CN101774643A - Process for preparing tungstic oxide hydrate from sodium tungstate solution - Google Patents
Process for preparing tungstic oxide hydrate from sodium tungstate solution Download PDFInfo
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- CN101774643A CN101774643A CN201010022046A CN201010022046A CN101774643A CN 101774643 A CN101774643 A CN 101774643A CN 201010022046 A CN201010022046 A CN 201010022046A CN 201010022046 A CN201010022046 A CN 201010022046A CN 101774643 A CN101774643 A CN 101774643A
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- sodium tungstate
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- tungstate solution
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Abstract
The invention relates to a process for preparing a tungstic oxide hydrate from a sodium tungstate solution, which comprises the following steps: putting the sodium tungstate aqueous solution, CO2 gas, inorganic acid, organic acid, organic sugar or derivatives together into a high pressure reactor for hydro-thermal treatment to obtain WO3.nH2O seriflux, and obtaining a tungstic oxide product through filtering separation and roasting at a low temperature. The invention has mild preparation conditions, simple operation, has no high requirement on equipment and low cost; the quality of the product is better than that of the traditional method, does not contain impurity elements such as Na and the like, and the decomposing conversion rate of the sodium tungstate solution is more than 98%; compared with the traditional process, the method saves the production steps of ammonium tungstate and APT, greatly simplifies the process flow; and the whole flow can form a closed cycle, does not discharge pollutants of any type, and avoids the pollution from the source.
Description
Technical field
The present invention relates to a kind of mineral acid, organic acid or derivatives thereof, organic carbohydrate or derivatives thereof of adopting and do the method that additive hydrothermal decomposition sodium wolframate prepares tungstic oxide hydrate, belong to inorganic chemicals industry production and powder body material preparation field.
Background technology
Tungsten oxide 99.999 mainly is used as the preparation tungsten, also is widely used in various fields such as metallurgy, preparation functional materials, photoelectrochemistry, catalyzer, tinting material simultaneously.The scientific research personnel finds the many characteristic of Tungsten oxide 99.999 at aspects such as optics, magnetics, electronics again successively in recent years, and its Application and Development is also more and more attracted attention.
In existing tungsten smelting system owing to contain Determination of Multi-Impurities in the thick solution of industrial sodium wolframate, and must could all remove through the substep removal of impurities, cause whole smelting flow process tediously long, in a large number expend the energy, increase environmental stress.The process of wherein removing Na is the most loaded down with trivial details, need increase ammonium tungstate, two kinds of intermediate products of APT effectively to remove, its major cause is: the method that directly precipitates W elements in conventional thought from sodium tungstate solution can only be the preparation wolframic acid, and the sodium tungstate solution acidifying prepares in the sedimentary process of wolframic acid, can produce the tungsten multi-acid salt and the heteropolyacid salt of multiple complexity, generate with the white tungstic acid that is difficult to filtration washing simultaneously, cause the Na element to be entrained in inevitably in the precipitation, must be by the Ex-all of ammonio method ability.A kind of effective way that addresses this problem is to find very little tungsten oxide of a kind of solubleness or tungsten oxyhydroxide in slight alkali environment.
Summary of the invention
The invention provides a kind of technology that adopts hydrothermal method to decompose sodium tungstate solution, the tungstic oxide hydrate that adopts this explained hereafter to go out does not contain the Na element, simplify the Tungsten oxide 99.999 Production Flow Chart greatly, reduced production cost, and do not discharged any type of pollutent in the whole process of production.
A kind ofly prepare the technology of tungstic oxide hydrate, may further comprise the steps from sodium tungstate solution:
The certain density sodium wolframate aqueous solution of 1 allotment;
2 place autoclave to carry out hydrothermal decomposition with additive according to suitable proportioning the sodium wolframate aqueous solution, and the pH of adjustment and control system is stabilized in certain scope in the reaction process, obtains WO
30.5H
2The O slip;
3 washings, filtering separation slip obtain WO
30.5H
2O filter cake and mother liquor;
4 filter cakes carry out low-temperature bake in stoving oven;
5 mother liquors carry out evaporation concentration, crystallisation by cooling, filtering separation, obtain solid sodium salt and crystalline mother solution;
The concentration of step (1) sodium tungstate solution preferably is controlled at 30%～45%.
