CN102442700A - Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation - Google Patents

Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation Download PDF

Info

Publication number
CN102442700A
CN102442700A CN2011102864033A CN201110286403A CN102442700A CN 102442700 A CN102442700 A CN 102442700A CN 2011102864033 A CN2011102864033 A CN 2011102864033A CN 201110286403 A CN201110286403 A CN 201110286403A CN 102442700 A CN102442700 A CN 102442700A
Authority
CN
China
Prior art keywords
niobium
niobium oxide
peroxo
container
nbo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011102864033A
Other languages
Chinese (zh)
Inventor
张宗国
徐忠亭
张必灵
张伟宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGDONG ZHIYUAN NEW MATERIALS Co Ltd
Original Assignee
GUANGDONG ZHIYUAN NEW MATERIALS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GUANGDONG ZHIYUAN NEW MATERIALS Co Ltd filed Critical GUANGDONG ZHIYUAN NEW MATERIALS Co Ltd
Priority to CN2011102864033A priority Critical patent/CN102442700A/en
Publication of CN102442700A publication Critical patent/CN102442700A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses a method for preparing high-purity spherical niobium oxide by peroxidizing precipitation, which comprises the steps of: adding hydrogen peroxide H2O2 and liquid ammonia into a fluooxycolumbic acid solution H2NbOF5 to obtain (NH4)3NbO8 crystals; and roasting the crystals at a controlled temperature to obtain niobium oxide having a corresponding phase state and a granularity of 0.3-1 mum. According to the method disclosed by the invention, ammonium niobate crystals which are obtained from precipitation process are free from package, adsorption, and impurities and filtered easily. Consequently, high product purity is obtained in a case of the same raw materials and technological conditions; the ammonium niobate is then roasted at 150-1300 DEG C to obtain fluorine-free niobium oxide which is obviously spherical, uniform in particle and has the granularity of 0.3-1 mum; and niobium oxide at alpha, beta and gamma phase states can be obtained by controlling the roasting temperature according to application requirements. The method disclosed by the invention leaves out washing, drying as well as grinding and sieving procedures, saves plenty of manpower, material resources and energy sources.

