CN108441629A - A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder - Google Patents
A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder Download PDFInfo
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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Abstract
The present invention relates to a kind of acid to decompose the Scheelite-Wolframite Mixed Mine method for preparing tungsten oxide and tungsten powder, this method using Scheelite-Wolframite Mixed Mine as raw material, including：(1) Leach reaction；(2) filtration washing；(3) extraction tungsten is decomposed in hydrogen peroxide extraction；(4) hydrogen peroxide repeatedly dissolves decomposition purification wolframic acid；(5) calcining of pure tungsten acid prepares tungstic acid；(6) peroxide tungstic acid spray pyrolysis prepares tungsten oxide and tungsten powder.The method of the invention actually only consumes cheap and easily-available sulfuric acid, greatly reduces Scheelite-Wolframite Mixed Mine disaggregated cost；It is decomposed using acid, decomposition slag is gypsum, can be used as building materials, not generate dangerous waste soda boiling slag, greatly reduces enterprise's production and operation cost；Extractant using hydrogen peroxide as wolframic acid, does not generate ammonia nitrogen waste water, has got rid of Tungsten smelting and has continued to use the technique for generating ammonia nitrogen waste water for many years, has greatly reduced environmentally friendly cost；The end product and tungsten powder for directly producing various tungsten, improve the added value of product of Tungsten smelting enterprise.
Description
Technical field
The present invention relates to chemical production fields, and in particular to it is a kind of acid decompose Scheelite-Wolframite Mixed Mine prepare tungsten oxide and tungsten powder
Method.
Background technology
The mainstream technology of industrial processing Scheelite-Wolframite Mixed Mine is first to obtain coarse sodium tungstate using sodium hydroxide autoclaving at present
Solution and soda boiling slag.Coarse sodium tungstate carries out being transformed into ammonium tungstate by ion exchange technique after a large amount of water dilutions are added
Solution is also had and is made the transition into ammonium tungstate solution using solvent-extracted method.This mainstream technology faces several serious ask at present
Topic：First, basic pressure digestion needs to consume the alkali such as sodium hydroxide or sodium carbonate, and the current price of these reagents is expensive to be reached, especially
Sodium hydroxide reaches 5000~6000 yuan/ton, therefore Scheelite-Wolframite Mixed Mine disaggregated cost is very high；Second, basic pressure digestion will will produce
Soda boiling slag, has been cited as National Hazard waste catalogue at present, and Tungsten smelting enterprise must not arbitrarily be handled, it is necessary to be given qualified
Enterprise is handled with compensation, and country also collects the dangerous waste soda boiling slag of generation 2000 yuan/ton of environmentally friendly tax, these are significantly greatly increased
The cost of Tungsten smelting；Third must also be used to produce the tungsten product of impurity content qualification in current Tungsten smelting technical process
To the Ammonias reagent such as ammonium hydroxide or ammonium chloride as transition reagent, therefore it is useless unavoidably to will produce a large amount of ammonia nitrogens in production process
Water causes to pollute environment.In order to solve the problems, such as that current Tungsten smelting faces economical and environmentally friendly, there is an urgent need for develop a kind of new Tungsten smelting
Technology.
