CN106379941A - Preparation method of high-purity tungsten trioxide - Google Patents
Preparation method of high-purity tungsten trioxide Download PDFInfo
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Abstract
The invention discloses a preparation method of high-purity tungsten trioxide. According to the method, firstly, tungsten is precipitated through hydrolysis; insoluble impurities are removed through the filtering under the acidic condition; then, obtained tungsten hydrolysate is added into a potassium hydroxide solution; precipitates are removed through filtering; next, a potassium carbonate solution is added; stirring is performed, and then, precipitates are removed through filtering; finally, a trace of polyvalent metal cation impurities are removed through cation exchange resin. The method has the advantages that the high-purity tungsten trioxide is obtained through preparation; the process is simple; the operation is easy; the technological flow process is shortened; the preparation cost is low; high economic benefits are realized; the problems of high production cost, product quality instability, great quantity of waste water in the production process and process complexity during the high-purity tungsten trioxide preparation in the prior art are solved.
Description
Technical field：
The present invention relates to tungstic acid preparing technical field, it is specifically related to a kind of preparation side of high-purity tungstic acid
Method.
Background technology：
Metal oxide serves key effect to the development of many advanced function materials and intelligent device.Numerous
In metal oxide, tungstic acid is a kind of more unique material, receives much concern because it has multifunctionality, three oxidations
Tungsten is a kind of N-type semiconductor, has multiple crystal formations, energy gap 2.5-2.8eV, has visible light-responded characteristic.Therefore three oxidations
Tungsten can serve as photo-sensing device, such as photochromic device and transparency electrode etc.；Tungstic acid also can be used as visible ray simultaneously
Photochemical catalyst, using the dirty organic pollutants of light power degraded and heavy metal ion, environmentally friendly and economical；Ring indoors
Border context of detection, tungstic acid can make gas sensor.
The synthesis preparation method of tungstic acid has a lot, Yong etc. with purity be 99.9% leaf as substrate, purity is
99.99% tungstic acid is raw material, has synthesized tungsten trioxide nanowires by vapours sedimentation.By leaf and tungstic acid
Put into tube furnace after the diverse location being placed on one piece of aluminium flake, tube furnace is warming up to 900-1000 DEG C, treat that it is cooled to room temperature, in base
Tungsten trioxide nanowires can be obtained on bottom, the method operating procedure is more, degradation efficiency not high it is therefore desirable to find new conjunction
One-tenth method, simple to operate, degradation efficiency can be improved again.
Content of the invention：
It is an object of the invention to provide a kind of preparation method of tungstic acid, for solving prior art high-purity three oxygen
Change tungsten to prepare the production cost height existing, unstable product quality, become to produce the problem that spent process water amount is big, technique is loaded down with trivial details.
For achieving the above object, the present invention employs the following technical solutions：
A kind of preparation method of high-purity tungstic acid, comprises the steps：First with hydrolytic precipitation tungsten, in acid bar
It is filtered to remove insoluble impurity under part；Again the tungsten hydrolysate of gained is added potassium hydroxide solution, be filtered to remove precipitation；Then add
It is filtered to remove precipitation after solution of potassium carbonate stirring；Finally go the multivalent metal cation of eliminating minute miscellaneous using cationic ion-exchange resin
Matter.
Preferably, described preparation method comprises the following steps：
The first step：Dissolving, is filtered to remove precipitated impurities after tungsten ore potassium hydroxide solution is dissolved；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 10-35g/L, pH
It is worth for 2.0-2.5, temperature value is 70-85 DEG C, stirring reaction 60-70 minute hydrolytic precipitation tungsten；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution, is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, and in adjustment solution, the concentration of tungsten is 30-
35g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 20-25%, the addition of solution of potassium carbonate is 1-1.5 times of the solution quality that the 4th successive step obtains, and is filtered to remove miscellaneous
Add sulfuric acid after matter, precipitate tungsten；
6th step：Three dissolvings, add after the tungsten interpolation potassium hydroxide solution that the 5th step precipitation is filtrated to get and go
In ionized water adjustment solution, W content is 20-25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained passes through example with the flow velocity of 1BV/h-2BV/h
Exchange column, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, regulation pH value is 8-9, adds ammonium sulfate, stirring reaction 60-
70 minutes, stand 1-2 hour；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its purity is more than
99.99%.
