CN104445406B - Preparation method of ultrahigh-purity niobium oxide and prepared ultrahigh-purity niobium oxide - Google Patents
Preparation method of ultrahigh-purity niobium oxide and prepared ultrahigh-purity niobium oxide Download PDFInfo
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Abstract
The invention discloses a preparation method of ultrahigh-purity niobium oxide. The preparation method comprises the steps of acidity regulation, extraction separation, neutralization, precipitation, drying and calcining by taking a fluoroniobic acid solution as a raw material. In the extraction separation step, sec-octyl alcohol is used for extracting the regulated niflumic acid material liquid to obtain an organic phase; subsequently the organic phase is pickled by a pickling agent; finally the pickled organic phase is re-extracted by an anti-niobium agent to obtain the ultrahigh-purity niobium oxide. The invention also provides the ultrahigh-purity niobium oxide prepared by the method; the percentage composition of Nb2O5 is larger than or equal to 99.995%; the content of each impurity satisfies the regulations of the standard YS/T548-2007 on product grades F Nb2O5-048 and F Nb2O5-045.
Description
Technical field
The invention belongs to metallochemistry field of smelting is and in particular to a kind of preparation method of ultra-high purity niobium oxide, and
The ultra-high purity niobium oxide that the method prepares.
Background technology
High purity niobium oxide（99.99%）, it is important source material and the functional material of hi tech and new material industry, be used for preparing lithium
Salt crystal (lithium niobate) and chip, in sound table device, precision optics glass, optical fiber communication, sensing technology, particularly military thunder
Reach, are used widely in electronic countermeasure, the sophisticated technology field such as navigation.In existing professional standard YS/T548-2007, high-purity
The product grade of degree niobium oxide is FNb2O5- 04, wherein F represents powder, Nb2O5Represent niobium pentaoxide（Niobium oxide）Molecule
Formula, the purity of 04 expression product is 99.99%.
In prior art, the preparation of described high-purity mangesium oxide niobium, generally with ferro-niobium as raw material, using sec-octyl alcohol-HF-H2SO4
Extraction separation method.As publication number CN102424420A（April 2 2012 publication date）Chinese invention patent application " with niobium
The method that iron prepares niobium pentaoxide for raw material ", discloses a kind of method preparing niobium pentaoxide for raw material with ferro-niobium, including
Dissolution of raw material, extraction, neutralization, calcining, carry out by following technique：1）Dissolution of raw material, with inorganic acid, hydrofluoric acid, dissolves ferro-niobium
And control its acidity, obtain niobium and adjust liquid；2）Extraction：It is organic phase with octanol as extractant, obtain pickling organic phase；3）Back extraction：With
Pure water is made anti-niobium agent and is carried out back extraction to pickling organic phase, obtains niobium liquid；4）Precipitation hydrogen manufacturing niobium oxide and calcining oxygenerating niobium product：
Back extraction gained niobium liquid is precipitated, washed and is dried, and obtains niobium hydroxide；Niobium hydroxide is calcined, obtains final product niobium oxide product.Warp
Test finds, the product purity that the method prepares is 99.99%, meets overpassed standard GB/T/T10578-2003
The middle trade mark is FNb2O5- 04 product quality requires.
But, with the development of hi tech and new material industry, large scale lithium salts in high frequency sound table device for the application and preparation
Crystal (lithium niobate) and chip necessarily require the purity of niobium oxide more than 99.995%.Obviously above-mentioned high purity niobium oxide can not
Fully meet the demand in market.
Content of the invention
For above-mentioned technical problem, the present invention provides a kind of preparation method of ultra-high purity niobium oxide.The method is existing
Sec-octyl alcohol-the HF-H of technology2SO4On the basis of extract and separate system, modified technique flow process, optimizing technology parameters, make niobium oxide
Purity reaches more than 99.995%.
In order to realize foregoing invention purpose, present invention employs following technical scheme：
A kind of preparation method of ultra-high purity niobium oxide, with fluorine niobic acid solution as raw material, including acidity allotment, extraction point
From, neutralization precipitation, drying and calcining.
Preferably, the preparation method of described ultra-high purity niobium oxide, after neutralization precipitation step, also includes adjusting eccysis fluorine.
Preferably, described fluorine niobic acid solution, with (Ta+Nb)2O5Calculate, oxide aggregate is 110 ~ 180g/L.
