in 700 DEG C of calcinings of temperature, obtain High-density Niobium Oxide.Analysis niobium oxide pine fills close
Degree, scaling loss, tantalum, iron, tungsten, nickel, chromium, silicon, the content data of fluorine are listed in table 1.
Table 1
From the results shown in Table 1, the niobium oxide produced according to the inventive method has high apparent density, can be used for
Produce niobium bar, niobium carbide and its alloy.
Claims (6)
1. the preparation method of High-density Niobium Oxide, comprises the following steps：
1) tantalum niobium concentrate is provided, is ground；
2) add hydrofluoric acid and sulfuric acid is dissolved, generate fluorotantalic acid and fluorine niobic acid；
3) extract and be stripped through sec-octyl alcohol, isolate fluorine niobic acid；
4) ammonia neutralization is passed through for the first time, is neutralized to pH=5-6, controls no white precipitate to produce；
5) it is cooled to 20-40 DEG C；
6) ammonia neutralization is passed through for the second time, is neutralized to pH=9, the neutralization time is 30-150 minutes；
7) circulating filtration is washed to fluorine ion ＜ 1000ppm
8) separation of solid and liquid is carried out with filter press,
9) and then at 200 DEG C of temperature dried；
10) in 700-900 DEG C of calcining of temperature, High-density Niobium Oxide is obtained；
Wherein, the flow that ammonia is passed through in step 4) is 1-15 liters/min；
Wherein, the flow that ammonia is passed through in step 6) is 1-15 liters/min.
2. the preparation method of High-density Niobium Oxide as claimed in claim 1, it is characterised in that step 7) uses pottery
Porcelain film carries out circulating filtration washing.
3. the preparation method of High-density Niobium Oxide as claimed in claim 1, it is characterised in that the step 5) is cold
But to 30 DEG C.
4. the preparation method of High-density Niobium Oxide as claimed in claim 1, it is characterised in that in the step 6)
It it is 120 minutes with the time.
5. the preparation method of High-density Niobium Oxide as claimed in claim 1, it is characterised in that in the step 7),
Add pH=9 ammoniacal liquor.
6. the preparation method of High-density Niobium Oxide as claimed in claim 1, it is characterised in that in step 10)
Calcined at 750 DEG C.
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| CN109292822B (en) * | 2018-12-17 | 2021-01-26 | 株洲硬质合金集团有限公司 | Preparation method of niobium pentoxide with high apparent density |
| CN114180626B (en) * | 2021-12-29 | 2022-10-18 | 江门富祥电子材料有限公司 | Preparation method of niobium pentoxide with low tap density |
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| CN102285687A (en) * | 2011-06-10 | 2011-12-21 | 江门富祥电子材料有限公司 | Method and device for preparing superfine niobium oxide |
| CN104310478B (en) * | 2014-10-10 | 2016-12-07 | 九江有色金属冶炼有限公司 | The preparation method of a kind of big tap density niobium oxide and the big tap density niobium oxide of preparation thereof |
| CN104445406B (en) * | 2014-11-19 | 2017-02-08 | 九江有色金属冶炼有限公司 | Preparation method of ultrahigh-purity niobium oxide and prepared ultrahigh-purity niobium oxide |
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