Preferably, in the described first step, the 4th step and the 6th step, the mass concentration of potassium hydroxide solution is 30-35%.
Preferably, in described second step solution, the concentration of tungsten is 15-30g/L, and pH value is 2.2-2.5, and temperature value is 80-85
DEG C, stirring reaction 65-70 minute.
Preferably, by acidic precipitation waste liquid, alkaline sedimentation waste liquid and scrub raffinate cycling and reutilization after treatment.
Preferably, will regenerate after the 7th step ion exchange resin adsorption saturation：
First by the hydrochloric acid solution drip washing 40-50 minute of 3-4 times of bed volume, then 1-2 times of bed volume, mass concentration are 9-
10% sodium chloride solution is the potassium hydroxide mixed solution drip washing 50-60 minute of 5-6% with mass concentration, finally uses deionization
It is washed to neutrality；After hydrochloric acid solution after parsing is used repeatedly, through distillation, the hydrogen chloride gas in solution are eliminated row
Put, hydrogen chloride gas reuse after water absorbs and becomes hydrochloric acid solution, and NaOH or sodium chloride solution are through pervaporation
After concentration, crystallisation by cooling obtains sodium chloride or sodium sulfate crystal, Returning utilization.
Preferably, the calcining heat of described tenth step high temperature calcining is 520-530 DEG C, and calcination time is 3.5-4 hour.
Tungstic acid traditional preparation methods are to be obtained by acid adding after tungsten ore and soda ash congruent melting.The important mineral of tungsten are wolframic acid
Salt.The cation being combined with [WO4] 2- complex anion in mineralization process is only several, mainly have Ca2+, Fe2+,
Mn2+, Pb2+, are secondly Cu2+, Zn2+, Al3+, Fe3+, Y3+ etc., thus mineral species are limited, nowadays only find in the earth's crust
There are more than 20 kind tungsten minerals and contain tungsten mineral, i.e. wolframite race：Huebnerite, ferberite, wolframite；Scheelite race：Scheelite (calcium tungsten
Ore deposit), seyrigite, cuproscheelite；Wolfram ocher class mineral：Wolfram ocher, the hydrotungstite, ferritungsite, yttrium wolfram ocher, cuprotungstite, anthoinite；
Uncommon tungsten mineral：Stolzite, raspite, chillagite, sammarthinite, russellite, scheteligite, yttrocrasite (contain
Tungsten), tungstenite etc..
Traditional ion exchange removal of impurities is with the anion in resin anion (R.A.) adsorbent solution, then after being purified after parsing
Tungsten solution, the ion exchange resin amount that this method needs is big, and the waste liquid producing is also many, and ion exchange resin makes simultaneously
Cycle is short, complex manufacturing.The application is combined with cationic ion-exchange resin after hydrolytic precipitation tungsten again, will simultaneously
Acid precipitation and alkaline sedimentation combine, and tentatively remove partial impurities in acid condition, then will add hydroxide in hydrolysate
Potassium solution dissolves, and removes precipitated impurities, then repeats potassium hydroxide solution washing after solution of potassium carbonate washing impurity-removing, in conjunction with
Cationic ion-exchange resin removal of impurities it is ensured that the stability of the yield and quality of product, considerably reduces containing of impurity in solution
Amount, and extend the usage cycles of ion exchange resin, increase service life, Simplified flowsheet, reduce production cost.
The invention has the advantages that：
(1) preparation process is simple of high-purity tungstic acid of the present invention, and do not need to add removal of impurities in preparation process
Agent, tungstic acid purity height, product yield and the stable performance preparing, waste liquid recoverable.
(2) the application is combined with cationic ion-exchange resin after hydrolytic precipitation tungsten again, simultaneously by acid precipitation and alkalescence
Precipitation combines, and tentatively removes partial impurities in acid condition, then will add potassium hydroxide solution dissolving in hydrolysate, removes
Go precipitated impurities, then repeat potassium hydroxide solution washing after solution of potassium carbonate washing impurity-removing, in conjunction with cation exchange tree
Fat removal of impurities, it is ensured that the stability of the yield and quality of product, considerably reduces the content of impurity in solution, and extends
The usage cycles of ion exchange resin, increase service life, Simplified flowsheet, reduce production cost, have higher economic benefit.
