CN104986800B - The method preparing niobium hydroxide precipitation for raw material with fluorine niobic acid - Google Patents
The method preparing niobium hydroxide precipitation for raw material with fluorine niobic acid Download PDFInfo
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- CN104986800B CN104986800B CN201510410570.2A CN201510410570A CN104986800B CN 104986800 B CN104986800 B CN 104986800B CN 201510410570 A CN201510410570 A CN 201510410570A CN 104986800 B CN104986800 B CN 104986800B
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- niobic acid
- ammonia
- fluorine niobic
- raw material
- niobium hydroxide
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Abstract
The present invention provides a kind of method preparing niobium hydroxide precipitation for raw material with fluorine niobic acid, it is for the deficiency of existing technique, use and be passed through ammonia under pressure condition certain in enclosed system, prepare niobium hydroxide precipitate, including fluorine niobic acid raw material, it is in airtight reaction unit, under certain reaction temperature and pressure and solvent existence condition, solution containing fluorine niobic acid makes in airtight reaction system ammonia and fluorine niobic acid react, prepares niobium hydroxide precipitate；Both accelerated response speed, and be capable of again, to the control being passed through ammonia amount, having saved production cost to greatest extent simultaneously, owing to there is no the effusion of ammonia, breach the way that logical ammonia neutralizes under unlimited system at present, it is achieved that the zero-emission of ammonia, will not be to the pollution problem of environment.
Description
Technical field:
The present invention relates to a kind of method preparing niobium hydroxide precipitation, especially with the method preparing niobium hydroxide precipitation with fluorine niobic acid for raw material in enclosed system.
Technical background:
Niobium is important rare metal, is widely used in the industrial circles such as space flight and aviation, atomic energy, metallurgy, telecommunications, petrochemical industry, glass ceramics, and countries in the world government pays much attention to the development of niobium industry strategy material.
Niobium oxide is a kind of important niobium product, is positioned at the source in niobium industrial chain, the other products of nearly all niobium, is all to prepare with niobium oxide as raw material.The important source material that niobium oxide or ceramic material, superconductor, lithium niobate monocrystal, optical glass, hard alloy, catalyst etc. are conventional.In recent years, the consumption of niobium oxide is the most active, and world's niobium demand annual amplification is stable more than 10%, and China is that niobium consumes big country, and average annual amplification is close to 30%.Along with the application of niobium deepens constantly, it is contemplated that the demand of following niobium oxide will continue to keep higher growth rate.
The commonly used HF-H of preparation method of niobium oxide at present2SO4-MIBK hydrometallurgical processes, its technological process is, after tantalum-niobium concentrate grinds, to use HF-H2SO4Nitration mixture decomposes, and decomposed solution organic solvent extracts, and after tantalum niobium organic facies purification and impurity removal, obtains fluorine niobic acid aqueous solution, fluorine niobic acid aqueous solution alkali neutralization precipitation with anti-niobium liquid back extraction, then filters, dries, calcines and can produce Nb2O5.Wherein neutralization precipitation one step of fluorine niobic acid, commercial production generally uses liquefied ammonia to precipitate after being converted into ammonia.The advantage of ammonia is relative inexpensiveness, and impurity is easily removed, beneficially large-scale production, so in the preparation of niobium oxide, ammonia is the precipitant that commercial production is the most frequently used.Existing frequently with technique be that the fluorine niobic acid system that ammonia is passed through in open system acidity is translated into niobium hydroxide and is neutralized precipitation, the method can be inevitably present escaping in a large number of ammonia, cause the increase of production cost, bring bigger pressure to environment protection treating simultaneously.
On the other hand, prepare with fluorine niobic acid system niobium hydroxide sedimentary during, owing to being to carry out in the process units still opened, therefore, being typically to produce at normal temperatures and pressures, thus exist in course of reaction, response speed is slower, use the existing mode of production simultaneously, there is certain hidden danger in the safety in production to operator, and the usage amount of ammonia accordingly increases, and causes certain waste, environment is also resulted in pollution, and has accordingly increased the production cost of niobium oxide.
Summary of the invention:
The present invention seeks to provide a kind of method preparing niobium hydroxide precipitation for raw material with fluorine niobic acid, it is for the deficiency of existing technique, use and be passed through ammonia under pressure condition certain in enclosed system, prepare niobium hydroxide precipitate, both response speed had been accelerated, it is capable of again the control being passed through ammonia amount simultaneously, save production cost to greatest extent, owing to there is no the effusion of ammonia, breach the way that logical ammonia neutralizes under unlimited system at present, achieve the zero-emission of ammonia, will not be to the pollution problem of environment。
The present invention provides a kind of method preparing niobium hydroxide precipitation for raw material with fluorine niobic acid, including fluorine niobic acid raw material, it is in airtight reaction unit, under certain reaction temperature and pressure and solvent existence condition, solution containing fluorine niobic acid makes in airtight reaction system ammonia and fluorine niobic acid react, prepares niobium hydroxide precipitate；The quality mol ratio controlling described ammonia and fluorine niobic acid is 20:1-1:20.