Preferably, described acidity adaptation step, adds dense hydrofluoric acid and the concentrated sulfuric acid including in described fluorine niobic acid solution, makes
In feed liquid after allotment, with (Ta+Nb)2O5Calculate, oxide aggregate be not less than 95g/L, hydrofluoric acid molar concentration=7.2 ±
0.1moL/L, sulfuric acid molar concentration=3.6 ± 0.05moL/L.
Preferably, allotment is 36mol/L with the molar concentration of dense hydrofluoric acid, and the molar concentration of the allotment concentrated sulfuric acid is
18mol/L.
Preferably, described extract and separate step, including：Feed liquid after sec-octyl alcohol extraction allotment, obtains organic phase, then with sour
Organic phase described in lotion pickling, finally with the organic phase after pickling described in anti-niobium agent back extraction, obtains ultra-high purity fluorine niobic acid material
Liquid；Wherein, described allotment after feed liquid, sec-octyl alcohol, mordant, anti-niobium agent volume ratio be 1 ~ 1.2: 1: 0.3 ~ 0.5: 0.8 ~
1.2, preferably 1:1:0.3:1.
Preferably, described sec-octyl alcohol, the percentage by weight of ketone is not more than 15%, pH=7.0.
Preferably, the sulfuric acid for molar concentration=3.2 ~ 3.5 mol/L for the described mordant, more preferably molar concentration=
The sulfuric acid of 3.5mol/L.
Preferably, described anti-niobium agent is ultra-pure water, wherein Si≤0.1ppm, Fe, Al, K, Na, Ca, Mg all≤0.01ppm.
Preferably, described extraction step is carried out in extraction tank, enters groove flow and is respectively：Feed liquid after described allotment
1000mL/min, described sec-octyl alcohol 1000mL/min, described mordant 300mL/min, described anti-niobium agent 1000mL/min.
It is also preferred that described extraction step is carried out in extraction tank, the extraction tank series of sec-octyl alcohol extraction is 10 grades, pickling
The extraction tank series of agent pickling is 10 grades, and the extraction tank series of anti-niobium agent back extraction is 10 grades.
After extract and separate step terminates, in described ultra-high purity fluorine niobic acid feed liquid, with (Ta+Nb)2O5Calculate, oxide is total
Amount >=90g/L.
Preferably, described neutralization precipitation step, including adding liquefied ammonia to described ultra-high purity fluorine niobic acid feed liquid, to pH=9
~ 10, obtain ultra-high purity niobium hydroxide slurry.
Preferably, described tune eccysis fluorine step, is transferred to filter press mistake including by described ultra-high purity niobium hydroxide slurry
Filter, filter cake carries out adjusting eccysis fluorine, Oil repellent≤0.01g/L to slip with 60 ~ 70 DEG C of hot pure waters containing ammonia 5 ~ 8%, filters, obtains
To ultra-high purity niobium hydroxide filter cake.
Preferably, described baking step, 130 ~ 180 DEG C of drying temperature, 5 ~ 8 hours time.
Preferably, described calcining step, calcining low-temperature space temperature control at 350 ~ 450 DEG C, calcining heat is controlled to 850 ~
1050 DEG C, the time is 10 ~ 15 hours.
It is also preferred that described calcining step is carried out in continuous boat pushing stove, the fltting speed of push-plate is 12 ~ 15 minutes/pushes away
Disk.
Preferably, the preparation method of ultra-high purity niobium oxide of the present invention, after calcining step, also includes screening step
Suddenly, concrete operations are：The ultra-high purity niobium oxide powder obtaining through calcining step passes through 60 mesh sieves, extracting screen underflow, obtains final product.