(3) using mass concentration, the solution of potassium carbonate for 20-25% is filtered to remove impurity to the application, the adding of solution of potassium carbonate
Plus one side can improve the purity of product, on the other hand can accelerate the exchange process of cationic ion-exchange resin, shorten technique
Process, reduces the time cost producing.
(4) waste water and waste liquid of the application can be with recycling, and the problem of a large amount of waste liquids of resin regeneration has also obtained place
Reason, had both solved a waste liquid difficult problem, had saved supplies consumption again, reduced production cost, had higher economic benefit and ecology
Benefit.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
Release the present invention, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 30%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 10g/L, and pH value is
2.0, temperature value is 70 DEG C, 60 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 30%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 20%, the addition of solution of potassium carbonate is 1 times of the solution quality that the 4th successive step obtains, add after being filtered to remove impurity
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 30%) afterwards add deionized water adjustment solution in W content be 20g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 1BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 8, adds ammonium sulfate, 60 points of stirring reaction
Clock, stands 1 hour；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 520
DEG C, calcination time is 3.5 hours, and its purity is more than 99.99%.
Embodiment 2
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 35%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 35g/L, and pH value is
2.5, temperature value is 85 DEG C, 70 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 35%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 35g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 25%, the addition of solution of potassium carbonate is 1.5 times of the solution quality that the 4th successive step obtains, and adds after being filtered to remove impurity
Plus sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 35%) afterwards add deionized water adjustment solution in W content be 25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 2BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 9, adds ammonium sulfate, 70 points of stirring reaction
Clock, stands 2 hours；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 530
DEG C, calcination time is 4 hours, and its purity is more than 99.99%.
Embodiment 3
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 30%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 35g/L, and pH value is
2.0, temperature value is 85 DEG C, 60 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 35%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 25%, the addition of solution of potassium carbonate is 1 times of the solution quality that the 4th successive step obtains, add after being filtered to remove impurity
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 35%) afterwards add deionized water adjustment solution in W content be 25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 1BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 8, adds ammonium sulfate, 70 points of stirring reaction
Clock, stands 1 hour；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 530
DEG C, calcination time is 3.5 hours, and its purity is more than 99.99%.
Embodiment 4
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 35%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 10g/L, and pH value is
2.5, temperature value is 70 DEG C, 70 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 30%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 35g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 20%, the addition of solution of potassium carbonate is 1.5 times of the solution quality that the 4th successive step obtains, and adds after being filtered to remove impurity
Plus sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 30%) afterwards add deionized water adjustment solution in W content be 25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 2BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 8, adds ammonium sulfate, 60 points of stirring reaction
Clock, stands 2 hours；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 530
DEG C, calcination time is 3.5 hours, and its purity is more than 99.99%.
Embodiment 5
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 35%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 15g/L, and pH value is
2.2, temperature value is 80 DEG C, 65 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 35%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 20%, the addition of solution of potassium carbonate is 1 times of the solution quality that the 4th successive step obtains, add after being filtered to remove impurity
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 35%) afterwards add deionized water adjustment solution in W content be 25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 1BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 8, adds ammonium sulfate, 65 points of stirring reaction
Clock, stands 2 hours；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 530
DEG C, calcination time is 3.5 hours, and its purity is more than 99.99%.
Embodiment 6
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 35%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 30g/L, and pH value is
2.2, temperature value is 85 DEG C, 65 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 35%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 25%, the addition of solution of potassium carbonate is 1 times of the solution quality that the 4th successive step obtains, add after being filtered to remove impurity
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 35%) afterwards add deionized water adjustment solution in W content be 25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 2BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 8, adds ammonium sulfate, 60 points of stirring reaction
Clock, stands 1 hour；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 525
DEG C, calcination time is 4 hours, and its purity is more than 99.99%.