Description

A kind of peroxo-deposition is produced the method for High Purity Spherical niobium oxides
Technical field
The present invention relates to a kind of method of producing spherical niobium oxides, be meant a kind of method that adopts the peroxo-depositing technology to produce the High Purity Spherical niobium oxides especially.
Background technology
Niobium hydroxide deposition optimum size control problem is a great problem in the performance function ceramic fabrication technique, belongs to the new and high technology research and development that state key is supported, is an important ring that satisfies large vol multi-layer ceramic capacitor and tantalum niobium artificial lens demand.The existing preparation Technology is: the resulting fluooxycolumbic acid solution of SX is used ammonia precipitation, obtain unformed cotton-shaped niobium hydroxide slip (granularity 1-3 μ m), through filtering, after the washing, drying, roasting, mill sieve obtain Niobium Pentxoxide.Its precipitin reaction mechanism is: H 2NbOF 5+ 5NH 3+ 4H 2O=Nb (OH) 5↓+5NH 4F.
The niobium oxides that this Technology is produced, different by purity, divides three ranks: i.e. technical grade, opticglass level, high-purity grade.Technical grade product is used for carbon reduction production metal niobium or makes the raw material of ceramic condenser, and opticglass level product is used to produce opticglass; High-purity grade of product is used to produce lithium niobate monocrystal, further processing and fabricating SAW filter or optical communication device.
The subject matter that exists in the existing niobium hydroxide precipitation technology is: (1) gained throw out is unformed floss or coacervate, particle is thick, quality is low; (2) behind deposition and the slurry filtration, a large amount of de-ionized washing fluorine be used, however, still the lithium niobate crystals quality problems can be caused frequently.Cause the major cause of the problems referred to above to be:
1, coprecipitation mode and settling apparatus problem.World's hydrometallurgy is less to coprecipitation mode and settling apparatus research, and therefore physical properties such as the granularity to precipitated product guarantees not have sophisticated scientific payoffs, do not form degree of supersaturation by species precipitate (1) solution; (2) generate nucleus and nucleus growth; (3) a series of objective law design coprecipitation modes of deposition growth and ageing and selection equipment.Therefore; The product particle that obtains of deposition is thick, and density is little, suitable ceramic condenser level product requirement (in July, 1991; The Tokyo technology can be according to the application of niobium oxides at the large vol multi-layer ceramic capacitor, and the mean particle size that proposes niobium oxides first requires 0.32 μ m); Throw out is prone to take place coalescence and forms " druse " in addition, and therefore the parcel mother liquor influences the finished product purity.
2, with ammonia precipitation niobium liquid (H 2NbOF 5), conceivable is NbO 5NH 2O, the fluooxycolumbic acid ammonia (NH that can actually obtain 4) NbOF 5, be difficult to washing, obtain NbO through roasting 2Therefore F causes Nb 2O 5Middle fluorine is high, when drawing artificial lens, is prone to produce " fluorine gas bubble ", or makes crystal " muddiness ".
Summary of the invention
The objective of the invention is to adopt the peroxo-precipitation technology, produce spherical high-density, highly purified niobium oxides, to be applicable to the demand of large vol multi-layer ceramic capacitor and optical grade lithium niobate monocrystal.
Designed the method that a kind of peroxo-deposition is produced the High Purity Spherical niobium oxides according to above-mentioned purpose, this method is with using oxydol H 2O 2Add the fluooxycolumbic acid Solution H with liquefied ammonia 2NbOF 5In, obtain peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystallization, through the controlled temperature roasting, acquisition needs the niobium oxides of phase, and concrete steps do,
1) gets a certain amount of niobium liquid and place container;
2) press Nb 2O 5: H 2O 2=1 mole: 8 moles of consumptions that calculate 30% ydrogen peroxide 50 add ydrogen peroxide 50 and mix in container;
3) in container, feed ammonia, reach 8, realize the deposition fully of niobium mud until pH value;
4) solution in the container and throw out are filtered, obtain peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystal;
5) in 150～1200 ℃ temperature range to peroxo-niobic acid ammonium (NH 4) 3NbO 8The crystal roasting obtains the niobium oxides of α, β, the various phases of γ respectively; Wherein,
Nb in the niobium liquid 2O 5Content be 80～150g/L, the concentration of ydrogen peroxide 50 is 30%wt.
At this moment, gained niobium oxides granularity 0.3～1 μ m.
The inventive method compared with prior art advantage shows:
1, operation obtains is niobic acid ammonium crystal in deposition, do not have parcel, do not have absorption, do not have be mingled with, easy filtration, therefore under same raw material and processing condition, the product purity height.
2, the niobic acid ammonium is through 150～1300 ℃ of roastings, and the niobium oxides that obtains is floride-free, and it is obviously spherical that product is, and uniform particles is consistent, granularity 0.3～1 μ m; According to application demand,, can obtain the niobium oxides of α, β, the different phases of γ through the control of maturing temperature.
3, save washing, oven dry, three operations of mill sieve, saved a large amount of manpowers, the material resources and the energy.
Embodiment
The present invention be directed to prior art and can only use liquid ammonia deposition niobium liquid (H 2NbOF 5), and obtain unformed cotton-shaped Nb (OH) 5(Nb 2O 5NH 2O) throw out prepares the niobium oxides product of granularity 1-3 μ m thus, and the problem that operation is many, operating process is complicated, cost is high has proposed the employing oxydol H 2O 2Precipitate niobium liquid H with liquefied ammonia 2NbOF 5Obtain eight oxidation niobic acid ammonium (NH 4) 3NbO 8Crystallization, through filtering, roasting obtains the operational path of the spherical niobium oxides of 0.3～1 μ m.General planning of the present invention is to use oxydol H 2O 2Add the fluooxycolumbic acid Solution H with liquefied ammonia 2NbOF 5In, obtain peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystallization, through the controlled temperature roasting, acquisition needs the niobium oxides of phase, and concrete steps do,
1) gets a certain amount of niobium liquid and place container;
2) press Nb 2O 5: H 2O 2=1 mole: 8 moles of consumptions that calculate 30% ydrogen peroxide 50 add ydrogen peroxide 50 and mix in container;
3) in container, feed ammonia, reach 8, realize the deposition fully of niobium mud until pH value;
4) solution in the container and throw out are filtered, obtain peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystal;
5) in 150～1300 ℃ temperature range to peroxo-niobic acid ammonium (NH 4) 3NbO 8The crystal roasting obtains the niobium oxides of α, β, the various phases of γ respectively; Wherein,
Nb in the niobium liquid 2O 5Content be 80～150g/L, the concentration of ydrogen peroxide 50 is 30%wt.
The transformation temperature of niobium oxides is following: when temperature is higher than 150 ℃ during until 950 ℃, oxidation niobic acid ammonium (NH 4) 3NbO 8Crystal generation heat decomposition temperature begins to obtain α phase oxidation niobium; In the time of 1100～1150 ℃, obtain β phase oxidation niobium; When temperature＞1200 ℃, obtain γ phase oxidation niobium.
At this moment, gained niobium oxides granularity 0.3～1 μ m.Below in conjunction with specific embodiment the present invention is made further detailed description.
Embodiment:
1. calculate the materials ratio
Get 1L niobium liquid, contain Nb 2O 5137.5g/L.Calculate H 2O 2Consumption: 137.5/226*8=4.16molH 2O 2,
Folding H 2O 2Consumption: 4.16mol*34g/mol=141.4g/L
Folding 30%H 2O 2Consumption: 141.4/0.3=472ml
Then: 1 liter of (Nb 2O 5137.5g/L) niobium liquid uses H 2O 2472ml
2. operation
1. getting concentration is Nb 2O 5137.5g/L niobium liquid 1000ml places beaker;
2. in beaker, add 472mlH 2O 2(concentration 30%) begins to stir;
3. in beaker, add NH 4OH, until pH value 8, deposition is fully;
4. stop to stir, filter, obtain (NH 4) 3NbO 8Crystal;
5. with crystal roasting 6 hours in the 10KW retort furnace, the tool transformation temperature is following:
150 ℃: thermolysis;＜950 ℃, get α-Nb 2O 51100～1150 ℃ get β-Nb 2O 5＞1200 ℃, get γ-Nb 2O 5Get Nb 2O 5Color even is consistent, all is ball-type, granularity 0.3～1 μ m.