As one kind preferred embodiment, the present invention provides a kind of preparation method of ultra-high purity niobium oxide, including acid
Spend allotment, extract and separate, neutralization precipitation, adjust eccysis fluorine, drying and calcining, specific embodiment is：
I. acidity allotment
Described acidity allotment is carried out in acid adjustment groove；
The fluorine niobic acid raw material that oxide aggregate is 110 ~ 180g/L adds acid adjustment groove；Molar concentration is added in acid adjustment groove
The dense hydrofluoric acid of=36moL/L and the concentrated sulfuric acid of molar concentration=18moL/L, make in the feed liquid after allotment, oxide aggregate is with (Ta
+Nb)2O5Calculate and be not less than 95g/L, hydrofluoric acid molar concentration=7.2 ± 0.1moL/L, sulfuric acid molar concentration=3.6 ± 0.05moL/
L；Start stirring 30 ~ 60min, the feed liquid after being allocated；
II. extract and separate
Described extract and separate step is carried out in extraction tank；Start extraction tank, the feed liquid after the allotment that rate-determining steps I obtains
Entering groove flow is 1000mL/min, and the groove flow that enters of sec-octyl alcohol is 1000mL/min, and the groove flow that enters of mordant is 300mL/
Min, the groove flow that enters of anti-niobium agent is 1000mL/min；First with the feed liquid after sec-octyl alcohol extraction allotment, obtain organic phase, then with sour
Organic phase described in lotion pickling, finally with the organic phase after pickling described in anti-niobium agent back extraction, obtains ultra-high purity fluorine niobic acid material
Liquid, oxide aggregate is with (Ta+Nb)2O5Calculating >=90g/L；The extraction tank series of described sec-octyl alcohol extraction is 10 grades, described pickling
The extraction tank series of agent pickling is 10 grades, and the extraction tank series of described anti-niobium agent back extraction is 10 grades；
Wherein, sec-octyl alcohol, the percentage by weight of ketone is not more than 15%, pH=7.0；Mordant is molar concentration=3.2 ~ 3.5
The sulfuric acid of mol/L；Anti- niobium agent is ultra-pure water, wherein Si≤0.1ppm, Fe, Al, K, Na, Ca, Mg all≤0.01ppm；
III. neutralization precipitation
Described neutralization precipitation step is carried out in neutralization chamber；
The ultra-high purity fluorine niobic acid feed liquid that step II is obtained proceeds to neutralization chamber, slowly opens ammonia valve and adds liquefied ammonia, neutralization
It is precipitated to pH=9 ~ 10, obtain ultra-high purity niobium hydroxide slip；
IV. adjust eccysis fluorine
Described tune eccysis fluorine step is carried out in filter press；
Ultra-pure niobium hydroxide slip that step III is obtained proceeds to filter press, adds 60 ~ 70 DEG C to contain the pure of ammonia 5 ~ 8%
Water, adjusts and is washed till Oil repellent≤0.01g/L in slip, press filtration obtains ultra-pure niobium hydroxide filter cake；
V. dry
Described baking step is carried out in an oven；
Ultra-pure niobium hydroxide filter cake that step IV is obtained is contained in charging tray, loads baking oven, heats 5 ~ 8 at 130 ~ 180 DEG C
Hour, dry and obtain ultra-high purity niobium hydroxide powder；
VI. calcine
Described calcining step is carried out in pushing away boat stove；
The ultra-high purity niobium hydroxide powder that step V is obtained goes to and pushes away boat stove, and the fltting speed of push-plate is 12 ~ 15 points
Clock/push-plate, calcining low-temperature space temperature control is 350 ~ 450 DEG C, and calcining heat is controlled to 850 DEG C ~ 1050 DEG C, and calcination time is 10
~ 15 hours, calcining obtained ultra-high purity niobium oxide powder.
VII. sieve
The ultra-high purity niobium oxide powder obtaining through calcining step passes through 60 mesh sieves, extracting screen underflow, obtains final product.
The present invention also provides a kind of ultra-high purity niobium oxide, is obtained by above-mentioned preparation method, Nb2O5Percentage composition >=
99.995%, every impurity content meets in standard YS/T548-2007 to product grade F Nb2O5- 048 and F Nb2O5- 045
Regulation.
Preparation method of the present invention, technology is stable, easy to operate, and existing production equipment need not be transformed.
The containing of the ultra-high purity niobium oxide product preparing, tantalum niobium good separating effect, either principal component content, or every impurity
Amount, has all reached product grade F Nb in professional standard YS/T548-20072O5- 048 and F Nb2O5- 045 regulation.Product carries
Crystal-pulling, monocrystalline outward appearance is transparent colourless, and polarization is completely.Obtain ultra-high purity niobium oxide product using preparation method of the present invention,
Tantalum niobium separating effect and part of impurity elements are better than same kind of products at abroad, disclosure satisfy that domestic and international market optical grade crystal industry
And its needs of deep processing.
