CN106379941B - A kind of preparation method of high-purity tungstic acid - Google Patents
A kind of preparation method of high-purity tungstic acid Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of high-purity tungstic acid, first with hydrolytic precipitation tungsten, insoluble impurity is filtered to remove in acid condition；The tungsten hydrolysate of gained is added into potassium hydroxide solution again, precipitation is filtered to remove；Then it is filtered to remove precipitation after the stirring of addition solution of potassium carbonate；Micro multivalent metal cation impurity is finally removed using cationic ion-exchange resin.The inventive method prepares a kind of tungstic acid of high-purity, technique is simple to operation, shorten technological process, prepare cost low, with higher economic benefit, solve prior art high-purity tungstic acid and prepare the production cost height existed, unstable product quality, into the problem of production spent process water amount is big, technique is cumbersome.
Description
Technical field：
The present invention relates to tungstic acid preparing technical field, a kind of preparation side of high-purity tungstic acid is specifically related to
Method.
Background technology：
Development of the metal oxide to many advanced function materials and intelligent device serves key effect.Numerous
In metal oxide, tungstic acid is a kind of material of more uniqueness, because it has multi-functional and receives much concern, three oxidations
Tungsten is a kind of N-type semiconductor, there is a variety of crystal formations, energy gap 2.5-2.8eV, with visible light-responded characteristic.Therefore three oxidation
Tungsten may be used as photo-sensing device, such as photochromic device and transparency electrode；Tungstic acid can also be used as visible ray simultaneously
Photochemical catalyst, utilizes the dirty organic pollutants of light power degraded and heavy metal ion, environmentally friendly and economy；Ring indoors
Border context of detection, tungstic acid can make gas sensor.
The synthesis preparation method of tungstic acid has a lot, Yong etc. using purity be 99.9% leaf as substrate, purity is
99.99% tungstic acid is raw material, and tungsten trioxide nanowires have been synthesized by vapours sedimentation.By leaf and tungstic acid
Tube furnace is put into after the diverse location for being placed on one piece of aluminium flake, tube furnace is warming up to 900-1000 DEG C, treats that it is cooled to room temperature, in base
Tungsten trioxide nanowires can be obtained on bottom, this method operating procedure is more, and degradation efficiency is not high, it is therefore desirable to find new conjunction
It is simple to operate into method, degradation efficiency can be improved again.
The content of the invention：
It is an object of the invention to provide a kind of preparation method of tungstic acid, for solving the oxygen of prior art high-purity three
Change tungsten and prepare the production cost height existed, unstable product quality, into the problem of production spent process water amount is big, technique is cumbersome.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of high-purity tungstic acid, comprises the following steps：First with hydrolytic precipitation tungsten, in acid bar
Insoluble impurity is filtered to remove under part；The tungsten hydrolysate of gained is added into potassium hydroxide solution again, precipitation is filtered to remove；Then add
Precipitation is filtered to remove after solution of potassium carbonate stirring；It is miscellaneous finally micro multivalent metal cation to be removed using cationic ion-exchange resin
Matter.
It is preferred that, the preparation method comprises the following steps：
The first step：Dissolving, precipitated impurities are filtered to remove after tungsten ore is dissolved with potassium hydroxide solution；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution is 10-35g/L, pH
It is worth for 2.0-2.5, temperature value is 70-85 DEG C, 60-70 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for the tungsten that the 3rd step is obtained, then adds hydroxide
Potassium solution, is filtrated to get the solution of tungstenic, and the concentration for continuing to add tungsten in deionized water, adjustment solution into filtrate is 30-
35g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 20-25%, 1-1.5 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove miscellaneous
Sulfuric acid is added after matter, tungsten is precipitated；
6th step：Three dissolvings, the 5th step is precipitated to add after the tungsten addition addition potassium hydroxide solution being filtrated to get and gone
W content is 20-25g/L in ionized water adjustment solution；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained passes through example with 1BV/h-2BV/h flow velocity
Exchange column, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8-9, adds ammonium sulfate, stirring reaction 60-
70 minutes, stand 1-2 hours；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, obtains tungstic acid, its purity is more than after the 9th step is washed after solid high-temperature calcining
99.99%.
