CN105905947A - Method for preparing tungstate solution by treating wolframite with sulfuric acid - Google Patents

Method for preparing tungstate solution by treating wolframite with sulfuric acid Download PDF

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Publication number
CN105905947A
CN105905947A CN201610341860.0A CN201610341860A CN105905947A CN 105905947 A CN105905947 A CN 105905947A CN 201610341860 A CN201610341860 A CN 201610341860A CN 105905947 A CN105905947 A CN 105905947A
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China
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solution
ammonium
transition
wolframite
sulfuric acid
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CN201610341860.0A
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Inventor
李小斌
崔源发
周秋生
罗建新
齐天贵
李建圃
刘桂华
徐双
彭志宏
申雷霆
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Jiangsu Hi-Tech Development Application Co Ltd
Central South University
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Jiangsu Hi-Tech Development Application Co Ltd
Central South University
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Priority to CN201610341860.0A priority Critical patent/CN105905947A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates

Abstract

The invention provides a method for preparing a tungstate solution by treating wolframite with sulfuric acid. The method comprises the following steps: wolframite transformation: preparing a sulfuric acid solution with a certain mass concentration, controlling proper liquid-solid ratio and temperature, adding wolframite with certain granularity to the sulfuric acid solution to undergo transformation reaction and carrying out filtration after the reaction is finished, thus obtaining transformation filtrate and a transformation material; dissolution of the transformation material: preparing an ammonium salt or sodium salt solution with a certain concentration, controlling proper liquid-solid ratio and temperature, mixing the transformation material with the ammonium salt or sodium salt solution to react, and after reacting for a certain time, carrying out filtration, thus obtaining an ammonium tungstate solution or a sodium tungstate solution; treatment of the transformation filtrate: adding a theoretical quantity of ammonium salt to the transformation filtrate, so that a crystal membrane appears on the surface of the solution, standing and cooling until an ammonium ferrous sulfate crystal is completely separated by crystallization and carrying out vacuum filtration, thus obtaining the ammonium ferrous sulfate crystal, supplementing the crystallization mother liquor with sulfuric acid and then returning to the step of wolframite transformation to treat wolframite. The method has the advantages of no pollutant discharge, low production cost, low energy consumption, convenience in operation and easiness in industrialization.