Specific embodiment
Below by specific embodiment, the present invention is elaborated.It will be appreciated by those skilled in the art that these enforcements
Example is merely to illustrate the present invention, and it limits the scope of the present invention never in any form.
Experimental technique in following embodiments, if no special instructions, is conventional method.Used each in following embodiments
Plant fibrous material, if no special instructions, be commercially available purchase product.
Embodiment 1The preparation of ultra-high purity niobium oxide
1st, acidity allotment：
（1）Fluorine niobic acid raw material 850L, after measured, total oxide concentration is with (Ta+Nb)2O5It is calculated as 155g/L, hydrofluoric acid mole
Concentration is 2.8moL/L, and sulfuric acid molar concentration is 1.3moL/L, puts in acid adjustment groove；
（2）By calculating, chemistry pure dense hydrofluoric acid 138.78L, chemical pure concentrated sulfuric acid 146.72L need to be added；
（3）The dense hydrofluoric acid calculating and the concentrated sulfuric acid are separately added in acid adjustment groove, start stirring 30min, after allotment
Fluorine niobic acid feed liquid cumulative volume is 1135.50L, and total oxide concentration is with (Ta+Nb)2O5It is calculated as 116.02g/L, hydrofluoric acid mole is dense
Spend for 7.2moL/L, sulfuric acid molar concentration is 3.6moL/L.
2nd, extract and separate：
（1）Fluorine niobic acid feed liquid after allotment proceeds in extraction tank；Extraction and separation technology condition is：
Extraction series：10 grades of extraction section, washes miscellaneous section 10 grades, puies forward 10 grades of tantalum section, 10 grades of anti-niobium section；
Stream compares parameter：Fluorine niobic acid feed liquid after allotment: sec-octyl alcohol: mordant: anti-niobium agent=1: 1: 0.3: 1；
Wherein, sec-octyl alcohol：Purity 85%, containing ketone≤15%, pH=7.0；
Feed liquid：(Ta+Nb)2O5=116.02g/L, acidity HF=7.2moL/L, H2SO4=3.6moL/L；
Mordant：H2SO4, molar concentration=3.5moL/L；
Anti- niobium agent：Ultra-pure water, wherein Si≤0.1ppm, Fe, Al, K, Na, Ca, Mg all≤0.01ppm.
（3）Fluting produces：
Start extraction tank, according to stream ratio parameter, controlling the fluorine niobic acid feed liquid after allotment to enter extraction tank flow is 1000mL/
Min, sec-octyl alcohol is 1000mL/min, and mordant is 300mL/min, and anti-niobium agent is 1000mL/min；First extracted with sec-octyl alcohol and adjust
Feed liquid after joining, obtains organic phase, then with organic phase described in mordant pickling, finally with after pickling described in anti-niobium agent back extraction
Organic phase, produces ultra-high purity fluorine niobic acid feed liquid, oxide aggregate is with Nb2O5Meter=131.09kg.
3rd, neutralization precipitation：
（1）The ultra-high purity fluorine niobic acid feed liquid that extract and separate step is obtained proceeds to neutralization chamber；
（2）Slowly open ammonia valve and add liquefied ammonia, neutralization precipitation to pH=9, form ultra-high purity niobium hydroxide slip, oxidation
Thing total amount is with Nb2O5Meter=127.81kg.
4th, adjust eccysis fluorine：
（1）Ultra-high purity niobium hydroxide slip is proceeded to filter press；
（2）Add 65 DEG C of pure water containing ammonia（The weight percentage of ammonia is 5%）Carry out adjusting eccysis fluorine；
（3）Tune is washed till fluorine in slip（F）≤ 0.01g/L, press filtration forms ultra-pure niobium hydroxide filter cake, oxide aggregate with
Nb2O5=127.17kg.
5th, dry：
（1）Ultra-high purity niobium hydroxide filter cake is contained in charging tray, loads drying baker；
（2）Oven temperature is controlled to 130 DEG C ~ 140 DEG C, and the time is 8 hours, dries and forms ultra-high purity niobium hydroxide powder
End, oxide aggregate is with Nb2O5=126.53kg.