The temperature of step (2) hydro-thermal reaction is 100～250 ℃, and the time is 5～25 hours; Additive amount is 110%～200% of a sodium wolframate by chemical equation metering mol ratio; System pH is controlled between 6.5～9.0.Wherein hydrothermal system pH preferably is controlled at about 7.0, has so both avoided generation tungsten multi-acid salt, can guarantee speed of reaction faster again.
The described additive of step (2) comprises inorganic acids (as carbonic acid, hydrochloric acid, sulfuric acid etc.), organic acid (as tartrate, maleic acid etc.) or/and its derivative, organic carbohydrate (as sucrose, maltose etc.) or/and its derivative, or any mixture between them.
The described maturing temperature of step (4) is 300～450 ℃, need not protective atmosphere.
The described crystalline mother solution of step (5) returns ore and leaches operation or sodium wolframate aqueous solution allotment operation.
The present invention regulates and control the pH value of sodium wolframate hydrothermal system in 6.5～9.0 scope, avoids positive wolframate radical that complicated the transformation taken place, and prepares the WO that does not contain the Na element
30.5H
2O precipitates, thereby can save the production process of ammonium tungstate, APT, greatly reduces energy consumption, alleviates environmental pressure, and has a clear superiority on the preparation superfine powder.
Among the present invention, the hydro-thermal reaction product is the tungstic oxide hydrate that does not contain Na, need not to generate operation through intermediates ammonium tungstate, APT, so technical process is simple, equipment is simple, and is simple to operate, and cost is low.Whole technology forms closed cycle, has realized the recycle of mother liquor and washing lotion, does not discharge any type of pollutent in the whole process, has avoided pollution from the source.In addition, the Tungsten oxide 99.999 diameter of particle that this invention is prepared is evenly distributed, and median size is about 1.0 μ m, has great advantage in the preparation of superfine powder.
Description of drawings
Fig. 1: the present invention prepares the technical process of Tungsten oxide 99.999 principle, and (with the additive is CO
2Be example) synoptic diagram.
Embodiment
Embodiment 1:
In autoclave, put into massfraction and be 45% sodium tungstate solution, under elevated pressures, force to feed CO
2Gas is about 7 to pH, the lasting CO that feeds
2And to keep hydrothermal temperature be 180 ℃, and in 24 hours reaction times, the rate of decomposition of sodium tungstate solution is 99.25%.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 400 ℃ of roastings 3 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates is back to the ore extract technology after washing lotion is carried out evaporation concentration, realize the recycle of alkali.Whole flow process forms closed cycle, does not discharge any type of pollutent in the whole process, has avoided pollution from the source.
Embodiment 2:
In autoclave, put into massfraction and be 25% sodium tungstate solution 100ml, it is 6.5 that dilute hydrochloric acid with 5% is adjusted pH, is heated to 150 ℃, adds dilute hydrochloric acid in the reaction process system pH is remained at about 7.5, in 18 hours reaction times, the rate of decomposition of sodium tungstate solution is 98.13%.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 4 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Embodiment 3:
Put into massfraction and be 30% sodium tungstate solution 100ml in autoclave, add maleic acid, be heated to 160 ℃, pH remains at about 7.2～7.5 in the reaction process, and in 24 hours reaction times, the rate of decomposition of sodium tungstate solution is 99.22%.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 4 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Embodiment 4:
In autoclave, put into massfraction and be 40% sodium tungstate solution 100ml, add sucrose to pH be 9.5, be heated to 180 ℃, pH remains at about 7.9～8.2 in the reaction process, in 72 hours reaction times, the rate of decomposition of sodium tungstate solution is 98.48% as a result.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 5 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Embodiment 5:
In autoclave, put into massfraction and be 45% sodium tungstate solution 100ml, add sucrose to pH be 9.5, adjusting pH with 5% dilute hydrochloric acid again is 6.5, be heated to 170 ℃, pH is remained at about 7.6～8.2, in 60 hours reaction times, the rate of decomposition of sodium tungstate solution is 98.71% as a result.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 5 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Embodiment 6:
In autoclave, put into massfraction and be 43% sodium tungstate solution 100ml, add sucrose acid to pH be 8.5, be heated to 180 ℃, reaction process can make pH remain at about 7.5～8.2, in 48 hours reaction times, the rate of decomposition of sodium tungstate solution is 98.92% as a result.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 5 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Embodiment 7:
In autoclave, put into massfraction and be 45% sodium tungstate solution 100ml, add the butadiene dilute acid formicester to pH be 9.5, adjusting pH with 5% dilute hydrochloric acid again is 6.5, be heated to 160 ℃, pH is remained at about 7.6～8.2, in 40 hours reaction times, the rate of decomposition of sodium tungstate solution is 98.87% as a result.The slip that obtains is easy to filtering separation, and the WO30.5H2O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 5 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Embodiment 8:
In autoclave, put into massfraction and be 44% sodium tungstate solution 100ml, add the butadiene dilute acid formicester, be heated to 170 ℃, pH is remained at about 7.7～8.3, in 50 hours reaction times, the rate of decomposition of sodium tungstate solution is 98.78% as a result.The slip that obtains is easy to filtering separation, WO
30.5H
2The O filter cake is cleaned with deionized water, then wet cake is put into stoving oven, and 300 ℃ of roastings 5 hours, Tungsten oxide 99.999 got product.Mother liquor after slip separates carries out evaporative crystallization, separation, and the crystalline mother solution that obtains returns the sodium tungstate solution preparation process.
