CN108559841A - A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product - Google Patents

A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product Download PDF

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CN108559841A
CN108559841A CN201810360985.7A CN201810360985A CN108559841A CN 108559841 A CN108559841 A CN 108559841A CN 201810360985 A CN201810360985 A CN 201810360985A CN 108559841 A CN108559841 A CN 108559841A
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acid
tungsten
peroxide
scheelite
reaction
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CN108559841B (en
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陈星宇
赵中伟
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction 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
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/30Obtaining chromium, molybdenum or tungsten
    • C22B34/36Obtaining tungsten
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention relates to a kind of acid to decompose the method that Scheelite-Wolframite Mixed Mine prepares tungsten product, and this method includes the following steps using Scheelite-Wolframite Mixed Mine as raw material:(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 only consumes cheap and easily-available sulfuric acid, greatly reduces Scheelite-Wolframite Mixed Mine disaggregated cost;Using sulfuric acid decomposition, 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

A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product
Technical field
The present invention relates to chemical production fields, and in particular to a kind of acid decomposition Scheelite-Wolframite Mixed Mine prepares the side of tungsten product 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, a kind of quasi- acid of offer decomposes Scheelite-Wolframite Mixed Mine and prepares tungsten The method of product.
Specifically, the method flow schematic diagram that acid decomposition Scheelite-Wolframite Mixed Mine provided by the invention prepares tungsten product can join It examines shown in Fig. 1.
The method of the invention includes the following steps:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in sulfuric acid solution and carries out Leach reaction;
(2) filtration washing:Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add 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 hydrogenperoxide steam generator be mixed The extraction reaction for carrying out tungsten is closed, reaction product obtains peroxide tungstic acid and gypsum after filtering;By the peroxide tungstic acid Heat or be passed through SO2It is decomposed completely to peroxide wolframic acid and wolframic acid is precipitated;
(4) repeatedly extraction-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 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:Impurity content is met into mark dissolving and carries out tungsten Extraction reaction, obtains pure peroxide tungstic acid;
(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:A concentration of 50~500g/L of the sulfuric acid solution.It is described to react A certain amount of solid wolframic acid can also be added in journey, a certain amount of CaSO can also be added4As crystal seed, the solid wolframic acid and CaSO4Addition be the 0~20% of Scheelite-Wolframite Mixed Mine quality;A certain amount of oxidant can also be added in reaction process To promote the progress of reaction, such as it is passed through oxygen, nitric acid, hydrogen peroxide, sodium hypochlorite.The liquid-solid ratio of the step reaction is preferably 3:1~10:1.As a preferred embodiment, the reaction of step (1) can carry out under the conditions of 50~250 DEG C, 0~10Mpa, reaction Time is preferably 1~6 hour.
In step (2) the of the present invention filtration washing:A certain amount of acid is added in the leachate, makes the concentration of acid solution It is identical as the concentration using acid in step (1), it then can return to step (1) and carry out Leach reaction as raw material.
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 and calcium sulfate slag (i.e. gypsum) is obtained by filtration.Then the peroxide tungstic acid is heated to 50~90 DEG C, or directly SO is passed through into peroxide tungstic acid2And sulfuric acid concentration 0.1mol/L~2.0mol/L in solution is controlled, until Peroxide wolframic acid decomposes completely, and wolframic acid can be precipitated.
The visual raw material difference of operation of the multiple dissolving-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 is then directly used in subsequent step by alignment request, can directly omit purification process;When Scheelite-Wolframite Mixed Mine grade When relatively low, impurity content is above standard requirements in wolframic acid obtained by step (3), then needs the addition hydrogen peroxide in the wolframic acid molten Liquid repeats step (3) and operates at least once, i.e., is purified using hydrogen peroxide, is met the requirements of the standard until obtaining impurity content Wolframic acid.After the present invention controls the impurity content in wolframic acid by step (4), then calcined in subsequent step Or 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 national standard GB/T in the wolframic acid of acquisition When 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 acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, and main advantage is embodied in The following:
The first, the present invention uses cheap and easily-available decomposing agents sulfuric acid, 200~500 yuan/ton of price, only sodium hydroxide The 10% of reagent cost greatly reduces tungsten ore disaggregated cost;
The second, it is gypsum that the present invention, which uses sulfuric acid decomposition Scheelite-Wolframite Mixed Mine, decomposition slag, can be used as building materials, not generate Dangerous waste soda boiling slag greatly reduces 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
Present embodiments provide a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, the raw material that this method uses It is 40% for grade, granularity is 120 μm of Scheelite-Wolframite Mixed Mine, and the method is specially:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in the sulfuric 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, 0.5Mpa 3 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;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add 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 20% 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 and gypsum after filtering;By the peroxide wolframic acid Solution is heated to 80 DEG C, until peroxide wolframic acid decomposes completely is precipitated wolframic acid;After testing, impurity content meets state in gained wolframic acid GB/T 10116-2007 are marked, subsequent step is can be directly used for;
(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 2
Present embodiments provide a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, the raw material that this method uses It is 52% for grade, granularity is 50 μm of Scheelite-Wolframite Mixed Mine, and the method is specially:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in the sulfuric acid solution of concentration 400g/L, add account for it is described black The liquid-solid ratio of the calcium sulfate of white tungsten composite ore quality 5%, system is 10:1, it carries out leaching under the conditions of 200 DEG C, 1.85Mpa anti- It answers 1 hour, 99.3% tungsten is converted to wolframic acid;