Claims (2)

1. a peroxo-precipitates the method for producing the High Purity Spherical niobium oxides,
This method is with oxydol H 2O 2Add the fluooxycolumbic acid Solution H with liquefied ammonia 2NbOF 5In, obtain peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystallization, through the controlled temperature roasting, acquisition needs the niobium oxides of phase,
Concrete steps are:
1) gets niobium liquid and place container;
2) press Nb 2O 5: H 2O 2=1 mole: 8 moles of consumptions that calculate 30% ydrogen peroxide 50 add ydrogen peroxide 50 and mix in container;
3) in container, feed ammonia, reach 8, realize the deposition fully of niobium mud until pH value;
4) solution in the container and throw out are filtered, obtain peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystal;
5) in 150～1300 ℃ temperature range to peroxo-niobic acid ammonium (NH 4) 3NbO 8Crystal fuses, and obtains the niobium oxides of α, β, the various phases of γ respectively;
Wherein, Nb in the niobium liquid 2O 5Content be 80～150g/L, the concentration of ydrogen peroxide 50 is 30%wt.
2. peroxo-deposition according to claim 1 is produced the method for High Purity Spherical niobium oxides, it is characterized in that gained niobium oxides granularity 0.3～1 μ m.
CN2011102864033A 2011-09-16 2011-09-16 Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation Pending CN102442700A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011102864033A CN102442700A (en) 2011-09-16 2011-09-16 Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011102864033A CN102442700A (en) 2011-09-16 2011-09-16 Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation

Publications (1)

Publication Number Publication Date
CN102442700A true CN102442700A (en) 2012-05-09

Family

ID=46005698

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011102864033A Pending CN102442700A (en) 2011-09-16 2011-09-16 Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation

Country Status (1)