In order to reduce tungsten ore disaggregated cost, while not generating dangerous waste soda boiling slag again cannot use alkaline reagent to carry out black and white
The decomposition of tungsten composite ore, then can only just acid reagent be used to carry out tungsten ore decomposition.In fact, having very early using hydrochloric acid and nitre
Acid decomposes Scheelite-Wolframite Mixed Mine, but to decompose discomposing effect limited；Li little Bin etc. decomposes Scheelite-Wolframite Mixed Mine using sulfuric acid,
Scheelite-Wolframite Mixed Mine can be decomposed largely under the experiment condition of optimization.Tungsten ore is converted into wolframic acid after peracid decomposes.In order to prepare
Qualified tungsten product, the wolframic acid generally use ammonium hydroxide being converted into are dissolved to obtain ammonium tungstate solution, also be had using ammonium carbonate
Dissolving dissolves wolframic acid to obtain ammonium tungstate solution.When decomposing slag progress ammonia or ammonium carbonate dissolving washing to acid, can not keep away
Exempt to will produce nitrogen-containing wastewater.It dissolves obtained ammonium tungstate dissolving and prepares APT through evaporative crystallization again, will produce in this process
Raw a large amount of steam containing ammonia, need special device to carry out absorption processing to ammonia.Some enterprises use absorption by Hydrochloric Acid ammonia after again
It is incorporated in waste water, shape high-concentration ammonia nitrogenous wastewater.Crystalline mother solution is a saturation ammonium tungstate solution, when carrying out processing recycling tungsten
The ammonia nitrogen waste water that will produce.Environmental protection at present is extremely stringent to the discharge management and control of Tungsten smelting ammonia nitrogen waste water, it is desirable to qualified discharge, it is necessary to add
The input of big Ammonia Wastewater Treatment, will certainly increase the production cost of enterprise.In addition, in order to produce (the oxidation of subsequent tungsten product
Tungsten), the head product APT of tungsten powder or tungsten carbide, tungsten must also pass through calcination process.And calcination process also will largely be generated containing ammonia
Exhaust gas, air will directly be polluted by not handling, yet need harmless treatment that could discharge after special arrangement absorbs.Thus may be used
See, current Tungsten smelting technique is can not to avoid the generation of ammonia nitrogen, the pollution that can cause ammonia nitrogen to a certain extent inevitable in this way.
In traditional Tungsten smelting technical process based on acid system, introducing ammonia is detached with other impurity for the ease of wolframic acid.
Since ammonium hydroxide or ammonium carbonate are a kind of weak base, other impurity are but difficult to dissolve while dissolving wolframic acid, thus are conducive to tungsten
The selective dissolution of acid.Since ammonia can cause ammonia and nitrogen pollution and cannot use, that either with or without other reagents also can selectivity it is molten
Solve wolframic acidSome researches show that hydrogen peroxide very early has very strong complexing power to tungsten, therefore someone is in sour Decomposition of Tungsten
A certain amount of hydrogen peroxide is added in the process and forms soluble peroxide wolframic acid to avoid forming wolframic acid package in decomposable process
And the acid for influencing Scheelite-Wolframite Mixed Mine decomposes.Use hydrogen peroxide can be with described in the technical solution of patent document CN105200246A
The mixed acid of wolframic acid and molybdic acid is obtained after the mixed solution of dissolving acid decomposition sodium tungstate and sodium molybdate.Due to the invention hydrogen peroxide
The wolframic acid and molybdic acid of dissolving are relatively pure, contain only the sodium ion for being not easy washes clean, and without other impurity, dissolving is opposite
It is easy.And main purpose of its invention be according to peroxide wolframic acid and peroxo-polymolybdic acid acid solution stablize difference to tungsten into
Row separation, does not relate to the method for purification of tungsten.
Peroxide wolframic acid is a kind of unstable complex, is easier to decompose generation wolframic acid.Jiang Anren etc. is just by sodium tungstate
A certain amount of hydrogen peroxide is added in solution, and adjusts solution acidity, then peroxynitrite decomposition tungstate radicle, wolframic acid is prepared.In addition
Wolframic acid and hydrogen peroxide are prepared by mixing into the precursor liquid that concentration is only 0.005mol/L by Guo Liejin etc., then pass through ullrasonic spraying
Precursor liquid is sprayed onto in 250 DEG C of ito glass matrix by pyrolysis, obtains the film of one layer of wolframic acid first, then passes through subsequent 550
DEG C heat treatment can just obtain WO 3 film, the essence of this process is the method for preparing wolframic acid film by spray pyrolysis.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, intend providing a kind of side extracting tungsten from Scheelite-Wolframite Mixed Mine
Method.
Specifically, the present invention provides a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder, the party
The flow diagram of method can refer to shown in Fig. 1.