6th, calcine：
（1）The ultra-high purity niobium hydroxide of drying is gone to and pushes away boat stove and carry out high-temperature calcination；
（2）The fltting speed of push-plate is 12 ~ 15 minutes/push-plate, and calcining low-temperature space temperature control is 350 ~ 400 DEG C, calcining
Temperature control is 850 ~ 950 DEG C, and the time is 15 hours, and calcining forms ultra-high purity niobium oxide powder, and oxide aggregate is with Nb2O5
Meter=125.89kg.
7th, sieve：
Ultra-high purity niobium oxide powder after calcining is passed through 60 mesh sieves, extracting screen underflow obtains final product target product, and oxide is total
Amount is with Nb2O5=125.26kg.
8th, detect operation：
The ultra-high purity niobium oxide powder sampling that screening is obtained, is analyzed detecting according to GB/T5314 regulation, main one-tenth
Divide and impurity content is shown in Table 1.
Embodiment 2The preparation of ultra-high purity niobium oxide
1st, acidity allotment：
（1）Fluorine niobic acid raw material volume is 1120L, and after measured, total oxide concentration is with (Ta+Nb)2O5It is calculated as 161g/L, hydrogen
Fluoric acid molar concentration is 2.5moL/L, and sulfuric acid molar concentration is 1.6moL/L, puts in acid adjustment groove；
（2）By calculating, chemistry pure dense hydrofluoric acid 192.87L, chemical pure concentrated sulfuric acid 164.43L need to be added；
（3）The dense hydrofluoric acid calculating and the concentrated sulfuric acid are separately added in acid adjustment groove, start stirring 60min, after allotment
Fluorine niobic acid feed liquid cumulative volume is 1477.30L, and total oxide concentration is with (Ta+Nb)2O5It is calculated as 122.06g/L, hydrofluoric acid mole is dense
Spend for 7.2moL/L, sulfuric acid molar concentration is 3.6moL/L.
2nd, extract and separate operation：
（1）Fluorine niobic acid feed liquid after allotment proceeds in extraction tank；Extraction and separation technology condition is：
Extraction series：10 grades of extraction section, washes miscellaneous section 10 grades, puies forward 10 grades of tantalum section, 10 grades of anti-niobium section；
Stream compares parameter：Fluorine niobic acid feed liquid after allotment: sec-octyl alcohol: mordant: anti-niobium agent=1: 1: 0.3: 1；
Wherein, sec-octyl alcohol：Purity 85%, containing ketone≤15%, pH=7.0；
Feed liquid：(Ta+Nb)2O5=122.06g/L, HF=7.2moL/L, H2SO4=3.6moL/L；
Mordant：H2SO4, molar concentration=3.5moL/L；
Anti- niobium agent：Ultra-pure water, wherein Si≤0.1ppm, Fe, Al, K, Na, Ca, Mg all≤0.01ppm.
（3）Fluting produces：
Start extraction tank, according to stream ratio parameter, controlling the fluorine niobic acid feed liquid after allotment to enter extraction tank flow is 1000mL/
Min, sec-octyl alcohol is 1000mL/min, and mordant is 300mL/min, and anti-niobium agent is 1000mL/min；First extracted with sec-octyl alcohol and adjust
Feed liquid after joining, obtains organic phase, then with organic phase described in mordant pickling, finally with after pickling described in anti-niobium agent back extraction
Organic phase, produces ultra-high purity fluorine niobic acid feed liquid, oxide aggregate is with Nb2O5Meter=178.51kg.
3rd, neutralization precipitation operation：
（1）The ultra-high purity fluorine niobic acid feed liquid that extract and separate step is obtained proceeds to neutralization chamber；
（2）Slowly open ammonia valve and add liquefied ammonia, neutralization precipitation to PH=10, form ultra-pure niobium hydroxide slip, oxide
Total amount is with Nb2O5Meter=174.04kg.
4th, adjust eccysis fluorine operation：
（1）Ultra-pure niobium hydroxide slip is proceeded to filter press；
（2）Add 70 DEG C of pure water containing ammonia（The weight percentage of ammonia is 8%）Carry out adjusting eccysis fluorine；
（3）Tune is washed till fluorine in slip（F）≤ 0.01g/L, press filtration forms ultra-pure niobium hydroxide filter cake, oxide aggregate with
Nb2O5=173.17kg.