Embodiment 7
A kind of preparation method of high-purity tungstic acid, comprises the following steps：
The first step：Dissolving, miscellaneous by being filtered to remove precipitation after tungsten ore potassium hydroxide solution (mass concentration is 30%) dissolving
Matter；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 20g/L, and pH value is
2.5, temperature value is 80 DEG C, 70 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution (mass concentration is 30%), is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, adjusts solution
The concentration of middle tungsten is 35g/L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the quality of solution of potassium carbonate is dense
Spend for 20%, the addition of solution of potassium carbonate is 1- times of the solution quality that the 4th successive step obtains, and adds after being filtered to remove impurity
Plus sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds potassium hydroxide solution (mass concentration
For 35%) afterwards add deionized water adjustment solution in W content be 25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 2BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, adjusting pH value is 8.5, adds ammonium sulfate, stirring reaction 65
Minute, stand 2 hours；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning,
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its calcining heat is 520
DEG C, calcination time is 4 hours, and its purity is more than 99.99%.
Comparative example 1
Embodiment 7 deletes the 5th step, does not adopt solution of potassium carbonate to process.
Comparative example 2
Embodiment 7 deletes the 7th step, does not adopt cation exchange removal of impurities to process.
Comparative example 3
Sulfuric acid precipitation tungsten will be adopted in 5th step, intermediate processing is identical with the second step of embodiment 7 in embodiment 7.
The acidic precipitation waste liquid, alkaline sedimentation waste liquid and the scrub raffinate that produce in above-described embodiment and comparative example are through processing
Posterior circle recycles.
Regenerate after above-described embodiment and comparative example ion exchange resin adsorption saturation, its renovation process is：
First by the hydrochloric acid solution drip washing 40-50 minute of 3-4 times of bed volume, then 1-2 times of bed volume, mass concentration are 9-
10% sodium chloride solution is the potassium hydroxide mixed solution drip washing 50-60 minute of 5-6% with mass concentration, finally uses deionization
It is washed to neutrality；After hydrochloric acid solution after parsing is used repeatedly, through distillation, the hydrogen chloride gas in solution are eliminated row
Put, hydrogen chloride gas reuse after water absorbs and becomes hydrochloric acid solution, and NaOH or sodium chloride solution are through pervaporation
After concentration, crystallisation by cooling obtains sodium chloride or sodium sulfate crystal, Returning utilization.
The important mineral of above-mentioned tungsten are tungstates.Can be with [WO in mineralization process4] combination of 2- complex anion
Cation is only several, mainly has Ca2+、Fe2+、Mn2+、Pb2+, secondly it is Cu2+、Zn2+、Al3+、Fe3+、Y3+Deng, thus mineral species
Class is limited, nowadays only finds to have more than 20 kind tungsten minerals in the earth's crust and contains tungsten mineral, i.e. wolframite race：Huebnerite, ferberite, black
Tungsten ore；Scheelite race：Scheelite (scheelite), seyrigite, cuproscheelite；Wolfram ocher class mineral：Wolfram ocher, the hydrotungstite, high ferrotungsten
China, yttrium wolfram ocher, cuprotungstite, anthoinite；Uncommon tungsten mineral：Stolzite, raspite, chillagite, sammarthinite, tungsten bismuth
Ore deposit, scheteligite, yttrocrasite (tungstenic), tungstenite etc..
Table one：Same tungsten ore is using different purification mode Comparative result
Table two：Comparative result different material being purified using the application method level comparative example method
The element determination method of table one and table two is ICP spectroscopic methodology.From table one it will be seen that utilizing alkali soluble solution complex acid
The effect on driving birds is not good of removing impurity by means of precipitation, may introduce new other impurities on the contrary；The method of purification of ion exchange is coordinated with alkali soluble solution
Acid precipitation matches, and ion exchange only needs to adsorb a small amount of cation impurity, can greatly improve cationic ion-exchange resin
Usage cycles.Using solution of potassium carbonate processing solution, the purity of product can be improved well, ratio is repeated several times alkali dissolving acid
Precipitation operation has and becomes apparent from excellent effect, can reduce energy consumption of reaction with Simplified flowsheet, improve tungstic acid purity.This
The different tungsten ore of three kinds of the Methods For Purification of application, all can prepare highly purified tungstic acid, illustrate that the method produces preparation
Product quality and yield all more stable.
Claims (7)
1. a kind of preparation method of high-purity tungstic acid is it is characterised in that comprise the steps：
First with hydrolytic precipitation tungsten, it is filtered to remove insoluble impurity in acid condition；
Again the tungsten hydrolysate of gained is added potassium hydroxide solution, be filtered to remove precipitation；
Then it is filtered to remove precipitation after adding solution of potassium carbonate stirring；
The multivalent metal cation impurity of eliminating minute is finally removed using cationic ion-exchange resin.