The method of the invention includes the following steps：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in acid solution and carries out Leach reaction；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
Sulfuric acid is added in the leachate and carries out conversion reaction generation gypsum, reaction gained acid solution is added after regeneration
The sour return to step (1) of consumption carries out Leach reaction as raw material；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It will be decomposed obtained by step (2) after wash heat is washed and hydrogenperoxide steam generator be mixed
The extraction reaction for carrying out tungsten is closed, reaction product obtains peroxide tungstic acid after filtering；By the peroxide tungstic acid heating or
It is passed through SO2It is decomposed completely to peroxide wolframic acid and wolframic acid is precipitated；
(4) repeatedly dissolving-decomposition purifies wolframic acid to hydrogen peroxide：Impurity content in wolframic acid obtained by step (3) is detected,
If impurity content is met the requirements of the standard, the wolframic acid is directly used in subsequent step, is added if impurity content is above standard requirement
Enter hydrogenperoxide steam generator and repeat step (3) operation at least once, until obtaining the wolframic acid crystal that impurity content is met the requirements of the standard；
The wolframic acid met the requirements of the standard using the impurity content is raw material, using following steps (5) or step (6)~(7)
It is handled：
(5) calcining of pure tungsten acid prepares tungstic acid：The wolframic acid that impurity content is met the requirements of the standard is calcined, powder is obtained
Shape tungstic acid；
(6) peroxide tungstic acid spray pyrolysis prepares tungsten oxide and tungsten powder：The wolframic acid that impurity content is met the requirements of the standard
With hydrogenperoxide steam generator mixed dissolution, pure peroxide tungstic acid is obtained；
(7) the pure peroxide tungstic acid under non reducing conditions is subjected to ultrasonic spray pyrolysis, obtains ultrafine spherical
Tungstic acid；And/or the pure peroxide tungstic acid is subjected to ultrasonic spray pyrolysis under the reducing conditions, obtain ultra-fine ball
Shape blue tungsten oxide, tungstic violet oxide and/or tungsten powder.
The grade of targeted raw material Scheelite-Wolframite Mixed Mine of the invention is 10~65%, and granularity is less than 300 μm.
In step (1) the of the present invention Leach reaction：The acid that reaction is added can be selected hydrochloric acid or nitric acid, the hydrochloric acid or
Concentration of nitric acid is 50~300g/L.A certain amount of solid wolframic acid can also be added in the reaction process, addition is described black
The 0~20% of white tungsten composite ore quality.Oxygen can also be passed through in reaction process to promote the progress of reaction.The step reaction
Liquid-solid ratio is preferably 3:1~10:1.As a preferred embodiment, the reaction of step (1) can be in 50~250 DEG C, 0~10Mpa items
It is carried out under part, the reaction time is preferably 1~6 hour.
In step (2) the of the present invention filtration washing：A certain amount of sulfuric acid is added in the leachate convert instead
It answers, generates CaSO4Slag (i.e. gypsum), the conversion reaction be added sulfuric acid amount and calcium ion content in leachate molar ratio it is excellent
It is selected as 0.9~1:1.As a preferred embodiment, the conversion reaction can react 0.5~2.0 hour under the conditions of 25~60 DEG C.
It is transformed acid through regeneration (such as：First pass through the modes such as column chromatography and remove metal ion in liquid, then add acid to concentration with
Leach reaction use acid concentration it is identical) after obtain hydrochloric acid or nitric acid, can return to step (1) as raw material carry out Leach reaction.
In step (3) the hydrogen peroxide extraction of the present invention-decomposition extraction tungsten：The mass concentration of the hydrogenperoxide steam generator
It is 5~30%；The addition of hydrogen peroxide with decompose wolframic acid in slag mole preferably than 0.5~2:1.As a kind of preferred side
Case, extraction reaction react 10min~2.0h under the conditions of 10~40 DEG C of temperature.After the completion of the extraction reaction, to product
Through peroxide tungstic acid is obtained by filtration.Then the peroxide tungstic acid is heated to 50~90 DEG C, or directly to peroxide tungsten
SO is passed through in acid solution2And sulfuric acid concentration 0.1mol/L~2.0mol/L in solution is controlled, until peroxide wolframic acid decomposes completely, it can
Wolframic acid is precipitated.
