CN108425011A - A method of extracting tungsten from high seyrigite - Google Patents
A method of extracting tungsten from high seyrigite 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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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B34/00—Obtaining refractory metals
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Abstract
The method that the present invention relates to a kind of to extract tungsten from high seyrigite, including：High seyrigite is leached with sulfuric acid solution, leachate is extracted into extraction molybdenum；Leached mud is extracted with hydrogen peroxide, obtains the solution of wolframic acid containing peroxide and peroxo-polymolybdic acid, heats or be passed through SO2, obtain wolframic acid and the solution containing peroxo-polymolybdic acid；Wolframic acid is dissolved with hydrogen peroxide, acquired solution is heated or be passed through SO2, obtain wolframic acid and the solution containing peroxo-polymolybdic acid；Repeatedly, until obtaining pure tungsten acid；Pure tungsten acid is prepared into tungstic acid or tungsten powder；Solution containing peroxo-polymolybdic acid is heated or is passed through SO2, gained molybdic acid is dissolved with hydrogenperoxide steam generator, peroxo-polymolybdic acid solution is made, ultrasonic spray pyrolysis prepares molybdenum trioxide powder or molybdenum powder.This method good separating effect, operating process is simple and easy to control, is easy to industrial application.
Description
Technical field
The present invention relates to metallurgy of rare metal technical fields, and in particular to a kind of side extracting tungsten from high seyrigite
Method.
Background technology
The mainstream technology of the high seyrigite of industrial processing is first to use the alkalinity examination such as sodium hydroxide or sodium carbonate at present
Agent obtains coarse sodium tungstate and soda boiling slag by autoclaving.Coarse sodium tungstate contains a certain amount of molybdenum, needs first to be vulcanized,
Then to carry out acidification, make molybdenum molybdenum trisulfide form precipitation separation.This process will unavoidably will produce largely
Toxic gas hydrogen sulfide.It is therein using alkalescent extractant or weak-base ion-exchange resin absorption to be acidified later solution
Then tungsten is stripped by ammonium hydroxide or desorption obtains ammonium tungstate solution.This mainstream technology faces several serious problems at present：
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 hydrogen-oxygen
Change sodium and reach 5000~6000 yuan/ton, therefore scheelite disaggregated cost is very high；Second, basic pressure digestion will will produce soda boiling slag, at present
National Hazard waste catalogue is had been cited as, Tungsten smelting enterprise must not arbitrarily be handled, it is necessary to give qualified enterprise and locate with compensation
Reason, and country also collects the dangerous waste soda boiling slag of generation 2000 yuan/ton of environmentally friendly tax, these be significantly greatly increased Tungsten smelting at
This；Third needs addition sulfide to carry out vulcanization Separation of Molybdenum, will will produce in the process to detach the molybdenum of association in scheelite
Toxic gas hydrogen sulfide harm production and environment；4th, in order to produce the tungsten product of impurity content qualification, current Tungsten smelting work
It is inevitable as transition reagent, therefore in production process that the Ammonias reagent such as ammonium hydroxide or ammonium chloride must also be used during skill
A large amount of ammonia nitrogen waste waters are will produce, cause 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 open
The Tungsten smelting technology that send out a kind of new.
In order to reduce tungsten ore disaggregated cost, while not generating dangerous waste soda boiling slag again cannot use alkaline reagent to carry out white tungsten
The decomposition of mine, then can only just acid reagent be used to carry out tungsten ore decomposition.Divided using hydrochloric acid and nitric acid in fact, having very early
Scheelite is solved, good discomposing effect is also achieved；Li little Bin etc. decomposes scheelite using sulfuric acid, in the experiment condition of optimization
Lower scheelite can also decompose completely.Scheelite is converted into wolframic acid after peracid decomposes.In order to prepare qualified tungsten product, conversion
The wolframic acid generally use ammonium hydroxide of generation is dissolved to obtain ammonium tungstate solution, is also had and is dissolved to wolframic acid using ammonium carbonate dissolving
Obtain ammonium tungstate solution.When decomposing slag progress ammonia or ammonium carbonate dissolving washing to acid, nitrogen-containing wastewater unavoidably will produce.
It dissolves obtained ammonium tungstate dissolving and prepares APT through evaporative crystallization again, a large amount of steam containing ammonia will be will produce in this process, needed
Special device carries out absorption processing to ammonia.Some enterprises are incorporated in waste water again after using absorption by Hydrochloric Acid ammonia, shape high concentration
Ammonia nitrogen waste water.Crystalline mother solution is a saturation ammonium tungstate solution, the ammonia nitrogen waste water that also will produce when carrying out processing recycling tungsten.Mesh
Preceding environmental protection 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 increase the throwing of Ammonia Wastewater Treatment
Enter, the production cost of enterprise will certainly be increased.In addition, in order to produce subsequent tungsten product (tungsten oxide), tungsten powder or tungsten carbide,
The head product APT of tungsten must also pass through calcination process.And calcination process also will largely generate ammonia-contaminated gas, not handling will be direct
Air is polluted, yet needs harmless treatment that could discharge after special arrangement absorbs.It can be seen that current Tungsten smelting technique is
It can not 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 decomposes.Chinese patent 201510698722.3, which discloses, uses hydrogen peroxide that can decompose wolframic acid with dissolving acid
The mixed acid of wolframic acid and molybdic acid is obtained after the mixed solution of sodium and sodium molybdate.Due in this method hydrogen peroxide dissolve wolframic acid and
Molybdic acid is relatively pure, contains only the sodium ion for being not easy washes clean, and without other impurity, dissolving is relatively easy.And its
The main purpose of invention is to stablize difference in acid solution according to peroxide wolframic acid and peroxo-polymolybdic acid to detach tungsten, 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.