2. a kind of preparation method of high-purity tungstic acid according to claim 1 is it is characterised in that described preparation method
Comprise the following steps：
The first step：Dissolving, is filtered to remove precipitated impurities after tungsten ore potassium hydroxide solution is dissolved；
Second step:Hydrolytic precipitation tungsten, adds sulfuric acid in first step solution, and in solution, the concentration of tungsten is 10-35g/L, and pH value is
2.0-2.5, temperature value is 70-85 DEG C, stirring reaction 60-70 minute hydrolytic precipitation tungsten；
3rd step：Filter, above-mentioned solution is filtrated to get hydrolysate and the acid waste liquid of tungsten；
4th step：Secondary dissolving, adds deionized water in the hydrolysate of the tungsten that the 3rd step is obtained, then it is molten to add potassium hydroxide
Liquid, is filtrated to get the solution of tungstenic, and continues to add deionized water in filtrate, and in adjustment solution, the concentration of tungsten is 30-35g/
L；
5th step：Filter, in the solution that the 4th successive step is obtained, add solution of potassium carbonate, the mass concentration of solution of potassium carbonate is
20-25%, the addition of solution of potassium carbonate is 1-1.5 times of the solution quality that the 4th successive step obtains, after being filtered to remove impurity
Add sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the tungsten that the 5th step precipitation is filtrated to get adds and adds deionization after potassium hydroxide solution
In water adjustment solution, W content is 20-25g/L；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged by example with the flow velocity of 1BV/h-2BV/h
Post, obtains tungstenic scavenging solution；
8th step：Precipitation tungsten, in the state of stirring, regulation pH value is 8-9, adds ammonium sulfate, and stirring reaction 60-70 is divided
Clock, stands 1-2 hour；
9th step：Filter, after solution described in the 8th step is filtered, solid spends ion-cleaning；
Tenth step：Calcining, obtains tungstic acid by after solid high-temperature calcining after the 9th step washing, its purity is more than 99.99%.
3. a kind of high-purity tungstic acid according to claim 2 preparation method it is characterised in that：The described first step,
In 4th step and the 6th step, the mass concentration of potassium hydroxide solution is 30-35%.
4. a kind of high-purity tungstic acid according to claim 2 preparation method it is characterised in that：Described second step is molten
In liquid, the concentration of tungsten is 15-30g/L, and pH value is 2.2-2.5, and temperature value is 80-85 DEG C, stirring reaction 65-70 minute.
5. a kind of high-purity tungstic acid according to claim 2 preparation method it is characterised in that：Acidic precipitation is given up
Liquid, alkaline sedimentation waste liquid and scrub raffinate cycling and reutilization after treatment.
6. a kind of high-purity tungstic acid according to claim 2 preparation method it is characterised in that：By the 7th step ion
Regenerate after exchanger resin adsorption saturation, its renovation process is：First by the hydrochloric acid solution drip washing 40-50 minute of 3-4 times of bed volume,
The potassium hydroxide being 5-6% by 1-2 times of bed volume, the sodium chloride solution for 9-10% for the mass concentration with mass concentration again mixes molten
Liquid drip washing 50-60 minute, last deionized water is washed till neutrality；After hydrochloric acid solution after parsing is used repeatedly, Jing Guozheng
Evaporate and the hydrogen chloride gas in solution are eliminated discharge, hydrogen chloride gas reuse after water absorbs and becomes hydrochloric acid solution, hydrogen
Sodium oxide molybdena or sodium chloride solution crystallisation by cooling after being concentrated by evaporation obtain sodium chloride or sodium sulfate crystal, Returning utilization.
7. a kind of high-purity tungstic acid according to claim 2 preparation method it is characterised in that：In described tenth step
The calcining heat of high-temperature calcination is 520-530 DEG C, and calcination time is 3.5-4 hour.
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| CN112642420A (en) * | 2020-12-22 | 2021-04-13 | 湖南工业大学 | High-concentration molybdenum-doped tungsten trioxide photocatalytic nano material and preparation method thereof |
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