It is preferred that, the mass concentration of potassium hydroxide solution is 30-35% in the first step, the 4th step and the 6th step.
It is preferred that, the concentration of tungsten is 15-30g/L in the second step solution, and pH value is 2.2-2.5, and temperature value is 80-85
DEG C, stirring reaction 65-70 minutes.
It is preferred that, by acidic precipitation waste liquid, alkaline sedimentation waste liquid and scrub raffinate cycling and reutilization after treatment.
It is preferred that, it will be regenerated after the 7th step ion exchange resin adsorption saturation：
The hydrochloric acid solution of 3-4 times of bed volume is eluted 40-50 minute first, then by 1-2 times of bed volume, mass concentration is 9-
10% sodium chloride solution is eluted 50-60 minutes with mass concentration for 5-6% potassium hydroxide mixed solution, finally uses deionization
It is washed to neutrality；After hydrochloric acid solution after parsing is used repeatedly, the hydrogen chloride gas in solution is eliminated into row by distillation
Put, hydrogen chloride gas is reused after water absorption becomes hydrochloric acid solution, and sodium hydroxide or sodium chloride solution are through pervaporation
Crystallisation by cooling obtains sodium chloride or sodium sulfate crystal, Returning utilization after concentration.
It is preferred that, the calcining heat of the tenth step high temperature calcining is 520-530 DEG C, and calcination time is 3.5-4 hours.
Tungstic acid traditional preparation methods are obtained by acid adding after tungsten ore and soda ash congruent melting.The important mineral of tungsten are wolframic acid
Salt.The cation that can be combined in mineralization process with [WO4] 2- complex anions is only several, mainly have Ca2+, Fe2+,
Mn2+, Pb2+, are secondly Cu2+, Zn2+, Al3+, Fe3+, Y3+ etc., thus mineral species are limited, nowadays only found in the earth's crust
There are more than 20 kind tungsten minerals and containing 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 after being purified with the anion in resin anion (R.A.) adsorbent solution, then after parsing
Tungsten solution, the ion exchange resin amount that this method needs is big, and the waste liquid produced is also more, while ion exchange resin makes
Cycle is short, complex manufacturing.The application simultaneously will by being combined again with cationic ion-exchange resin after hydrolytic precipitation tungsten
Acid precipitation and alkaline sedimentation are combined, preliminary in acid condition to remove partial impurities, then hydroxide will be added 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 for impurity in solution
Amount, and the usage cycles of ion exchange resin are extended, increase service life, simplify technique, reduce production cost.
The invention has the advantages that：
(1) preparation technology of high-purity tungstic acid of the present invention is simple, and need not add in preparation process removal of impurities
Agent, the tungstic acid purity prepared is high, and product yield and performance are stable, waste liquid recoverable.
(2) the application with cationic ion-exchange resin by being combined again after hydrolytic precipitation tungsten, while acid is precipitated and alkalescence
Precipitation is combined, preliminary in acid condition to remove partial impurities, then potassium hydroxide solution dissolving will be added in hydrolysate, removed
Precipitated impurities are gone, then potassium hydroxide solution washing is repeated 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, simplify technique, production cost are reduced, with higher economic benefit.
(3) the application uses mass concentration to be filtered to remove impurity for 20-25% solution of potassium carbonate, and solution of potassium carbonate adds
Plus the purity of product on the one hand can be improved, it on the other hand can accelerate the exchange process of cationic ion-exchange resin, shorten technique
Process, reduces the time cost of production.
(4) waste water and waste liquid of the application can also obtain place with recycling, the problem of a large amount of waste liquids of resin regeneration
Reason, had both solved waste liquid problem, supplies consumption has been saved again, and reduced production cost, with higher economic benefit and ecology
Benefit.