In view of this, the present invention provides a kind of method for extracting tungsten from high seyrigite.
Invention content
Present invention aims at a kind of method for extracting tungsten from high seyrigite is provided, this method has separating effect
The advantages that good, operating process is simple and easy to control, at low cost, environmental protection, flow is short, is easy to industrial application.
To achieve the above object, the present invention adopts the following technical scheme that：
A method of extracting tungsten from high seyrigite, the flow diagram of this method can refer to shown in Fig. 1, specifically
Include the following steps：
1) Leach reaction：High seyrigite is added in sulfuric acid solution and carries out Leach reaction；After the completion of reaction, filter
To decomposition slag and leachate.
Further, at 50~200 DEG C, reaction pressure is controlled in 0~10Mpa for the Leach reaction temperature control.
Further, the liquid-solid ratio of a concentration of 50~500g/L of the sulfuric acid solution, reaction are 3:1~10:1, reaction
Time is 1~6 hour.
To further increase Leach reaction efficiency, a certain amount of solid wolframic acid can also be added during Leach reaction, add
Enter 0~20% that amount is tungsten ore quality, preferably the 5~10% of tungsten ore quality；And/or it can also add during Leach reaction
Enter a certain amount of CaSO4As crystal seed, addition is the 0~20% of tungsten ore quality, preferably the 5~15% of tungsten ore quality.
Further, WO in the high seyrigite3Content is that 10~65%, Mo contents are 1~25%；Further
The granularity on ground, the high seyrigite is less than 300 μm.
2) extraction extraction molybdenum：Leachate obtained by step 1) is mixed with extractant, extracts molybdenum therein.
The extractant includes P204, P507, N235, LIX63, TRPO, any one of Cyanex272, HBL101 etc.
Or it is several.The above extractant is all well known, can be commercially available by commercially available.
Further, appropriate diluent kerosene can also be added in extraction process.
Specifically, the extractant is optional " 30%N235+10%TBP+ kerosene "；" 40%P204+ kerosene "；Or " 35%
LIX63+ kerosene ".
Further, extraction reaction temperature is 30~50 DEG C, and extraction time is 5~30min, organic phase and water phase when extraction
Volume ratio is 4:1~1:5.
Further, further include obtaining raffinate after the completion of extracting to add return to step 1 after the sulfuric acid of consumption) leach it is anti-
It answers.
3) tungsten is extracted in hydrogen peroxide extraction-decomposition：Leached mud obtained by step 1) is added in hydrogenperoxide steam generator and is carried out
Extraction filters after the completion of reaction, obtains the solution and calcium sulfate slag of wolframic acid containing peroxide and peroxo-polymolybdic acid；Then contained by described in
The solution of oxygen wolframic acid and peroxo-polymolybdic acid heats (being preferably heated to 50~90 DEG C), or directly to the wolframic acid containing peroxide and peroxide
It is passed through SO in the solution of molybdic acid2(it is 0.1mol/L~4.0mol/L preferably to control hydrogen ion concentration in reaction system, more preferably
0.5mol/L~2.0mol/L, until peroxide wolframic acid decomposes completely is precipitated wolframic acid, and most of peroxo-polymolybdic acid then stays in the solution；
Filtering, obtains wolframic acid (may also contain a small amount of molybdic acid) and the solution containing peroxo-polymolybdic acid.
Further, a concentration of the 5~30% of the hydrogenperoxide steam generator.
Further, the hydrogen peroxide adds molybdic acid (to refer to and decompose wolframic acid and molybdic acid in slag with wolframic acid in the decomposition slag
The sum of amount of substance) molar ratio be 0.5~2:1.
Further, the temperature of the extraction reaction is 10~40 DEG C, and the reaction time is 10min~2.0h.
4) repeatedly dissolving-decomposition purifies tungsten to hydrogen peroxide：Wolframic acid (may also contain a small amount of molybdic acid) obtained by step 3) is added
Enter in hydrogenperoxide steam generator and dissolved, is filtered after the completion of reaction, obtain the solution of wolframic acid containing peroxide and peroxo-polymolybdic acid again；So
The solution of the wolframic acid containing peroxide and peroxo-polymolybdic acid is heated into (being preferably heated to 50~90 DEG C) afterwards, or was directly contained to described
It is passed through SO in the solution of oxygen wolframic acid and peroxo-polymolybdic acid2(preferably control reaction system in hydrogen ion concentration be 0.1mol/L~
4.0mol/L, more preferably 0.5mol/L~2.0mol/L), until peroxide wolframic acid decomposes completely is precipitated wolframic acid, and peroxo-polymolybdic acid
It then stays in the solution；Filtering, obtains wolframic acid (may also contain a small amount of molybdic acid) and the solution containing peroxo-polymolybdic acid.