The visual raw material difference of operation of the multiple extraction-decomposition purification wolframic acid of step (4) the of the present invention hydrogen peroxide repeats
Number it is also different.When Scheelite-Wolframite Mixed Mine grade is high, impurity content can directly meet mark in wolframic acid crystal obtained by step (3)
The wolframic acid crystal is then directly used in subsequent step, can directly omit purification process by alignment request；Work as Scheelite-Wolframite Mixed Mine
When grade is relatively low, impurity content is above standard requirements in wolframic acid crystal obtained by step (3), then needs to add in the wolframic acid crystal
Enter hydrogenperoxide steam generator and repeat step (3) operation at least once, i.e., is purified using hydrogen peroxide, until obtaining impurity content
The wolframic acid crystal met the requirements of the standard.After the present invention controls the impurity content in wolframic acid crystal by step (4),
It is calcined or is pyrolyzed in subsequent step again, it can be ensured that final product has good yield and purity, and saves the energy, protects
Protect equipment.
The standard of impurity content of the present invention can artificially be made according to industrial production specification or to the actual demand of product
It orders, the present invention is not specifically limited.As a preferred embodiment of the present invention, when impurity content meets in the wolframic acid of acquisition
When national standard GB/T 10116-2007, you can assert that wolframic acid is qualified.
The qualified wolframic acid being prepared by previous step prepares oxidation tungsten product there are two types of optional mode.Wherein,
A kind of mode such as step (5) is described, directly obtains tungstic acid by calcining；The second way such as step (6)~(7) are described,
Spray pyrolysis prepares tungsten oxide and tungsten powder.
Step (5) the pure tungsten acid calcining of the present invention is prepared in tungstic acid：The temperature of the calcining is 750~900 DEG C.
The wolframic acid that impurity content is met the requirements of the standard is carried out calcining and powdery tungstic acid is prepared by this step.
Step (6) the peroxide tungstic acid spray pyrolysis of the present invention is prepared in tungsten oxide and tungsten powder：Impurity content is accorded with
Hydrogenperoxide steam generator (mass concentration is 5~30%) is added in the wolframic acid that standardization requires again, and it is molten that pure peroxide wolframic acid is obtained by the reaction
Liquid (wherein WO3Concentration is about 10~350g/L).
The pure peroxide tungstic acid is carried out ultrasonic spray pyrolysis by step (7) of the present invention, you can obtains ultrafine spherical production
Object.Specifically, the ultrasonic spray pyrolysis can carry out under non reducing conditions, obtain ultrafine spherical tungstic acid；It also can be also
It is carried out under old terms, obtains ultrafine spherical blue tungsten oxide or tungstic violet oxide or tungsten powder.
In practical operation, when ultrasonic spray pyrolysis, can be passed through inert gas (such as nitrogen or argon gas), lead to inertia
The purpose of gas is to bring solution by gas to be pyrolyzed.As a preferred embodiment, spray rate is 10~200ml/
Min, gas flow rate are 150~600ml/L, and the temperature of pyrolysis is 500~900 DEG C, and ultrafine spherical tungsten trioxide powder can be obtained.
In practical operation, when ultrasonic spray pyrolysis, can also be passed through reducibility gas (such as hydrogen), make pyrolysis also
It is carried out under old terms.As a preferred embodiment, spray rate is 10~200ml/min, and hydrogen flow rate is 50~600ml/L,
The temperature of pyrolysis is 500~900 DEG C, and ultrafine spherical tungstic violet oxide powder or ultrafine spherical blue oxide powder can be obtained.
As a preferred embodiment, spray rate is 10~200ml/min, and hydrogen flow rate is 100~800ml/L, and the temperature of pyrolysis is
900~1100 DEG C, ultrafine spherical tungsten powder can be obtained.When reduction temperature difference, the product of gained is different.
The present invention provides a kind of method that completely new slave Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder, and main advantage embodies
In the following：
The first, a small amount of nitric acid or hydrochloric acid are actually only consumed in decomposable process of the present invention, are mainly consumed cheap and easily-available
Sulfuric acid, 200~500 yuan/ton of price, only the 10% of sodium hydroxide reagent cost, greatly reduce tungsten ore disaggregated cost；
The second, the present invention is decomposed using acid, and decomposition slag is gypsum, can be used as building materials, not generate dangerous waste soda boiling slag, greatly
Reduce enterprise's production and operation cost；
Third, the present invention use extractant of the hydrogen peroxide as wolframic acid, do not generate ammonia nitrogen waste water, have got rid of Tungsten smelting edge
With the technique for generating ammonia nitrogen waste water for many years, environmentally friendly cost is greatly reduced；
4th, the present invention directly produces the end product (tungsten oxide) and tungsten powder of various tungsten, improves Tungsten smelting enterprise
Added value of product.