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 solution
The present invention is released, 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 30%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 20%, 1 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 20g/L for 30%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 1BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8, adds ammonium sulfate, 60 points of stirring reaction
Clock, stands 1 hour；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 35%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 35g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 25%, 1.5 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Plus sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 25g/L for 35%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 2BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 9, adds ammonium sulfate, 70 points of stirring reaction
Clock, stands 2 hours；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 30%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 25%, 1 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 25g/L for 35%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 1BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8, adds ammonium sulfate, 70 points of stirring reaction
Clock, stands 1 hour；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 35%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 35g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 20%, 1.5 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Plus sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 25g/L for 30%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 2BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8, adds ammonium sulfate, 60 points of stirring reaction
Clock, stands 2 hours；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 35%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 20%, 1 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 25g/L for 35%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 1BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8, adds ammonium sulfate, 65 points of stirring reaction
Clock, stands 2 hours；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 35%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 30g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 25%, 1 times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Sulfuric acid, precipitates tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 25g/L for 35%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 2BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8, adds ammonium sulfate, 60 points of stirring reaction
Clock, stands 1 hour；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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, is filtered to remove precipitation miscellaneous after tungsten ore is dissolved with potassium hydroxide solution (mass concentration is 30%)
Matter；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution 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：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Deionized water is added in secondary dissolving, the hydrolysate for 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 addition deionized water into filtrate, adjusts solution
The concentration of middle tungsten is 35g/L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, the quality of solution of potassium carbonate is dense
Spend for 20%, 1- times of the solution quality that the addition of solution of potassium carbonate obtains for the 4th successive step, be filtered to remove after impurity and add
Plus sulfuric acid, precipitate tungsten；
6th step：Three dissolvings, the 5th step are precipitated the tungsten addition addition potassium hydroxide solution (mass concentration being filtrated to get
It is 25g/L for 35%) addition deionized water adjusts W content in solution afterwards；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained is exchanged with 2BV/h flow velocity by example
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8.5, adds ammonium sulfate, stirring reaction 65
Minute, stand 2 hours；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step,
Tenth step：Calcining, tungstic acid is obtained after the 9th step is washed after solid high-temperature calcining, and 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 use solution of potassium carbonate to handle.
Comparative example 2
Embodiment 7 deletes the 7th step, does not use cation exchange removal of impurities to handle.
Comparative example 3
Sulfuric acid precipitation tungsten will be used in the 5th step in embodiment 7, intermediate processing is identical with the second step of embodiment 7.
Acidic precipitation waste liquid, alkaline sedimentation waste liquid and the scrub raffinate produced in above-described embodiment and comparative example is by processing
Posterior circle is recycled.
Regenerated after above-described embodiment and comparative example ion exchange resin adsorption saturation, its renovation process is：
The hydrochloric acid solution of 3-4 times of bed volume is eluted 40-50 minute first, then by 1-2 times of bed volume, mass concentration is 9-
10% sodium chloride solution is eluted 50-60 minutes with mass concentration for 5-6% potassium hydroxide mixed solution, finally uses deionization
It is washed to neutrality；After hydrochloric acid solution after parsing is used repeatedly, the hydrogen chloride gas in solution is eliminated into row by distillation
Put, hydrogen chloride gas is reused after water absorption becomes hydrochloric acid solution, and sodium hydroxide or sodium chloride solution are through pervaporation
Crystallisation by cooling obtains sodium chloride or sodium sulfate crystal, Returning utilization after concentration.
The important mineral of above-mentioned tungsten are tungstates.Can be with [WO in mineralization process4] combination of 2- complex anions
Cation is only several, mainly there is Ca2+、Fe2+、Mn2+、Pb2+, secondly it is Cu2+、Zn2+、Al3+、Fe3+、Y3+Deng, thus mineral species
Class is limited, nowadays only finds there are more than 20 kind tungsten minerals and containing tungsten mineral, i.e. wolframite race in the earth's crust：It is 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 uses different purification mode Comparative results
Table two：The Comparative result purified using the application method level comparative example method to different material
The element determination method of table one and table two is ICP spectroscopic methodologies.From table one it will be seen that utilizing alkali soluble solution complex acid
The effect of removing impurity by means of precipitation is not good, and new other impurities may be introduced on the contrary；The method of purification of ion exchange coordinates with alkali soluble solution
Acid precipitation is engaged, 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, than alkali dissolving acid is repeated several times
Precipitation operation has more obvious excellent effect, can simplify technique, reduces energy consumption of reaction, improves tungstic acid purity.This
The different tungsten ores of three kinds of Methods For Purification of application, can prepare the tungstic acid of high-purity, illustrate this method production preparation
Product quality and yield it is all more stable.