Step 4) is repeated repeatedly, until obtaining pure tungsten acid (being free of molybdic acid).
Further, a concentration of the 5~30% of the hydrogenperoxide steam generator.
Further, the hydrogen peroxide adds molybdic acid (to refer to and decompose wolframic acid and molybdic acid in slag with wolframic acid in the decomposition slag
The sum of amount of substance) molar ratio be 0.5~2:1.
Further, the temperature of the dissolving reaction is 10~40 DEG C, and the reaction time is 10min~2.0h.
5) pure tungsten acid calcining obtained by step 4) is prepared into tungstic acid (powdery)；Further, calcination temperature be 750~
900℃。
Alternatively, pure tungsten acid obtained by step 4) is dissolved with hydrogenperoxide steam generator to obtain pure peroxide tungstic acid, it is then ultrasonic
Spray pyrolysis (can use ultrasonic spray pyrolysis equipment) prepares tungsten trioxide powder, or prepares tungstic violet oxide powder or blue oxygen
Compound powder, or prepare tungsten powder.
Further, a concentration of the 5~30% of the hydrogenperoxide steam generator.
Further, WO in the pure peroxide tungstic acid3A concentration of 10~350g/L.
Further, the ultrasonic spray pyrolysis condition for preparing tungsten trioxide powder：Spray rate is 10~200mL/
min；The temperature of pyrolysis is 500~900 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L.
Further, the ultrasonic spray pyrolysis condition for preparing tungstic violet oxide powder or blue oxide powder：
Spray rate is 10~200mL/min；The temperature of pyrolysis is 500~900 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is
150~600mL/L；It is passed through reducibility gas hydrogen simultaneously, hydrogen flow rate is 50~600mL/L.
Further, the ultrasonic spray pyrolysis condition for preparing tungsten powder：Spray rate is 10~200mL/min；Pyrolysis
Temperature be 900~1100 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；It is passed through reproducibility simultaneously
Gas hydrogen, hydrogen flow rate are 100~800mL/L.
6) peroxo-polymolybdic acid decomposition-molten-spray pyrolysis of hydrogen peroxide weight prepares molybdenum oxide/molybdenum powder：By step 3) and/or step
Rapid solution heating (be preferably heated to 50~90 DEG C) of the 4) gained containing peroxo-polymolybdic acid, or it is passed directly into SO2, until peroxo-polymolybdic acid
It decomposes completely and molybdic acid is precipitated；The molybdic acid of precipitation is dissolved with hydrogenperoxide steam generator, filters and peroxo-polymolybdic acid solution is made, it is then ultrasonic
Spray pyrolysis (can use ultrasonic spray pyrolysis equipment) prepares molybdenum trioxide powder, or prepares molybdenum powder.
Further, a concentration of the 5~30% of the hydrogenperoxide steam generator.
Further, when preparing peroxo-polymolybdic acid solution with hydrogenperoxide steam generator dissolving, the hydrogen peroxide and the molybdic acid
Molar ratio be 0.5~2:1；And/or reaction temperature is 10~40 DEG C, the reaction time is 10min~2.0h.
Further, with a concentration of 10~350g/L of Mo in the peroxo-polymolybdic acid solution of hydrogenperoxide steam generator dissolving preparation.
Further, the ultrasonic spray pyrolysis condition for preparing molybdenum trioxide powder：Spray rate is 10~200mL/
min；The temperature of pyrolysis is 200~800 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L.
Further, the ultrasonic spray pyrolysis condition for preparing molybdenum powder：Spray rate is 10~200mL/min, pyrolysis
Temperature be 500~1100 DEG C, inert gas be nitrogen or argon gas, flow velocity be 150~600mL/L；It is passed through reproducibility simultaneously
Gas hydrogen, hydrogen flow rate are 50~600mL/L.
What the visual raw material difference of operation of the multiple dissolving-decomposition purification wolframic acid of the step 4) hydrogen peroxide of the present invention repeated
Number is also different.When high seyrigite grade is high, impurity content can directly be met the requirements of the standard in wolframic acid obtained by step 3), then
The wolframic acid is directly used in subsequent step, can directly omit purification process；When high seyrigite grade is relatively low, step
3) impurity content is above standard requirements in gained wolframic acid, then needs that hydrogenperoxide steam generator repetition step 3) is added in the wolframic acid
And/or step 4) operation is at least once, i.e., is purified using hydrogen peroxide, until obtaining what impurity content was met the requirements of the standard
Wolframic acid.After the present invention controls the impurity content in wolframic acid by step 4), then subsequent step carry out calcining or
Spray pyrolysis, it can be ensured that final product has good yield and purity, and saves the energy, protects 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 raw materials used in the present invention is commercially available to buy, or is prepared by this field conventional method.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined with each other each preferably to get the present invention
Example.