Description of the drawings
Fig. 1 is the flow chart of the method for the invention；In figure, dotted arrow and dotted line frame represent can select a selection and
Row process route.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder is present embodiments provided, this method uses
Raw material be grade be 40%, the Scheelite-Wolframite Mixed Mine that granularity is 150 μm, the method is specially：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in the hydrochloric acid solution of concentration 200g/L, the liquid-solid ratio of system is
6:1, Leach reaction is carried out under the conditions of 150 DEG C, 5Mpa 3 hours, 99.4% tungsten is converted to wolframic acid；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
It is added sulfuric acid in the leachate, the molar ratio of calcium ion content is 1 in the amount and leachate of the sulfuric acid:1,
Conversion reaction 1h is carried out under the conditions of 45 DEG C, generates gypsum；The acid that reaction gained acid solution adds consumption after regeneration returns to step
Suddenly (1) carries out Leach reaction as raw material；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It will be decomposed obtained by step (2) after wash heat is washed and mass concentration be 30%
Hydrogenperoxide steam generator mixing, the addition of hydrogen peroxide is 1.5 with the molar ratio for decomposing wolframic acid in slag:1, in 25 DEG C of items of temperature
1h is reacted in the extraction that tungsten is carried out under part, and reaction product obtains peroxide tungstic acid after filtering；The peroxide tungstic acid is added
Heat is to 80 DEG C, until peroxide wolframic acid decomposes completely is precipitated wolframic acid；
(4) repeatedly dissolving-decomposition purifies wolframic acid to hydrogen peroxide：It is to mass concentration is added in wolframic acid obtained by step (3)
30% hydrogenperoxide steam generator repeats step (3) and operates once, obtains the wolframic acid that impurity content is met the requirements of the standard；When the tungsten of acquisition
When impurity content meets national standard GB/T 10116-2007 in acid, you can assert that wolframic acid is qualified；
(5) by after wolframic acid washing obtained by step (4), then with mass concentration it is 25% hydrogenperoxide steam generator in 30 DEG C of items of temperature
Hybrid reaction 1h under part obtains pure peroxide tungstic acid again；
(6) the pure peroxide tungstic acid for obtaining step (5) is being passed through hydrogen, spray rate 120ml/min, hydrogen
Flow velocity is 350ml/L, pyrolysis temperature carries out ultrasonic spray pyrolysis under the conditions of being 500 DEG C, obtains ultrafine spherical blue oxide tungsten powder
End；Impurity content meets the requirement of national standard GB/T 3457-2013 (0 grade of product) in blue tungstic acid after testing.
Embodiment 2
A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder is present embodiments provided, this method uses
Raw material be grade be 55%, the Scheelite-Wolframite Mixed Mine that granularity is 80 μm, the method is specially：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in the hydrochloric acid solution of concentration 150g/L, the liquid-solid ratio of system is
6:1, while being passed through oxygen and carrying out Leach reaction under the conditions of 200 DEG C, 10Mpa 2 hours, 99.2% tungsten is converted to wolframic acid；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
It is added sulfuric acid in the leachate, the molar ratio of calcium ion content is 1 in the amount and leachate of the sulfuric acid:1,
Conversion reaction 0.5h is carried out under the conditions of 60 DEG C, generates gypsum；The acid that reaction gained acid solution adds consumption after regeneration returns
Step (1) carries out Leach reaction as raw material；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It will be decomposed obtained by step (2) after wash heat is washed and mass concentration be 30%
Hydrogenperoxide steam generator mixing, the addition of hydrogen peroxide is 1 with the molar ratio for decomposing wolframic acid in slag:1, in 40 DEG C of conditions of temperature
10min is reacted in the lower extraction for carrying out tungsten, and reaction product obtains peroxide tungstic acid after filtering；Directly into peroxide tungstic acid
It is passed through SO2And sulfuric acid concentration 1.5mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated wolframic acid；After testing, gained
Impurity content meets national standard GB/T10116-2007 in wolframic acid, can be directly used for subsequent step；
(4) by after wolframic acid washing obtained by step (3), then with mass concentration it is 30% hydrogenperoxide steam generator in 25 DEG C of items of temperature
Hybrid reaction 1h under part obtains pure peroxide tungstic acid again；
(5) the pure peroxide tungstic acid for obtaining step (4) is being passed through nitrogen, spray rate 120ml/min, nitrogen
Flow velocity is 400ml/L, pyrolysis temperature carries out ultrasonic spray pyrolysis under the conditions of being 700 DEG C, obtains ultrafine spherical tungsten trioxide powder；
Impurity content meets the requirement of national standard GB/T 3457-2013 (0 grade of product) in tungstic acid after testing.