5th, baking operation：
（1）Ultra-high purity niobium hydroxide filter cake is contained in charging tray, loads drying baker；
（2）Oven temperature is controlled to 170 ~ 180 DEG C, and the time is 5 hours, dries and forms ultra-pure niobium hydroxide powder, oxygen
Compound total amount is with Nb2O5=172.30kg.
6th, calcine：
（1）The ultra-high purity niobium hydroxide of drying is gone to and pushes away boat stove and carry out high-temperature calcination；
（2）The fltting speed of push-plate is 12 ~ 15 minutes/push-plate, and calcining low-temperature space temperature control is 400 ~ 450 DEG C, calcining
Temperature control be 1000 DEG C ~ 1050 DEG C, the time be 10 hours, calcining formed ultra high purity nitric oxide niobium powder, oxide aggregate with
Nb2O5=171.44kg.
7th, sieve：
Ultra high purity nitric oxide niobium powder is passed through 60 mesh sieves, extracting screen underflow obtains final product target product, and oxide aggregate is with Nb2O5=
170.58kg.
8th, detect operation：
The ultra-high purity niobium oxide powder sampling that screening is obtained, is analyzed detecting according to GB/T5314 regulation, main one-tenth
Divide and impurity content is shown in Table 1.
The quality measurements of the ultra-high purity niobium oxide of table 1 embodiment 1 and 2 preparation
| Embodiment 1 | Embodiment 2 | F Nb2O5-048a | F Nb2O5-045b | ||
| Principal component（Mass percent）, it is not less than | Nb2O5 | 99.99715 | 99.99779 | 99.998 | 99.995 |
| Impurity element（%）, no more than | Ta | 0.0002 | 0.0003 | 0.0003 | 0.0005 |
| Al | 0.00005 | 0.00005 | 0.0001 | 0.0002 | |
| As | 0.0001 | 0.00001 | 0.00001 | 0.00005 | |
| B | 0.00005 | 0.00005 | 0.00005 | 0.00005 | |
| Bi | 0.00005 | 0.00005 | 0.00005 | 0.0001 | |
| Ca | 0.00014 | 0.00014 | 0.0001 | 0.0003 | |
| Impurity element（%）, no more than | Cd | 0.00005 | 0.00005 | -c | -c |
| Co | 0.00001 | 0.00001 | 0.00001 | 0.00005 | |
| Cr | 0.00005 | 0.00005 | 0.00005 | 0.0001 | |
| Cu | 0.00005 | 0.00005 | 0.00005 | 0.0001 | |
| F | 0.0015% | 0.0015% | 0.0015 | 0.0030 | |
| Fe | 0.0001 | 0.00015 | 0.0001 | 0.0002 | |
| Ga | 0.00001 | 0.00001 | -c | -c | |
| K | 0.0002 | 0.0002 | 0.0001 | 0.0003 | |
| Mg | 0.00015 | 0.0001 | 0.0001 | 0.0001 | |
| Mn | 0.00005 | 0.00005 | 0.00005 | 0.0001 | |
| Mo | 0.00001 | 0.00001 | 0.00001 | 0.0001 | |
| Na | 0.0002 | 0.0001 | 0.0001 | 0.0003 | |
| Ni | 0.00005 | 0.00005 | 0.00005 | 0.0001 | |
| Pb | 0.00005 | 0.00005 | 0.00005 | 0.0003 | |
| Sb | 0.0001 | 0.0001 | 0.0002 | 0.0006 | |
| Si | 0.0005 | 0.0004 | 0.0005 | 0.0010 | |
| Sn | 0.0005 | 0.00005 | 0.00005 | 0.0001 | |
| Ti | 0.0001 | 0.0001 | 0.0001 | 0.0001 | |
| V | 0.00005 | 0.00005 | 0.00005 | 0.00005 | |
| W | 0.00002 | 0.00002 | 0.00002 | 0.0002 | |
| Zr | 0.00001 | 0.00001 | 0.00001 | 0.00005 |
a：Nb in professional standard YS/T548-20072O5- 048 product grade, for current purity highest product grade；
b：Nb in professional standard YS/T548-20072O5- 045 product grade；
c：Do not specify in professional standard YS/T548-2007.
From the data display of table 1, the main one-tenth of the ultra-high purity niobium oxide preparing according to preparation method of the present invention
Content is divided to be higher than existing industry highest standard, impurity content is far below existing industry highest standard.