Preferably, the above-mentioned method for extracting tungsten from high seyrigite, includes the following steps：
1) Leach reaction：
High seyrigite is added in sulfuric acid solution and carries out Leach reaction；After the completion of reaction, be obtained by filtration decompose slag and
Leachate；
At 50~200 DEG C, reaction pressure is controlled in 0~10Mpa for the Leach reaction temperature control；
The liquid-solid ratio of a concentration of 50~500g/L of the sulfuric acid solution, reaction are 3:1~10:1, the reaction time is 1~6
Hour；
A certain amount of solid wolframic acid is additionally added during Leach reaction, addition is the 0~20% of tungsten ore quality, preferably
The 5~10% of tungsten ore quality；
And/or it is additionally added a certain amount of CaSO during Leach reaction4As crystal seed, addition be tungsten ore quality 0~
20%, preferably the 5~15% of tungsten ore quality；
2) extraction extraction molybdenum：Leachate obtained by step 1) is mixed with extractant, extracts molybdenum therein；
The extractant includes P204, P507, N235, LIX63, TRPO, Cyanex272, any one of HBL101 or
It is several；
It is 30~50 DEG C to extract reaction temperature, and extraction time is 5~30min, and organic phase is with water phase volume ratio when extraction
4:1~1:5；
Further include obtaining raffinate after the completion of extracting to add return to step 1 after the sulfuric acid of consumption) Leach reaction；
3) tungsten is extracted in hydrogen peroxide extraction-decomposition：
Leached mud obtained by step 1) is added in hydrogenperoxide steam generator and is extracted, filters, was contained after the completion of reaction
The solution and calcium sulfate slag of oxygen wolframic acid and peroxo-polymolybdic acid；Then the solution of the wolframic acid containing peroxide and peroxo-polymolybdic acid is heated to
50~90 DEG C, or directly SO is passed through into the solution of the wolframic acid containing peroxide and peroxo-polymolybdic acid2, control reaction system in hydrogen from
Son a concentration of 0.1mol/L~4.0mol/L, preferably 0.5mol/L~2.0mol/L, until peroxide wolframic acid decomposes precipitation completely
Wolframic acid, and most of peroxo-polymolybdic acid then stays in the solution；Filtering, obtains wolframic acid and the solution containing peroxo-polymolybdic acid；
The hydrogen peroxide adds the molar ratio of molybdic acid to be 0.5~2 with wolframic acid in the decomposition slag:1；
The temperature of the extraction reaction is 10~40 DEG C, and the reaction time is 10min~2.0h；
4) repeatedly dissolving-decomposition purifies tungsten to hydrogen peroxide：
Wolframic acid obtained by step 3) is added in hydrogenperoxide steam generator and is dissolved, filters after the completion of reaction, is contained again
The solution of peroxide wolframic acid and peroxo-polymolybdic acid；Then the solution of the wolframic acid containing peroxide and peroxo-polymolybdic acid is heated to 50~90 DEG C,
Or directly SO is passed through into the solution of the wolframic acid containing peroxide and peroxo-polymolybdic acid2, controlling hydrogen ion concentration in reaction system is
0.1mol/L~4.0mol/L, preferably 0.5mol/L~2.0mol/L, until peroxide wolframic acid decomposes completely is precipitated wolframic acid, and mistake
Oxygen molybdic acid then stays in the solution；Filtering, obtains wolframic acid and the solution containing peroxo-polymolybdic acid；
Step 4) is repeated repeatedly, until obtaining pure tungsten acid；
A concentration of the 5~30% of the hydrogenperoxide steam generator；
The hydrogen peroxide adds the molar ratio of molybdic acid to be 0.5~2 with wolframic acid in the decomposition slag:1；
The temperature of the dissolving reaction is 10~40 DEG C, and the reaction time is 10min~2.0h；
5) pure tungsten acid calcining obtained by step 4) is prepared into tungstic acid；
Alternatively, pure tungsten acid obtained by step 4) is dissolved with hydrogenperoxide steam generator to obtain pure peroxide tungstic acid, it is then ultrasonic
Spray pyrolysis prepares tungsten trioxide powder, or prepares tungstic violet oxide powder or blue oxide powder, or prepares tungsten powder；
A concentration of the 5~30% of the hydrogenperoxide steam generator；
WO in the pure peroxide tungstic acid3A concentration of 10~350g/L；
The ultrasonic spray pyrolysis condition for preparing tungsten trioxide powder：Spray rate is 10~200mL/min；Pyrolysis
Temperature is 500~900 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；
The ultrasonic spray pyrolysis condition for preparing tungstic violet oxide powder or blue oxide powder：Spray rate is
10~200mL/min；The temperature of pyrolysis is 500~900 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/
L；It is passed through reducibility gas hydrogen simultaneously, hydrogen flow rate is 50~600mL/L；
The ultrasonic spray pyrolysis condition for preparing tungsten powder：Spray rate is 10~200mL/min；The temperature of pyrolysis is
900~1100 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；It is passed through reducibility gas hydrogen simultaneously,
Hydrogen flow rate is 100~800mL/L；
6) peroxo-polymolybdic acid decomposition-molten-spray pyrolysis of hydrogen peroxide weight prepares molybdenum oxide/molybdenum powder：
Solution containing peroxo-polymolybdic acid obtained by step 3 and step 4) is heated to 50~90 DEG C, or is passed directly into SO2, directly
It is decomposed completely to peroxo-polymolybdic acid and molybdic acid is precipitated；The molybdic acid of precipitation is dissolved with hydrogenperoxide steam generator, it is molten to filter obtained peroxo-polymolybdic acid
Liquid, then ultrasonic spray pyrolysis prepares molybdenum trioxide powder, or prepares molybdenum powder；
A concentration of the 5~30% of the hydrogenperoxide steam generator；
When preparing peroxo-polymolybdic acid solution with hydrogenperoxide steam generator dissolving, the molar ratio of the hydrogen peroxide and the molybdic acid is