Embodiment 3
A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder is present embodiments provided, this method uses
Raw material be grade be 65%, the Scheelite-Wolframite Mixed Mine that granularity is 50 μm, the method is specially：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in the salpeter solution of concentration 100g/L, add account for it is described black
The liquid-solid ratio of the solid wolframic acid of white tungsten composite ore quality 10%, system is 3:1, Leach reaction 6 is carried out under the conditions of 80 DEG C, 0Mpa
Hour, 99.1% tungsten is converted to wolframic acid；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
It is added sulfuric acid in the leachate, the molar ratio of calcium ion content is 1 in the amount and leachate of the sulfuric acid:1,
Conversion reaction 2h is carried out under the conditions of 25 DEG C, generates gypsum；The acid that reaction gained acid solution adds consumption after regeneration returns to step
Suddenly (1) carries out Leach reaction as raw material；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It is 5% with mass concentration that wash heat will be decomposed obtained by step (2) and washed afterwards
Hydrogenperoxide steam generator mixes, and the addition of hydrogen peroxide is 1 with the molar ratio for decomposing wolframic acid in slag:1, under the conditions of 10 DEG C of temperature
2h is reacted in the extraction for carrying out tungsten, and reaction product obtains peroxide tungstic acid after filtering；Directly it is passed through into peroxide tungstic acid
SO2And sulfuric acid concentration 0.5mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated wolframic acid；After testing, gained wolframic acid
Middle impurity content meets national standard GB/T 10116-2007, can be directly used for subsequent step；
(4) by after wolframic acid washing obtained by step (3), then with mass concentration it is 30% hydrogenperoxide steam generator in 35 DEG C of items of temperature
Hybrid reaction 1h under part obtains pure peroxide tungstic acid again；
(5) the pure peroxide tungstic acid for obtaining step (4) is being passed through hydrogen, spray rate 110ml/min, hydrogen
Flow velocity is 600ml/L, pyrolysis temperature carries out ultrasonic spray pyrolysis under the conditions of being 1050 DEG C, obtains ultrafine spherical tungsten powder.After testing
Impurity content meets the requirement of national standard GB/T 3458-2006 (FW-1 grades of products) in tungsten powder.