Solvent of the present invention is that the chemical substance of described liquid is the oxidation solvent in water and/or chemical constitution containing at least one oxygen atom at reaction conditions for the chemical substance of liquid.
The present invention preferably controls described reaction temperature and is-10 DEG C-150 DEG C.
It is to carry out under 1atm-10atm that the present invention preferably controls described reaction pressure.
The present invention preferably controls ammonia and the fluorine niobic acid response time is 1-2900 minute.
Oxidation solvent of the present invention is oxygen-containing hydrocarbon compounds, and described oxygen-containing hydrocarbon compounds is preferably in alcohols, ethers, ketone and similar compound thereof any one.
Oxidation solvent of the present invention more preferably C1-C10In any one alcohol compound or the mixing of compound of several alcohols.
The method that the present invention prepares niobium hydroxide precipitation with fluorine niobic acid for raw material, it is passed through ammonia under the conditions of using temperature and pressure certain in enclosed system, prepare niobium hydroxide precipitate, both response speed had been accelerated, it is capable of again the effective control being passed through ammonia amount simultaneously, save production cost to greatest extent, owing to there is no the effusion of ammonia, breach the way that logical ammonia neutralizes under unlimited system at present, achieve the zero-emission of ammonia, the pollution problem of environment will not be ensured the safety in production of operator simultaneously.
Detailed description of the invention:
By following embodiment, the present invention is described in further detail, and it will assist in and is further appreciated by technical solution of the present invention, but is not intended to present disclosure。
The present invention is achieved by the following technical solutions, in the reaction unit in a hermetic container filling fluorine niobic acid solution, is passed through ammonia under uniform temperature and pressure, and reaction stops logical ammonia after terminating, material enters lower one treatment process；
Method of the present invention can by the closed reaction vessel of any appropriate format or device such as fixed bed, transfer bed, fluid bed, stirring slurry or CSTR reactor and interval, continuously or semi-continuous mode is carried out, therefore reactant can react by the gross or sequentially；
The method of the present invention also requires to use a kind of solvent；Suitably solvent is included under the reaction condition during the present invention reacts any chemical substance for liquid, includes but not limited to oxygen-containing hydro carbons such as alcohols, Yi Jishui；Preferably solvent is the oxidation solvent in chemical constitution containing at least one oxygen atom.Described oxidation solvent includes water and oxygen-containing hydro carbons such as alcohols, ethers, ketone and the like；
Preferably oxidation solvent includes alcohols such as methanol, ethanol, isopropanol and the tert-butyl alcohol of low-carbon (LC) aliphatic C1-C10, or their mixture, Yi Jishui；May be used without the mixture of above-mentioned alcohol and water；One particularly preferred solvent is water；
Reaction according to the present invention be enough to obtain required fluorine niobic acid neutralize at a temperature of carry out, preferably carry out at 0-150 DEG C, more preferably carry out at 20-120 DEG C.About 1 minute-48 hours, the reaction of more preferably 1 minute-8 hours or the time of staying were that typical case is preferred.Although reaction also can be carried out at atmosheric pressure, but its advantageously 1-
Work under the pressure of 100 i.e. 1atm-10atm of atmospheric pressure；
The amount of ammonia used by the present invention can determine on the basis of being passed through the mol ratio of ammonia in the acidity contained by fluorine niobic acid system；General control ammonia is 20:1-1:20 with the quality mol ratio of fluorine niobic acid.
Embodiment
1
:
In airtight reaction unit system, it is passed through in ammonia and fluorine niobic acid prepares niobium hydroxide precipitation, the present embodiment uses solvent to be water, 250 mL containers add in equipped with the container of magnetic stirring apparatus 100 mL fluorine niobic acid aqueous solutions, content of niobium is 167g/L, reactor is closed, it is that 1 atm ammonia is passed through to above-mentioned reactor by pressure again, stirring reaction 3 h at temperature is 10 DEG C, the quality mol ratio controlling ammonia and fluorine niobic acid is 10:1, after reaction terminates, occur that a large amount of white solid is niobium hydroxide precipitation；The white solid that sucking filtration obtains prepares niobium oxide 16.50 g of 99% through washing, calcining.