0.5~2:1；And/or reaction temperature is 10~40 DEG C, the reaction time is 10min~2.0h；
With a concentration of 10~350g/L of Mo in the peroxo-polymolybdic acid solution of hydrogenperoxide steam generator dissolving preparation；
The ultrasonic spray pyrolysis condition for preparing molybdenum trioxide powder：Spray rate is 10~200mL/min；Pyrolysis
Temperature is 200~800 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；
The ultrasonic spray pyrolysis condition for preparing molybdenum powder：Spray rate is 10~200mL/min, and the temperature of pyrolysis is
500~1100 DEG C, inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；It is passed through reducibility gas hydrogen simultaneously,
Hydrogen flow rate is 50~600mL/L.
The present invention provides a kind of completely new method for extracting tungsten from high seyrigite, and main advantage is embodied in following several
Point：
(1) cheap and easily-available decomposing agents sulfuric acid, 200~500 yuan/ton of price, only sodium hydroxide reagent cost are used
10%, greatly reduce scheelite disaggregated cost；
(2) it is decomposed using acid, decomposition slag is gypsum, can be used as building materials, not generate dangerous waste soda boiling slag, greatly reduce enterprise
Production and operation cost；
(3) extractant of the hydrogen peroxide as wolframic acid is used, ammonia nitrogen waste water is not generated, Tungsten smelting has been got rid of and continues to use and produced for many years
The technique of raw ammonia nitrogen waste water greatly reduces environmentally friendly cost；
(4) end product (tungsten oxide) and tungsten powder for directly producing various tungsten, the product for improving Tungsten smelting enterprise are additional
Value；
(5) molybdenum separated, the output directly in the form of molybdenum oxide and molybdenum powder, the product for improving Tungsten smelting enterprise are attached
It is value added.
Description of the drawings
Fig. 1 is the method for the present invention process flow diagram；In figure, dotted arrow and dotted line frame representative can select a selection
Parallel processing 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..It is not specified in embodiment specific
Technology or condition person carry out according to technology or condition described in document in the art, or according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Embodiment 1
High seyrigite raw material used in the present embodiment：WO3Grade is that 40%, Mo grades are 5%, and granularity is 120 μm.
A method of tungsten being extracted from high seyrigite, is included the following steps：
(1) Leach reaction：High seyrigite is added in the sulfuric acid solution of concentration 150g/L, the liquid-solid ratio of system is 5:
1, Leach reaction is carried out at 150 DEG C, under the conditions of 0.5Mpa 3 hours；99.5% tungsten is converted to wolframic acid, and 10.5% molybdenum is converted into
The leaching rate of molybdic acid, molybdenum is 89.1%；
(2) molybdenum is extracted in leachate：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；To
Extractant (30%N235+10%TBP+ kerosene) is added in gained leachate, control organic phase is 1 with water phase volume ratio:1, it mixes
It closes, extraction 10 minutes is carried out under the conditions of 40 DEG C, to extract molybdenum therein；Then raffinate is added into return to step after sulfuric acid
(1) it is used as raw material to carry out Leach reaction；
(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 adds the molar ratio of molybdic acid to be 1.5 with wolframic acid in slag is decomposed:1, in temperature
1h is reacted in the extraction that tungsten and molybdenum are carried out under the conditions of 25 DEG C, and reaction product obtains wolframic acid containing peroxide and peroxo-polymolybdic acid solution after filtering
And calcium sulfate slag；The wolframic acid containing peroxide and peroxo-polymolybdic acid solution are heated to 80 DEG C, until peroxide wolframic acid decomposes precipitation completely
Wolframic acid；Wolframic acid (may also contain a small amount of molybdic acid) and the filtrate containing peroxo-polymolybdic acid is obtained by filtration；
(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
Mixed dissolution reacts 1h under part, obtains peroxide tungstic acid；Gained peroxide wolframic acid is heated to 80 DEG C, until peroxide wolframic acid divides completely
Parse wolframic acid；Wolframic acid and the filtrate containing peroxo-polymolybdic acid is obtained by filtration；Step 4) is repeated repeatedly, until obtaining pure tungsten acid (i.e. not
Containing molybdic acid)；
(5) by after pure tungsten acid elution obtained by step (4), then with mass concentration it is 30% hydrogenperoxide steam generator in 25 DEG C of temperature
Under the conditions of hybrid reaction 1h, obtain pure peroxide tungstic acid；
(6) the pure peroxide tungstic acid for obtaining step (5) 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；
(7) filtrate containing peroxo-polymolybdic acid obtained by step (3) and (4) is heated to 90 DEG C, until peroxo-polymolybdic acid decomposes analysis completely
Go out molybdic acid；Then after molybdic acid being washed, then with mass concentration it is that 30% hydrogenperoxide steam generator mix anti-under the conditions of 35 DEG C of temperature
1h is answered, obtains pure peroxo-polymolybdic acid solution again；
(8) the pure peroxo-polymolybdic acid solution for obtaining step (7) is being passed through nitrogen, spray rate 160mL/min, nitrogen
Flow velocity is 400ml/L, the temperature of pyrolysis carries out ultrasonic spray pyrolysis under the conditions of being 500 DEG C, obtains ultrafine spherical molybdenum trioxide powder
End；Impurity content meets the requirement of YS/T639-2007 (1 grade of product) in molybdenum trioxide after testing.