Embodiment 4
A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder is present embodiments provided, this method uses
Raw material be grade be 35%, the Scheelite-Wolframite Mixed Mine that granularity is 160 μm, the method is specially：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in the salpeter solution of concentration 50g/L, the liquid-solid ratio of system is
4:1, Leach reaction is carried out under the conditions of 90 DEG C, 0Mpa 4 hours, 99.2% tungsten is converted to wolframic acid；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
It is added sulfuric acid in the leachate, the molar ratio of calcium ion content is 1 in the amount and leachate of the sulfuric acid:1,
Conversion reaction 1h is carried out under the conditions of 45 DEG C, generates gypsum；The acid that reaction gained acid solution adds consumption after regeneration returns to step
Suddenly (1) carries out Leach reaction as raw material；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It will be decomposed obtained by step (2) after wash heat is washed and mass concentration be 30%
Hydrogenperoxide steam generator mixing, the addition of hydrogen peroxide is 1.2 with the molar ratio for decomposing wolframic acid in slag:1, in temperature 50 C item
1h is reacted in the extraction that tungsten is carried out under part, and reaction product obtains peroxide tungstic acid after filtering；Directly into peroxide tungstic acid
It is passed through SO2And sulfuric acid concentration 0.4mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated wolframic acid；After testing, gained
Impurity content meets national standard GB/T 10116-2007 in wolframic acid, can be directly used for subsequent step；
(4) by after wolframic acid washing obtained by step (3), then with mass concentration it is 30% hydrogenperoxide steam generator in 35 DEG C of items of temperature
Hybrid reaction 1h under part obtains pure peroxide tungstic acid again；
(5) the pure peroxide tungstic acid for obtaining step (4) is being passed through hydrogen, spray rate 150ml/min, hydrogen
Flow velocity is 400ml/L, pyrolysis temperature carries out ultrasonic spray pyrolysis under the conditions of being 800 DEG C, obtains ultrafine spherical tungstic violet oxide powder
End；Impurity content meets the requirement of national standard GB/T 3457-2013 (0 grade of product) in purple tungstic acid after testing.
Embodiment 5
A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder is present embodiments provided, this method uses
Raw material be grade be 45%, the Scheelite-Wolframite Mixed Mine that granularity is 100 μm, the method is specially：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in the salpeter solution of concentration 180g/L, the liquid-solid ratio of system is
4:1, while being passed through oxygen and carrying out Leach reaction under the conditions of 200 DEG C, 2.1Mpa 2 hours, 99.5% tungsten is converted to wolframic acid；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
It is added sulfuric acid in the leachate, the molar ratio of calcium ion content is 1 in the amount and leachate of the sulfuric acid:1,
Conversion reaction 1h is carried out under the conditions of 45 DEG C, generates gypsum；The acid that reaction gained acid solution adds consumption after regeneration returns to step
Suddenly (1) carries out Leach reaction as raw material；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It will be decomposed obtained by step (2) after wash heat is washed and mass concentration be 30%
Hydrogenperoxide steam generator mixing, the addition of hydrogen peroxide is 1.1 with the molar ratio for decomposing wolframic acid in slag:1, in 40 DEG C of items of temperature
1h is reacted in the extraction that tungsten is carried out under part, and reaction product obtains peroxide tungstic acid after filtering；It directly heats until peroxide wolframic acid
It decomposes completely and wolframic acid is precipitated；After testing, impurity content meets national standard GB/T10116-2007 in gained wolframic acid, can directly use
In subsequent step；
(4) by after wolframic acid washing obtained by step (3), yellow tungsten oxide is obtained after carrying out calcining 4.0h under the conditions of 850 DEG C.
Impurity content meets the requirement of national standard GB/T3457-2013 (0 grade of product) in yellow tungstic acid after testing.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of acid decomposes the method that Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder, which is characterized in that include the following steps：
(1) Leach reaction：Scheelite-Wolframite Mixed Mine is added in acid solution and carries out Leach reaction；
(2) filtration washing：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；
Sulfuric acid is added in the leachate and carries out conversion reaction generation gypsum, reaction gained acid solution adds consumption after regeneration
Sour return to step (1) as raw material carry out Leach reaction；
(3) tungsten is extracted in hydrogen peroxide extraction-decomposition：It will decompose obtained by step (2) after wash heat is washed and be mixed into hydrogenperoxide steam generator
The extraction of row tungsten is reacted, and reaction product obtains peroxide tungstic acid after filtering；The peroxide tungstic acid is heated or is passed through
SO2It is decomposed completely to peroxide wolframic acid and wolframic acid is precipitated；
(4) repeatedly dissolving-decomposition purifies wolframic acid to hydrogen peroxide：Impurity content in wolframic acid obtained by step (3) is detected, it is such as miscellaneous
Matter content is met the requirements of the standard, and the wolframic acid is directly used in subsequent step, is added if impurity content is above standard requirement
Hydrogen peroxide solution repeats step (3) and operates at least once, until obtaining the wolframic acid that impurity content is met the requirements of the standard；
The wolframic acid met the requirements of the standard using the impurity content is carried out as raw material using following steps (5) or step (6)~(7)
Processing：
(5) calcining of pure tungsten acid prepares tungstic acid：The wolframic acid that impurity content is met the requirements of the standard is calcined, powdery three is obtained
Tungsten oxide；
(6) peroxide tungstic acid spray pyrolysis prepares tungsten oxide and tungsten powder：The wolframic acid and mistake that impurity content is met the requirements of the standard
Hydrogen peroxide solution mixed dissolution obtains pure peroxide tungstic acid；
(7) the pure peroxide tungstic acid under non reducing conditions is subjected to ultrasonic spray pyrolysis, obtains three oxygen of ultrafine spherical
Change tungsten；And/or the pure peroxide tungstic acid is subjected to ultrasonic spray pyrolysis under the reducing conditions, obtain ultrafine spherical indigo plant
Color tungsten oxide, tungstic violet oxide and/or tungsten powder.