Embodiment
2
:
In the system of confined reaction device, it is passed through in ammonia and fluorine niobic acid prepares niobium hydroxide precipitation, 250 mL containers add in equipped with the container of magnetic stirring apparatus 100 mL fluorine niobic acid aqueous solutions, reactor is closed, it is that 5 atm ammonias are passed through to above-mentioned reactor by pressure again, at 30 DEG C, stirs 30 min.The quality mol ratio controlling ammonia and fluorine niobic acid is 1:10, after reaction terminates, a large amount of niobium hydroxide precipitate white solid occurs.The white solid that sucking filtration obtains obtains the niobium oxide 16.53 of 99% through washing, calcining
g。
Embodiment
3
:
Reaction condition in the present embodiment, in addition to the description below, remaining undeclared part is identical with embodiment 1 or 2, in the system of confined reaction device, it is passed through in ammonia and fluorine niobic acid prepares niobium hydroxide precipitation, the solvent used in the present embodiment is alcohols, ethanol and aqueous solution are preferably used, and the quality mol ratio controlling ammonia and fluorine niobic acid is 5:1, obtains niobium oxide 16.54 g of 99%.
Comparative example
1
:
Unlimited system is passed through in ammonia and fluorine niobic acid prepares niobium hydroxide precipitation, 250 mL containers add in equipped with the container of magnetic stirring apparatus 100 mL fluorine niobic acid aqueous solutions, ammonia is passed through to above-mentioned reactor under conditions of opening wide by reactor, stirs 8 h at 10 DEG C.After reaction terminates, a large amount of white solid occurs.The white solid that sucking filtration obtains obtains niobium oxide 16.39 g of 99% through washing, calcining.
Comparative example
2
:
Unlimited system is passed through in ammonia and fluorine niobic acid prepares niobium hydroxide precipitation, 250 mL containers add in equipped with the container of magnetic stirring apparatus 100 mL fluorine niobic acid aqueous solutions, ammonia is passed through to above-mentioned reactor under conditions of opening wide by reactor, stirs 4 h at 30 DEG C.After reaction terminates, a large amount of white solid occurs.The white solid that sucking filtration obtains obtains the niobium oxide 16.45g of 99% through washing, calcining.
The foregoing is only the preferred embodiments of the invention and oneself, not limit the practical range of the present invention with this, within all should being covered by the protection category that the claims is defined.
After table 1 below is for using the inventive method and using art methods to prepare niobium hydroxide precipitation, the result of reproduction niobium oxide.
Table 1 leads in ammonia and fluorine niobic acid prepares niobium hydroxide precipitation result
| Sample | Temperature | Pressure | Response time (h) | Fluorine niobic acid (g) | Ammonia usage (g) | Niobium oxide productivity |
| 1 | 10 ℃ | 1atm | 3 | 16.7 | 10.5 | 99% |
| 2 | 30 ℃ | 5atm | 0.5 | 16.7 | 10.5 | 99% |
| 1* | 10 ℃ | Normal pressure | 8 | 16.6 | 50.1 | 99% |
| 2* | 30 ℃ | Normal pressure | 4 | 16.5 | 36.7 | 99% |
Illustrate: 1*, 2* in table 1 represent and the present invention program embodiment 1,2 comparative examples, the consumption of ammonia in comparison embodiment is 3-5 times of the inventive method as can be seen from the above table, and the time reacted is longer；Reaction yield is lower slightly.
Claims (3)
1. the method preparing niobium hydroxide precipitation for raw material with fluorine niobic acid, including fluorine niobic acid raw material, it is characterized in that in airtight reaction unit, under certain reaction temperature and pressure and solvent existence condition, solution containing fluorine niobic acid makes in airtight reaction system ammonia and fluorine niobic acid react, prepares niobium hydroxide precipitate；The quality mol ratio controlling described ammonia and fluorine niobic acid is 20:1-1:20；
Described solvent is that the chemical substance of described liquid is the oxidation solvent in water and/or chemical constitution containing at least one oxygen atom at reaction conditions for the chemical substance of liquid；
Described oxidation solvent is oxygen-containing hydrocarbon compounds, described oxygen-containing hydrocarbon compounds be in alcohols, ethers, ketone compounds any one；
Control described reaction temperature and be-10 DEG C-30 DEG C；
Controlling described reaction pressure is to carry out under 1atm-5atm.
2. the method preparing niobium hydroxide precipitation with fluorine niobic acid for raw material as claimed in claim 1, is characterized in that controlling ammonia and the fluorine niobic acid response time is 1-2900 minute.
3. preparing, for raw material, the method that niobium hydroxide precipitates with fluorine niobic acid as claimed in claim 1, oxidation solvent described in its feature is C1-C10In any one alcohol compound or the mixing of compound of several alcohols.
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| CN114906884A (en) * | 2022-05-20 | 2022-08-16 | 天能新能源(湖州)有限公司 | Preparation method of fluorine-niobium double-doped lithium niobate-coated ternary material |
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