Embodiment 2
High seyrigite raw material used in the present embodiment：WO3Grade is that 30%, Mo grades are 25%, and granularity is 50 μm.
A method of tungsten being extracted from high seyrigite, is included the following steps：
(1) Leach reaction：High seyrigite is added in the sulfuric acid solution of concentration 300g/L, while being additionally added tungsten ore matter
The liquid-solid ratio of the calcium sulfate of amount 5%, system is 5:1, Leach reaction is carried out at 200 DEG C, under the conditions of 1.85Mpa 3 hours；99.5%
Tungsten be converted to wolframic acid, 8.5% molybdenum is converted into molybdic acid, and the leaching rate of molybdenum is 91.2%；
(2) molybdenum is extracted in leachate：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；To
Extractant (40%P204+ kerosene) is added in gained leachate, control organic phase is 2 with water phase volume ratio:1, mixing, at 40 DEG C
Under the conditions of carry out the extraction 10 minutes of molybdenum, return to step (1) carries out Leach reaction as raw material after raffinate adds sulfuric acid；
(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 adds the molar ratio of molybdic acid to be 1.2 with wolframic acid in slag is decomposed:1, in temperature
2h is reacted in the extraction that tungsten and molybdenum are carried out under the conditions of 30 DEG C, and reaction product obtains wolframic acid containing peroxide and peroxo-polymolybdic acid solution after filtering
And calcium sulfate slag；The wolframic acid containing peroxide and peroxo-polymolybdic acid solution are heated to 90 DEG C, until peroxide wolframic acid decomposes precipitation completely
Wolframic acid；Wolframic acid (may also contain a small amount of molybdic acid) and the filtrate containing peroxo-polymolybdic acid is obtained by filtration；
(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
Mixed dissolution reacts 1h under part, obtains peroxide tungstic acid；Gained peroxide wolframic acid is heated to 90 DEG C, until peroxide wolframic acid divides completely
Parse wolframic acid；Wolframic acid and the filtrate containing peroxo-polymolybdic acid is obtained by filtration；Step 4) is repeated repeatedly, until obtaining pure tungsten acid (i.e. not
Containing molybdic acid)；
(5) by after pure tungsten acid elution obtained by step (4), then with mass concentration it is 30% hydrogenperoxide steam generator in 35 DEG C of temperature
Under the conditions of hybrid reaction 1h, obtain pure peroxide tungstic acid；
(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；
(7) filtrate containing peroxo-polymolybdic acid obtained by step (3) and (4) is heated to 90 DEG C, until peroxo-polymolybdic acid decomposes analysis completely
Go out molybdic acid；Then after molybdic acid being washed, then with mass concentration it is that 30% hydrogenperoxide steam generator mix anti-under the conditions of 35 DEG C of temperature
1h is answered, obtains pure peroxo-polymolybdic acid solution again；
(8) the pure peroxo-polymolybdic acid solution for obtaining step (7) is being passed through hydrogen, spray rate 160mL/min, hydrogen
Flow velocity is 400ml/L, the temperature of pyrolysis carries out ultrasonic spray pyrolysis under the conditions of being 900 DEG C, obtains ultrafine spherical molybdenum powder；After testing
Impurity content meets the requirement of GB/T 3461-2006 (FM-1 grades of products) in molybdenum powder.
Embodiment 3
High seyrigite raw material used in the present embodiment：WO3Grade is that 55%, Mo grades are 2.5%, and granularity is 150 μm.