2. according to the method described in claim 1, it is characterized in that, the grade of the Scheelite-Wolframite Mixed Mine is 10~65%；Institute
The granularity for the Scheelite-Wolframite Mixed Mine stated is less than 300 μm.
3. method according to claim 1 or 2, which is characterized in that in the step (1), the acid for a concentration of 50~
The hydrochloric acid or nitric acid of 300g/L；
And/or the solid wolframic acid for being equivalent to the Scheelite-Wolframite Mixed Mine quality 0~20% is added in the reaction process；
And/or it is passed through oxygen in the reaction process；
And/or the reaction carries out under the conditions of 50~250 DEG C, 0~10Mpa.
4. according to the method described in claims 1 to 3 any one, which is characterized in that in the step (2), the conversion is anti-
The molar ratio of amount and calcium ion content in leachate that sulfuric acid should be added is 0.9~1:1；
And/or the conversion reaction carries out under the conditions of 25~60 DEG C.
5. according to the method described in Claims 1 to 4 any one, which is characterized in that in the step (3), the peroxidating
The mass concentration of hydrogen solution is 5~30%, the amount of hydrogen peroxide and mole for decomposing wolframic acid in slag in the hydrogenperoxide steam generator
Than being 0.5~2:1；
And/or extraction reaction carries out under the conditions of 10~40 DEG C of temperature.
6. according to the method described in claim 5, it is characterized in that, step (3) heating refers to that the peroxide wolframic acid is molten
Liquid is heated to 50~90 DEG C；
And/or described it is passed through SO2When should to control in solution sulfuric acid concentration be 0.1mol/L~2.0mol/L.
7. according to the method described in claim 1~6 any one, which is characterized in that the temperature of step (5) described calcining is
750~900 DEG C.
8. according to the method described in claim 1~7 any one, which is characterized in that when step (7) described ultrasonic spray pyrolysis
It is passed through inert gas, spray rate is 10~200ml/min, and gas flow rate is 150~600ml/L, the temperature of pyrolysis is 500~
900 DEG C, obtain ultrafine spherical tungsten trioxide powder.
9. according to the method described in claim 1~7 any one, which is characterized in that when step (7) described ultrasonic spray pyrolysis
It is passed through hydrogen, spray rate is 10~200ml/min, and hydrogen flow rate is 50~600ml/L, and the temperature of pyrolysis is 500~900
DEG C, obtain ultrafine spherical tungstic violet oxide powder/or ultrafine spherical blue oxide powder.
10. according to the method described in claim 1~7 any one, which is characterized in that step (7) described ultrasonic spray pyrolysis
When be passed through hydrogen, spray rate is 10~200ml/min, and hydrogen flow rate is 100~800ml/L, the temperature of pyrolysis is 900~
1100 DEG C, obtain ultrafine spherical tungsten powder.
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| CN114672672B (en) * | 2022-04-18 | 2024-04-16 | 江西钨业股份有限公司 | Method for recovering tungstic acid from tungsten-containing solution |
| CN115679127A (en) * | 2022-09-09 | 2023-02-03 | 江西理工大学 | Method for roasting and decomposing tungsten concentrate by utilizing acid gas |
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