Claims (6)
1. prepare the technology of tungstic oxide hydrate from sodium tungstate solution, may further comprise the steps:
1) the allotment sodium wolframate aqueous solution;
2) place autoclave to carry out hydro-thermal reaction with additive the sodium wolframate aqueous solution, obtain WO
30.5H
2The O slip;
3) the filtering separation slip obtains WO
30.5H
2O filter cake and mother liquor;
4) mother liquor carries out evaporation concentration, crystallisation by cooling, filtering separation, obtains solid sodium salt and crystalline mother solution;
5) filter cake carries out low-temperature bake and gets the Tungsten oxide 99.999 finished product in stoving oven;
It is characterized in that: described additive is inorganic acids, organic acid or/and its derivative, organic carbohydrate or/and its derivative, additive amount is 110%～200% of a sodium wolframate by chemical equation metering mol ratio; The temperature of hydro-thermal reaction is 100～250 ℃, and the time is 5～25 hours; The pH modification scope is 6.5～9.0 in the hydrothermal reaction process.
2. technology according to claim 1 is characterized in that: described organic acid comprises tartrate or maleic acid.
3. technology according to claim 1 is characterized in that: described mineral acid comprises carbonic acid or hydrochloric acid or sulfuric acid.
4. technology according to claim 1 is characterized in that: described organic carbohydrate comprises sucrose or maltose.
5. technology according to claim 1 is characterized in that: described derivative comprises sour sex change derivative or alkaline denaturation organism.
6. technology according to claim 1 is characterized in that: crystalline mother solution returns tungsten ore and leaches operation or sodium wolframate aqueous solution allotment operation, and reclaims in the crystalline mother solution the not additive of complete reaction.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102320662A (en) * | 2011-07-04 | 2012-01-18 | 大连工业大学 | Cesium tungsten bronze powder and preparation method thereof |
| CN102557138A (en) * | 2011-12-27 | 2012-07-11 | 江西稀有金属钨业控股集团有限公司 | Method for preparing molybdenum trioxide |
| CN102963932A (en) * | 2012-11-13 | 2013-03-13 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine molybdenum trioxide |
| CN102963935A (en) * | 2012-11-13 | 2013-03-13 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine tungsten trioxide |
| CN103272582A (en) * | 2013-05-09 | 2013-09-04 | 哈尔滨工业大学 | Method for synthesizing pyrochlore type cubic phase semihydrate tungsten trioxide photocatalyst |
| CN103420424A (en) * | 2013-05-21 | 2013-12-04 | 新疆大学 | Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough |
| CN105771963A (en) * | 2016-04-01 | 2016-07-20 | 东南大学 | Wool ball shaped tungsten trioxide (WO3) photocatalyst and green synthetic method thereof |
| CN105836806A (en) * | 2016-05-20 | 2016-08-10 | 中南大学 | Method for directly preparing pyrochlore type tungsten oxide from ammonium tungstate solution |
| CN105858731A (en) * | 2016-05-20 | 2016-08-17 | 江钨高技术开发应用有限公司 | Method for directly preparing pyrochlore type tungsten oxide from ammonium tungstate solution |
| CN106006742A (en) * | 2016-05-20 | 2016-10-12 | 江钨高技术开发应用有限公司 | Method for preparing pyrochlore tungsten oxide from ammonium paratungstate through hydrothermal conversion |
| CN106191455A (en) * | 2016-07-08 | 2016-12-07 | 大余县东宏锡制品有限公司 | A kind of tungsten essence artware preparation method refined from ammonium paratungstate solid slag |
| CN106311217A (en) * | 2016-08-19 | 2017-01-11 | 浙江师范大学 | Preparation method of Activated carbon functionalized tungsten oxide |
| CN108862389A (en) * | 2017-05-16 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of high-performance tungsten oxide nano-powder and its preparation method and application |