A method of tungsten being extracted from high seyrigite, is included the following steps：
(1) Leach reaction：High seyrigite is added in the sulfuric acid solution of concentration 200g/L, while being additionally added tungsten ore matter
The liquid-solid ratio of the wolframic acid of amount 10%, system is 7:1, Leach reaction is carried out under the conditions of 90 DEG C 4 hours；99.3% tungsten is converted to
Wolframic acid, 1.2% molybdenum are transformed into molybdic acid, and the leaching rate of molybdenum is 98.2%；
(2) molybdenum is extracted in leachate：Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate；To
Extractant (35%LIX63+ kerosene) is added in gained leachate, control organic phase is 1 with water phase volume ratio:1, mixing, 50
The extraction of molybdenum 20 minutes is carried out under the conditions of DEG C, return to step (1) carries out Leach reaction as raw material after raffinate adds sulfuric acid；
(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 30 DEG C of items of temperature
2h is reacted in the extraction that tungsten is carried out under part, and reaction product obtains tungstic acid containing peroxide and calcium sulfate slag after filtering；Directly to mistake
It is passed through SO in oxygen tungstic acid2And hydrogen ion concentration 1.5mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated tungsten
Acid；Wolframic acid (may also contain a small amount of molybdic acid) and the filtrate containing peroxo-polymolybdic acid is obtained by filtration；
(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；
(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.
Comparative example 1
Compared with Example 1, difference lies in, systems during reaction without pressurized treatments, in 90 DEG C of temperature
Under conditions of reacted, 86.5% tungsten is converted to wolframic acid, and 10.5% molybdenum is converted into molybdic acid, and the leaching rate of molybdenum is
69.2%.
Comparative example 2
Compared with Example 1, difference lies in directly dense with quality after wolframic acid that step (3) is obtained by filtration is washed
Degree is 30% hydrogenperoxide steam generator hybrid reaction 1h under the conditions of 35 DEG C of temperature, obtains peroxide tungstic acid again；It is being passed through nitrogen
Gas, spray rate 120ml/min, nitrogen flow rate 400ml/L, pyrolysis temperature carry out ullrasonic spraying heat under the conditions of being 700 DEG C
Solution, obtains ultrafine spherical tungsten trioxide powder；Impurity content does not meet national standard GB/T 3457-2013 in tungstic acid after testing
The requirement of (0 grade of product), has that molybdenum content is exceeded.
Comparative example 3
Compared with Example 2, difference lies in, system is added without the calcium sulfate of tungsten ore quality 5% during reaction,
The liquid-solid ratio of system is 5:1, Leach reaction is carried out at 200 DEG C, under the conditions of 1.85Mpa 3 hours；95.5% tungsten is converted to tungsten
Acid, 6.5% molybdenum are converted into molybdic acid, and the leaching rate of molybdenum is 82.2%.
Comparative example 4
Compared with Example 3, difference lies in, system is added without the wolframic acid of tungsten ore quality 10% during reaction,
The liquid-solid ratio of system is 7:1, Leach reaction is carried out under the conditions of 90 DEG C 4 hours；90.1% tungsten is converted to wolframic acid, 2.2%
Molybdenum is transformed into molybdic acid, and the leaching rate of molybdenum is 78.2%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of method for extracting tungsten from high seyrigite, which is characterized in that include the following steps：
1) Leach reaction：High seyrigite is added in sulfuric acid solution and carries out Leach reaction；It is obtained by filtration and decomposes slag and leachate；
2) extraction extraction molybdenum：Leachate obtained by step 1) is mixed with extractant, extracts molybdenum therein；Or further include that will extract
Raffinate is obtained after the completion adds return to step 1 after the sulfuric acid of consumption) Leach reaction；
3) tungsten is extracted in hydrogen peroxide extraction-decomposition：Leached mud obtained by step 1) is added in hydrogenperoxide steam generator and is extracted,
It is filtered after the completion of reaction, obtains the solution and calcium sulfate slag of wolframic acid containing peroxide and peroxo-polymolybdic acid；It then will the tungsten containing peroxide
The solution of acid and peroxo-polymolybdic acid heats, or is directly passed through SO thereto2, until peroxide wolframic acid decomposes completely is precipitated wolframic acid, mistake
Filter, obtains wolframic acid and the solution containing peroxo-polymolybdic acid；
4) repeatedly dissolving-decomposition purifies tungsten to hydrogen peroxide：Wolframic acid obtained by step 3) is added in hydrogenperoxide steam generator and is dissolved,
It is filtered after the completion of reaction, obtains the solution of wolframic acid containing peroxide and a small amount of peroxo-polymolybdic acid again；Then be heated, or directly to
Wherein it is passed through SO2, until peroxide wolframic acid decomposes completely is precipitated wolframic acid, and peroxo-polymolybdic acid then stays in the solution；Filtering, obtains wolframic acid
And the solution containing peroxo-polymolybdic acid；
Step 4) is repeated repeatedly, until obtaining pure tungsten acid；
5) pure tungsten acid calcining obtained by step 4) is prepared into tungstic acid；
Alternatively, pure tungsten acid obtained by step 4) is dissolved with hydrogenperoxide steam generator to obtain pure peroxide tungstic acid, then ullrasonic spraying
Pyrolysis prepares tungsten trioxide powder, or prepares tungstic violet oxide powder or blue oxide powder, or prepares tungsten powder；
6) peroxo-polymolybdic acid decomposition-molten-spray pyrolysis of hydrogen peroxide weight prepares molybdenum oxide/molybdenum powder：By step 3) and/or step 4)
Solution heating of the gained containing peroxo-polymolybdic acid, or it is passed directly into SO2, until peroxo-polymolybdic acid decomposes completely is precipitated molybdic acid；It will be precipitated
Molybdic acid dissolved with hydrogenperoxide steam generator, filter and peroxo-polymolybdic acid solution be made, then ultrasonic spray pyrolysis prepares molybdenum trioxide powder
End, or prepare molybdenum powder.