Specific description of embodiments of the present invention above is not intended to limit the present invention, and those skilled in the art can be according to this
Various changes or deformation are made in invention, without departing from the spirit of the present invention, all should belong to the model of claims of the present invention
Enclose.
Claims (7)
1. a kind of preparation method of ultra-high purity niobium oxide, with fluorine niobic acid solution as raw material, including acidity allotment, extract and separate,
Neutralization precipitation, tune eccysis fluorine, drying and calcining；Described fluorine niobic acid solution, with (Ta+Nb)2O5Calculate, oxide aggregate be 110～
180g/L；
Described acidity adaptation step, adds dense hydrofluoric acid and the concentrated sulfuric acid including in described fluorine niobic acid solution, makes the material after allotment
In liquid, with (Ta+Nb)2O5Calculate, oxide aggregate is not less than 95g/L, hydrofluoric acid molar concentration=7.2 ± 0.1moL/L, sulfuric acid
Molar concentration=3.6 ± 0.05moL/L；
Described extract and separate step, including：Feed liquid after sec-octyl alcohol extraction allotment, obtains organic phase, then with mordant pickling institute
State organic phase, finally with the organic phase after pickling described in anti-niobium agent back extraction, obtain ultra-high purity fluorine niobic acid feed liquid；Wherein, institute
State the feed liquid after allotment, sec-octyl alcohol, mordant, anti-niobium agent volume ratio be 1～1.2: 1: 0.3～0.5: 0.8～1.2；Described
Extraction step is carried out in extraction tank, and the extraction tank series of sec-octyl alcohol extraction is 10 grades, and the extraction tank series of mordant pickling is
10 grades, the extraction tank series of anti-niobium agent back extraction is 10 grades；Described mordant is the sulphur of molar concentration=3.2～3.5mol/L
Acid, described anti-niobium agent is ultra-pure water, wherein Si≤0.1ppm, Fe, Al, K, Na, Ca, Mg all≤0.01ppm；
Described neutralization precipitation step, adds liquefied ammonia including to described ultra-high purity fluorine niobic acid feed liquid, to pH=9～10, is surpassed
High-purity hydrogen niobium oxide slurry；
Described tune eccysis fluorine step, is transferred to Filter Press including by described ultra-high purity niobium hydroxide slurry, filter cake uses 60
～70 DEG C of hot pure waters containing ammonia 5～8% carry out adjusting eccysis fluorine, Oil repellent≤0.01g/L to slip, filter, obtain ultra-pure
Degree niobium hydroxide filter cake；
Described baking step, 130～180 DEG C of drying temperature, 5～8 hours time；
Described calcining step, at 350～450 DEG C, calcining heat is controlled to 850～1050 DEG C to calcining low-temperature space temperature control, when
Between be 10～15 hours；Described calcining step is carried out in continuous boat pushing stove, and the fltting speed of push-plate is 12～15 minutes/pushes away
Disk.
2. preparation method according to claim 1 it is characterised in that
Described acidity adaptation step, allotment is 36mol/L with the molar concentration of dense hydrofluoric acid, the molar concentration of the allotment concentrated sulfuric acid
For 18mol/L.
3. preparation method according to claim 1 is it is characterised in that described extract and separate step, the material after described allotment
Liquid, sec-octyl alcohol, mordant, the volume ratio of anti-niobium agent are 1:1:0.3:1.
4. preparation method according to claim 1 and 2 is it is characterised in that described mordant is molar concentration=3.5mol/
The sulfuric acid of L.
5. preparation method according to claim 1 and 2, it is characterised in that described extraction step is carried out in extraction tank, enters
Groove flow is respectively：Feed liquid 1000mL/min after described allotment, described sec-octyl alcohol 1000mL/min, described mordant 300mL/
Min, described anti-niobium agent 1000mL/min.
6. preparation method according to claim 1, it is characterised in that after calcining step, also including screening step, is specifically grasped
As：The ultra-high purity niobium oxide powder obtaining through calcining step passes through 60 mesh sieves, extracting screen underflow, obtains final product.