Country Link
CN (1) CN102442700A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102897836A (en) * 2012-10-23 2013-01-30 九江有色金属冶炼有限公司 Preparation method of ultrafine niobium oxide
CN104528827A (en) * 2014-12-31 2015-04-22 湖州师范学院 Hydrothermal preparation method for nanometer NbO2F powder
CN106517327A (en) * 2016-12-13 2017-03-22 广东致远新材料有限公司 Preparation method of spherical niobium pentoxide with big loose specific weight
CN106753359A (en) * 2016-11-10 2017-05-31 云南民族大学 A kind of blue light excites Mn4+The oxyfluoride red fluorescence powder and preparation method of doping
CN115818712A (en) * 2022-09-08 2023-03-21 季华实验室 Niobium oxide mixed with phosphoric acid in loose state and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5194232A (en) * 1990-09-28 1993-03-16 Hermann C. Starck Berlin Gmbh & Co. Kg Process for the preparation of tantalum/niobium hydroxides and oxides with a low fluoride content
CN1417128A (en) * 2002-03-30 2003-05-14 宁夏东方钽业股份有限公司 Production process of tantalate or niobate compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5194232A (en) * 1990-09-28 1993-03-16 Hermann C. Starck Berlin Gmbh & Co. Kg Process for the preparation of tantalum/niobium hydroxides and oxides with a low fluoride content
CN1417128A (en) * 2002-03-30 2003-05-14 宁夏东方钽业股份有限公司 Production process of tantalate or niobate compound

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
万明远: "煅烧温度对五氧化二铌物理性能的影响", 《稀有金属与硬质合金》 *
王伟: "低品位钽铌原料的湿法冶金新工艺研究", 《稀有金属快报》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102897836A (en) * 2012-10-23 2013-01-30 九江有色金属冶炼有限公司 Preparation method of ultrafine niobium oxide
CN102897836B (en) * 2012-10-23 2015-06-03 九江有色金属冶炼有限公司 Preparation method of ultrafine niobium oxide
CN104528827A (en) * 2014-12-31 2015-04-22 湖州师范学院 Hydrothermal preparation method for nanometer NbO2F powder
CN106753359A (en) * 2016-11-10 2017-05-31 云南民族大学 A kind of blue light excites Mn4+The oxyfluoride red fluorescence powder and preparation method of doping
CN106517327A (en) * 2016-12-13 2017-03-22 广东致远新材料有限公司 Preparation method of spherical niobium pentoxide with big loose specific weight
CN115818712A (en) * 2022-09-08 2023-03-21 季华实验室 Niobium oxide mixed with phosphoric acid in loose state and preparation method thereof
CN115818712B (en) * 2022-09-08 2024-05-07 季华实验室 Niobium oxide in loose state mixed with phosphoric acid and preparation method thereof

Similar Documents

Publication Publication Date Title
CN102978398B (en) Method for obviously lowering chlorine content in process of carbonic acid rare earth crystallization
CN102442700A (en) Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation
CN108910932B (en) Method for preparing narrow-distribution superfine yttrium oxide by sodium carbonate precipitation
CN112758968B (en) Alumina precursor and preparation method thereof, submicron alumina and preparation method thereof
EP2812284B1 (en) Method for producing mixed carbonates which can contain hydroxide(s)
CN114105172A (en) Method for producing high-purity lithium carbonate by causticizing and carbonizing rough lithium carbonate lime
CN104087790A (en) Addition method of grain growth inhibitor used for preparation of ultrafine hard alloy
CN111943240B (en) Method for preparing coarse-grained aluminum hydroxide by decomposing sodium aluminate solution with ultralow seed crystal amount
CN101838750A (en) Method for performing direct acid adjusting closed cycle on ammonium paratungstate crystallization mother liquor
CN103910381B (en) A kind of titanium liquid production method reducing acid consumption
EP2142477A1 (en) High-purity calcium compounds
CN104925844A (en) Method for refining high-purity cerium carbonate
CN114988383B (en) Efficient preparation method of battery-grade ferric phosphate
CN102583493A (en) Method for preparing large-particle Ce rich rare earth oxide
CN102633306A (en) High-purity trimanganese tetroxide and preparation method of same
CN110002477B (en) Preparation method of battery-grade lithium carbonate
CN116199270B (en) Treatment process for reducing wastewater in cobalt oxide production process
CN109553121B (en) Preparation method of high-purity low-sodium aluminum hydroxide
CN108516565B (en) Method for preparing P-type zeolite molecular sieve by using aluminum calcium powder reaction slag
CN114455618B (en) Method for preparing low-sodium low-iron superfine alpha-alumina and large-pore-volume pseudo-boehmite
CN103803623B (en) A kind of production method of high purity barium carbonate
KR20010084867A (en) Process for the production of extra fine powder of Cobalt
CN211920886U (en) Device for preparing battery-grade lithium carbonate by using membrane separation technology
RU2314259C1 (en) Method of processing tungsten-containing material
KR102271298B1 (en) Manufaturing method of zeolite using lithium residue

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120509