2. according to the method described in claim 1, it is characterized in that, being additionally added during the step 1) Leach reaction a certain amount of
Solid wolframic acid and/or CaSO4Crystal seed；
Preferably, the addition of solid wolframic acid is the 0~20% of tungsten ore quality, more preferably the 5~10% of tungsten ore quality；CaSO4
The addition of crystal seed is the 0~20% of tungsten ore quality, more preferably the 5~15% of tungsten ore quality.
3. method according to claim 1 or 2, which is characterized in that the control of step 1) the Leach reaction temperature 50~
200 DEG C, reaction pressure is controlled in 0~10Mpa；And/or
A concentration of 50~500g/L of the step 1) sulfuric acid solution.
4. according to claim 1-3 any one of them methods, which is characterized in that the step 2) extractant includes P204,
Any one of P507, N235, N1923, Lix63, TRPO, Cyanex272, HBL101 or several；
Preferably, step 2) the extraction reaction temperature is 30~50 DEG C, and organic phase and water phase volume ratio are 4 when extraction:1~1:
5。
5. according to claim 1-4 any one of them methods, which is characterized in that be passed through SO in step 3) and/or step 4)2It will
When peroxide wolframic acid decomposes precipitation wolframic acid, it is 0.1mol/L~4.0mol/L to control hydrogen ion concentration in reaction system, preferably
0.5mol/L~2.0mol/L.
6. according to claim 1-5 any one of them methods, which is characterized in that use peroxide in step 3) and/or step 4)
When carrying out extraction reaction in change hydrogen solution, hydrogen peroxide adds the molar ratio of molybdic acid to be 0.5~2 with wolframic acid:1；
And/or step 6) is with hydrogenperoxide steam generator dissolving when preparing peroxo-polymolybdic acid solution, mole of hydrogen peroxide and the molybdic acid
Than being 0.5~2:1；
Preferably, the temperature of the extraction reaction is 10~40 DEG C.
7. according to claim 1-6 any one of them methods, which is characterized in that WO in step 5) the pure peroxide tungstic acid3
A concentration of 10~350g/L.
8. according to claim 1-7 any one of them methods, which is characterized in that step 5) is described to prepare tungsten trioxide powder
Ultrasonic spray pyrolysis condition：Spray rate is 10~200mL/min；The temperature of pyrolysis is 500~900 DEG C；Inert gas is nitrogen
Gas or argon gas, flow velocity are 150~600mL/L；Alternatively,
Step 5) the ultrasonic spray pyrolysis condition for preparing tungstic violet oxide powder or blue oxide powder：Spray rate
For 10~200mL/min；The temperature of pyrolysis is 500~900 DEG C；Inert gas be nitrogen or argon gas, flow velocity be 150~
600mL/L；It is passed through reducibility gas hydrogen simultaneously, hydrogen flow rate is 50~600mL/L；Alternatively,
Step 5) the ultrasonic spray pyrolysis condition for preparing tungsten powder：Spray rate is 10~200mL/min；The temperature of pyrolysis is
900~1100 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；It is passed through reducibility gas hydrogen simultaneously,
Hydrogen flow rate is 100~800mL/L.
9. according to claim 1-8 any one of them methods, which is characterized in that step 6) is dissolved with hydrogenperoxide steam generator to be prepared
Peroxo-polymolybdic acid solution in a concentration of 10~350g/L of Mo；And/or
Step 6) the ultrasonic spray pyrolysis condition for preparing molybdenum trioxide powder：Spray rate is 10~200mL/min；Pyrolysis
Temperature be 200~800 DEG C；Inert gas is nitrogen or argon gas, and flow velocity is 150~600mL/L；Alternatively, step 6) is described
Prepare the ultrasonic spray pyrolysis condition of molybdenum powder：Spray rate is 10~200mL/min, and the temperature of pyrolysis is 500~1100 DEG C, lazy
Property gas be nitrogen or argon gas, flow velocity be 150~600mL/L；It is passed through reducibility gas hydrogen simultaneously, hydrogen flow rate is 50~
600mL/L。
10. according to claim 1-9 any one of them methods, which is characterized in that WO in the high seyrigite3Content is 10
~65%, Mo content are 1~25%；Preferably, the granularity of the high seyrigite is less than 300 μm.
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