| CN109449411A (en) * | 2018-10-30 | 2019-03-08 | 陕西科技大学 | A kind of method of confinement synthesis tungsten disulfide@C combination electrode material |
| CN114835165A (en) * | 2022-04-19 | 2022-08-02 | 云南锡业集团（控股）有限责任公司研发中心 | Method for directly producing tungsten oxide powder by adopting sodium tungstate solution |
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2010
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| CN102320662A (en) * | 2011-07-04 | 2012-01-18 | 大连工业大学 | Cesium tungsten bronze powder and preparation method thereof |
| CN102557138A (en) * | 2011-12-27 | 2012-07-11 | 江西稀有金属钨业控股集团有限公司 | Method for preparing molybdenum trioxide |
| CN102963932A (en) * | 2012-11-13 | 2013-03-13 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine molybdenum trioxide |
| CN102963935A (en) * | 2012-11-13 | 2013-03-13 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine tungsten trioxide |
| CN102963932B (en) * | 2012-11-13 | 2014-06-18 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine molybdenum trioxide |
| CN103272582A (en) * | 2013-05-09 | 2013-09-04 | 哈尔滨工业大学 | Method for synthesizing pyrochlore type cubic phase semihydrate tungsten trioxide photocatalyst |
| CN103272582B (en) * | 2013-05-09 | 2014-12-03 | 哈尔滨工业大学 | Method for synthesizing pyrochlore type cubic phase semihydrate tungsten trioxide photocatalyst |
| CN103420424A (en) * | 2013-05-21 | 2013-12-04 | 新疆大学 | Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough |
| CN103420424B (en) * | 2013-05-21 | 2015-05-20 | 新疆大学 | Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough |
| CN105771963B (en) * | 2016-04-01 | 2018-07-17 | 东南大学 | A kind of knitting wool bulk tungsten trioxide photocatalyst and its green synthesis method |
| CN105771963A (en) * | 2016-04-01 | 2016-07-20 | 东南大学 | Wool ball shaped tungsten trioxide (WO3) photocatalyst and green synthetic method thereof |
| CN105836806A (en) * | 2016-05-20 | 2016-08-10 | 中南大学 | Method for directly preparing pyrochlore type tungsten oxide from ammonium tungstate solution |
| CN105858731A (en) * | 2016-05-20 | 2016-08-17 | 江钨高技术开发应用有限公司 | Method for directly preparing pyrochlore type tungsten oxide from ammonium tungstate solution |
| CN106006742A (en) * | 2016-05-20 | 2016-10-12 | 江钨高技术开发应用有限公司 | Method for preparing pyrochlore tungsten oxide from ammonium paratungstate through hydrothermal conversion |
| CN106191455A (en) * | 2016-07-08 | 2016-12-07 | 大余县东宏锡制品有限公司 | A kind of tungsten essence artware preparation method refined from ammonium paratungstate solid slag |
| CN106311217A (en) * | 2016-08-19 | 2017-01-11 | 浙江师范大学 | Preparation method of Activated carbon functionalized tungsten oxide |
| CN106311217B (en) * | 2016-08-19 | 2020-04-17 | 浙江师范大学 | Preparation method of activated carbon functionalized tungsten oxide |
| CN108862389A (en) * | 2017-05-16 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of high-performance tungsten oxide nano-powder and its preparation method and application |
| CN109449411A (en) * | 2018-10-30 | 2019-03-08 | 陕西科技大学 | A kind of method of confinement synthesis tungsten disulfide@C combination electrode material |
| CN109449411B (en) * | 2018-10-30 | 2020-12-01 | 陕西科技大学 | Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain |
| CN114835165A (en) * | 2022-04-19 | 2022-08-02 | 云南锡业集团（控股）有限责任公司研发中心 | Method for directly producing tungsten oxide powder by adopting sodium tungstate solution |
| CN114835165B (en) * | 2022-04-19 | 2024-03-22 | 云南锡业集团（控股）有限责任公司研发中心 | Method for directly producing tungsten oxide powder by adopting sodium tungstate solution |
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Application publication date: 20100714 |