(2) filtration washing:Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add 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 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 and gypsum after filtering;Directly to peroxide wolframic acid SO is passed through in solution2And sulfuric acid concentration 1.5mol/L in solution is controlled, 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 rate 350ml/L, pyrolysis temperature carry out ullrasonic spraying under the conditions of being 500 DEG C Pyrolysis, obtains ultrafine spherical blue oxide tungsten powder;Impurity content meets national standard GB/T in blue tungstic acid after testing The requirement of 3457-2013 (0 grade of product).
Embodiment 3
Present embodiments provide a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, the raw material that this method uses It is 55% for grade, granularity is 100 μm of Scheelite-Wolframite Mixed Mine, and the method is specially:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in the sulfuric acid solution of concentration 250g/L, is passed through oxygen, system Liquid-solid ratio be 3:1, Leach reaction is carried out under the conditions of 180 DEG C, 2.5Mpa 4 hours, 99.3% tungsten is converted to wolframic acid;
(2) filtration washing:Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add sulfuric acid;
(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 and gypsum after filtering;Directly to peroxide tungstic acid In be passed through SO2And sulfuric acid concentration 0.5mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated wolframic acid;After testing, institute It obtains impurity content in wolframic acid and meets national standard GB/T10116-2007, 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
Present embodiments provide a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, the raw material that this method uses It is 45% for grade, granularity is 150 μm of Scheelite-Wolframite Mixed Mine, and the method is specially:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in the sulfuric acid solution of concentration 300g/L, time of 50g/L is added The liquid-solid ratio of sodium chlorate, system is 5:1, Leach reaction is carried out under the conditions of 90 DEG C, 0Mpa 4 hours, 99.1% tungsten is converted to Wolframic acid;
(2) filtration washing:Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add sulfuric acid;
(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 and gypsum after filtering;Directly to peroxide tungstic acid In be passed through SO2And sulfuric acid concentration 0.1mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated wolframic acid;After testing, institute It obtains impurity content in wolframic acid and meets national standard GB/T10116-2007, 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 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
Present embodiments provide a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, the raw material that this method uses It is 35% for grade, granularity is 80 μm of Scheelite-Wolframite Mixed Mine, and the method is specially:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in the sulfuric acid solution of concentration 250g/L, add account for it is described black The wolframic acid of white tungsten composite ore quality 10%, while the nitric acid of 100g/L is added, the liquid-solid ratio of system is 3:1,120 DEG C, Leach reaction is carried out under the conditions of 1.5Mpa 4 hours, 99.3% tungsten is converted to wolframic acid;
(2) filtration washing:Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add sulfuric acid;
(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 and gypsum after filtering;Directly to peroxide tungstic acid In be passed through SO2And sulfuric acid concentration 0.5mol/L in solution is controlled, until peroxide wolframic acid decomposes completely is precipitated wolframic acid;After testing, institute It obtains impurity content in wolframic acid and meets national standard GB/T10116-2007, can be directly used for subsequent step;
(4) by after wolframic acid washing obtained by step (3), yellow tungsten oxide is obtained after carrying out calcining 5.0h under the conditions of 800 DEG C. Impurity content meets the requirement of national standard GB/T3457-2013 (0 grade of product) in yellow tungstic acid after testing.
Embodiment 6
Present embodiments provide a kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product, the raw material that this method uses It is 48% for grade, granularity is 250 μm of Scheelite-Wolframite Mixed Mine, and the method is specially:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in the sulfuric acid solution of concentration 400g/L, hydrogen peroxide, body is added The liquid-solid ratio of system is 5:1, Leach reaction is carried out under the conditions of 160 DEG C, 2.0Mpa 5 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;In the leaching Return to step (1) carries out Leach reaction as raw material after going out in liquid to add 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 1.5 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 peroxide tungstic acid and gypsum after filtering;Directly heat peroxide tungsten Acid solution is to 90 DEG C, until peroxide wolframic acid decomposes completely is precipitated wolframic acid;After testing, impurity content meets state in gained wolframic acid GB/T 10116-2007 are marked, subsequent step is can be directly used for;
(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 argon gas, spray rate 120ml/min, argon gas Flow velocity is 400ml/L, pyrolysis temperature carries out ultrasonic spray pyrolysis under the conditions of being 850 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.
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 product, which is characterized in that include the following steps:
(1) Leach reaction:Scheelite-Wolframite Mixed Mine is added in sulfuric acid solution and carries out Leach reaction;
(2) filtration washing:Reaction product obtained by step (1) is filtered, obtains decomposing slag and leachate;In the leachate In add return to step (1) after sulfuric acid and carry out Leach reaction as raw material;
(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 and gypsum after filtering;The peroxide tungstic acid is heated Or it is passed through SO2It is decomposed completely to peroxide wolframic acid and wolframic acid is precipitated;
(4) repeatedly extraction-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 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 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 stating Scheelite-Wolframite Mixed Mine is less than 300 μm.
3. method according to claim 1 or 2, which is characterized in that in the step (1), a concentration of the 50 of the sulfuric acid ~500g/L;
And/or the reaction carries out under the conditions of 50~250 DEG C, 0~10Mpa.
4. according to the method described in claim 3, being equivalent to institute it is characterized in that, being added in the step (1), in reaction process The solid wolframic acid for stating Scheelite-Wolframite Mixed Mine quality 0~20% is reacted;
And/or the calcium sulfate for being equivalent to the Scheelite-Wolframite Mixed Mine quality 0~20% is added in reaction process as crystal seed;
And/or oxidant is added in reaction process to promote the progress of reaction, the oxidant to be selected from oxygen, nitric acid, peroxidating It is one or more in hydrogen, sodium hypochlorite.
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 and/or ultrafine spherical blue oxide tungsten 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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