Claims (6)
1. a kind of preparation method of high-purity tungstic acid, it is characterised in that the preparation method comprises the following steps：
The first step：Dissolving, precipitated impurities are filtered to remove after tungsten ore is dissolved with potassium hydroxide solution；
Second step:Hydrolytic precipitation tungsten, the concentration that tungsten in sulfuric acid, solution is added into first step solution is 10-35g/L, and pH value is
2.0-2.5, temperature value is 70-85 DEG C, 60-70 minutes hydrolytic precipitation tungsten of stirring reaction；
3rd step：Filtering, above-mentioned solution is filtrated to get the hydrolysate and acid waste liquid of tungsten；
4th step：Add deionized water in secondary dissolving, the hydrolysate for the tungsten that the 3rd step is obtained, then to add potassium hydroxide molten
Liquid, is filtrated to get the solution of tungstenic, and the concentration for continuing to add tungsten in deionized water, adjustment solution into filtrate is 30-35g/
L；
5th step：Solution of potassium carbonate is added in filtering, the solution that the 4th successive step is obtained, 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 is obtained, and is filtered to remove after impurity
Sulfuric acid is added, tungsten is precipitated；
6th step：Three dissolvings, the 5th step are precipitated the tungsten being filtrated to get and add addition deionized water tune after potassium hydroxide solution
W content is 20-25g/L in whole solution；
7th step：Ion exchange removal of impurities, the tungstenic solution that the 6th step is obtained passes through ion exchange with 1BV/h-2BV/h flow velocity
Post, obtains tungstenic scavenging solution；
8th step：Tungsten is precipitated, in the state of stirring, regulation pH value is 8-9, add ammonium sulfate, 60-70 points of stirring reaction
Clock, stands 1-2 hours；
9th step：Filtering, ion-cleaning is spent by solid after solution filtering described in the 8th step；
Tenth step：Calcining, obtains tungstic acid, its purity is more than 99.99% after the 9th step is washed after solid high-temperature calcining.
2. a kind of preparation method of high-purity tungstic acid according to claim 1, it is characterised in that：The first step,
The mass concentration of potassium hydroxide solution is 30-35% in 4th step and the 6th step.
3. a kind of preparation method of high-purity tungstic acid according to claim 1, it is characterised in that：The second step is molten
The concentration of tungsten is 15-30g/L in liquid, and pH value is 2.2-2.5, and temperature value is 80-85 DEG C, stirring reaction 65-70 minutes.
4. a kind of preparation method of high-purity tungstic acid according to claim 1, it is characterised in that：Acidic precipitation is given up
Liquid, alkaline sedimentation waste liquid and scrub raffinate cycling and reutilization after treatment.
5. a kind of preparation method of high-purity tungstic acid according to claim 1, it is characterised in that：By the 7th step ion
Regenerated after exchanger resin adsorption saturation, its renovation process is：The hydrochloric acid solution of 3-4 times of bed volume is eluted 40-50 minutes first,
The sodium chloride solution that 1-2 times of bed volume, mass concentration are 9-10% with the potassium hydroxide that mass concentration is 5-6% is mixed molten again
Liquid is eluted 50-60 minutes, is finally washed with deionized water to neutrality；After hydrochloric acid solution after parsing is used repeatedly, by steaming
Evaporate and the hydrogen chloride gas in solution is eliminated into discharge, hydrogen chloride gas is reused after water absorption becomes hydrochloric acid solution, hydrogen
Sodium oxide molybdena or the sodium chloride solution crystallisation by cooling after evaporation and concentration obtain sodium chloride or sodium sulfate crystal, Returning utilization.
6. a kind of preparation method of high-purity tungstic acid according to claim 1, it is characterised in that：In tenth step
The calcining heat of high-temperature calcination is 520-530 DEG C, and calcination time is 3.5-4 hours.
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