7. a kind of preparation method of ultra-high purity niobium oxide, including acidity allotment, extract and separate, neutralization precipitation, adjusts eccysis fluorine, baking
Do and calcine, specific embodiment is：
I. acidity allotment
Described acidity allotment is carried out in acid adjustment groove；
The fluorine niobic acid raw material that oxide aggregate is 110～180g/L adds acid adjustment groove；To in acid adjustment groove add molar concentration=
The dense hydrofluoric acid of 36moL/L and the concentrated sulfuric acid of molar concentration=18moL/L, make in the feed liquid after allotment, oxide aggregate is with (Ta
+Nb)2O5Calculate and be not less than 95g/L, hydrofluoric acid molar concentration=7.2 ± 0.1moL/L, sulfuric acid molar concentration=3.6 ±
0.05moL/L；Start stirring 30～60min, the feed liquid after being allocated；
II. extract and separate
Described extract and separate step is carried out in extraction tank；Start extraction tank, the feed liquid after the allotment that rate-determining steps I obtains enters groove
Flow is 1000mL/min, and the groove flow that enters of sec-octyl alcohol is 1000mL/min, and the groove flow that enters of mordant is 300mL/min, instead
The groove flow that enters of niobium agent is 1000mL/min；First with the feed liquid after sec-octyl alcohol extraction allotment, obtain organic phase, sourer with mordant
Wash described organic phase, finally with the organic phase after pickling described in anti-niobium agent back extraction, obtain ultra-high purity fluorine niobic acid feed liquid, oxidation
Thing total amount is with (Ta+Nb)2O5Calculating >=90g/L；The extraction tank series of described sec-octyl alcohol extraction is 10 grades, described mordant pickling
Extraction tank series be 10 grades, the extraction tank series of described anti-niobium agent back extraction is 10 grades；
Wherein, mordant is the sulfuric acid of molar concentration=3.2～3.5mol/L；Anti- niobium agent is ultra-pure water, wherein Si≤0.1ppm,
Fe, Al, K, Na, Ca, Mg all≤0.01ppm；
III. neutralization precipitation
Described neutralization precipitation step is carried out in neutralization chamber；
The ultra-high purity fluorine niobic acid feed liquid that step II is obtained proceeds to neutralization chamber, slowly opens ammonia valve and adds liquefied ammonia, neutralization precipitation
To pH=9～10, obtain ultra-high purity niobium hydroxide slip；
IV. adjust eccysis fluorine
Described tune eccysis fluorine step is carried out in filter press；
Ultra-pure niobium hydroxide slip that step III is obtained proceeds to filter press, adds 60～70 DEG C of pure water containing ammonia 5～8%,
Tune is washed till Oil repellent≤0.01g/L in slip, and press filtration obtains ultra-pure niobium hydroxide filter cake；
V. dry
Described baking step is carried out in an oven；
Ultra-pure niobium hydroxide filter cake that step IV is obtained is contained in charging tray, loads baking oven, and at 130～180 DEG C, heating 5～8 is little
When, dry and obtain ultra-high purity niobium hydroxide powder；
VI. calcine
Described calcining step is carried out in pushing away boat stove；
The ultra-high purity niobium hydroxide powder that step V is obtained goes to and pushes away boat stove, and the fltting speed of push-plate is 12～15 minutes/pushes away
Disk, calcining low-temperature space temperature control be 350～450 DEG C, calcining heat is controlled to 850 DEG C～1050 DEG C, calcination time be 10～
15 hours, calcining obtained ultra-high purity niobium oxide powder；
VII. sieve
The ultra-high purity niobium oxide powder obtaining through calcining step passes through 60 mesh sieves, extracting screen underflow, obtains final product.
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| CN106348343B (en) * | 2016-08-19 | 2017-12-08 | 江门富祥电子材料有限公司 | The preparation method of High-density Niobium Oxide |
| CN106929697A (en) * | 2017-04-18 | 2017-07-07 | 江苏圣亚有色金属材料有限公司 | A kind of purifying technique of pure niobium |
| 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 |
| CN110078122A (en) * | 2019-05-27 | 2019-08-02 | 九江有色金属冶炼有限公司 | A kind of preparation method of p-type high purity niobium oxide |
| CN110386623B (en) * | 2019-07-04 | 2022-04-19 | 江西海协稀有金属材料有限公司 | Method for preparing high-purity niobium oxide by filtering niobium ceramic membrane |
| CN112010348B (en) * | 2020-09-14 | 2022-08-19 | 宁夏东方钽业股份有限公司 | Preparation method of high-purity niobium oxide for high-purity niobium sheet for irradiation monitoring tube |
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