Description

A kind of method being prepared tungstate solution by sulfuric acid treatment wolframite
Technical field
The present invention relates to a kind of method that tungsten mineral material processes and prepares tungstate solution, particularly one and prepared tungsten by sulfuric acid treatment wolframite The method of acid salt solution, belongs to Tungsten smelting technical field.
Background technology
Industrial, the essential mineral of tungstenic is wolframite and scheelite.Although wolframite reserves are few, account for gross reserves less than 30%, but black tungsten Ore resources is prone to exploitation, selects smelting difficulty little, has innate advantage for comparing scheelite.
For the process technique of wolframite, mainly have following several:
Soda pressure leaching method, by tungsten mineral material and soda (Na at a temperature of 180～230 DEG C2CO3) solution reacts, and makes tungsten with tungsten Acid sodium form enters solution, and ferrum, calcium, manganese enter slag phase with carbonate (part ferrum is with oxide) form, thus realizes initial gross separation, should Method is applicable to process scheelite and Scheelite-Wolframite Mixed Mine, just can process black tungsten under conditions of improving soda consumption and adding appropriate NaOH Ore deposit.But, soda pressure leaching method temperature requirement is high, requires that liquid-solid ratio is big simultaneously, and correspondingly the big energy consumption of ore pulp equipment volume is high, and, Wolframite and Na2CO3The reaction of solution is more complicated, is actually needed more Na2CO3, discomposing effect is poor more than scheelite.
NaOH decomposition technique, by the WO in wolframite3All be converted into solubility sodium tungstate enter aqueous solution, and ferrum, manganese, calcium etc. all with The forms such as the oxide of indissoluble or hydroxide enter slag and separate with tungsten.The method mainly for the treatment of wolframite, process scheelite, with During the high wolframite of calcium content, alkali consumption is big, causes a large amount of harmful salt discharge, and processing cost is high, and in slurry dilution, residue washing mistake Being easy in journey back reaction, slag tungstenic increases.Alkali decomposition process processes wolframite technology maturation, is widely used, though but alkali consumption is relative Soda pressure leaching method has reduced, but still 1.5～4.5 times of Need Hierarchy Theory amount multiple, separate for follow-up tungsten alkali and alkali circulation brings difficulty.
Hydrochloric acid decomposition technique, by the WO in wolframite3Precipitating with the form of wolframic acid, ferrum, manganese enter solution with soluble-salt, thus Realize separating.Hydrochloric acid decomposition method flow process is short, low cost, but hydrochloric acid volatilization is serious in catabolic process, and operating environment deteriorates, Cl-To equipment Seriously corroded, has a large amount of containing Cl simultaneously-Discharge of wastewater, causes environmental pollution.
Other decomposition technique report processing wolframite is less.
" the wolframite acidity extraction new technology research " of Zhao Zhongwei seminar of Central South University research, utilizes sulphuric acid to replace HCl treatment wolframite, But it uses soaking while grinding and its equipment when processing wolframite, higher to equipment requirements, and adds hydrochloric acid or NaCl to improve resolution ratio, The most inherently solve Cl-Corrosion and the problem of HCl volatilization, and less to the further treatment research of subsequent solution and wolframic acid.
Summary of the invention
It is an object of the invention to provide a kind of by sulfuric acid treatment wolframite with the method preparing tungstate solution, its resolution ratio is high, energy consumption is low, nothing Pollution, low cost, easy to operate, environmental friendliness.
To this end, the invention provides a kind of by sulfuric acid treatment wolframite with the method preparing tungstate solution, its key step is as follows:
1) wolframite transition, the sulfuric acid solution of preparation certain mass concentration, the wolframite of certain particle size is added in this solution and reacts, Liquid-solid ratio is 2:1～10:1, and temperature is ＞ 70 DEG C, and the response time is ＞ 3h, and reaction is filtrated to get filtrate and material transition after terminating；
2) material dissolution transition, prepares certain density ammonium salt or sodium salt solution, and liquid-solid ratio is 2:1～6:1, and temperature is 10～50 DEG C, reaction 0.5～5h, it is filtrated to get ammonium tungstate solution or sodium tungstate solution after having reacted；
3) process of filtrate, adds theoretical amount in filtrate and obtains ammonium salt, (the NH in solution4)2SO4With FeSO4React at a certain temperature Occurring that epitaxial, standing are cooled to Ferrous ammonium sulfate crystal and separate out completely to solution surface, decompression excess obtains Ferrous ammonium sulfate crystal, and filtrate is mended After entering sulphuric acid, return processes wolframite.
Preferably, step 1) described in wolframite, it is also possible to be Scheelite-Wolframite Mixed Mine, containing WO3Mass percent is 10%～75%, Granularity is not more than 100 μm, preferably WO3Mass percent is ＞ 40%, granularity ＜ 30 μm；
Preferably, step 1) described in the sulfuric acid solution of certain mass concentration, concentration is with H2SO4Quality meter, H2SO4＞ 400g/L, excellent Elect 500～700g/L as；
Preferably, step 1) described in liquid-solid ratio be 2:1～10:1, preferably 3:1～5:1, more preferably 3:1；
Preferably, step 1) described in temperature be ＞ 70 DEG C, preferably 70～100 DEG C, more preferably 90～100 DEG C；
Preferably, step 1) described in response time be ＞ 3h, preferably 3～10h, more preferably 5～8h；
Preferably, step 2) described in ammonium salt be ammonia, ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate, ammonium phosphate etc. A series of ammonium salts, preferably ammonium carbonate, ammonia；
Preferably, step 2) described in certain density ammonium salt, concentration, with theoretical gauge, excess ＞ 50g/L, is preferably excess ＞ 100g/L；
Preferably, step 2) described in sodium salt be sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., sodium silicate, phosphoric acid A series of sodium salt such as sodium, preferably sodium carbonate, sodium hydroxide；
Preferably, step 2) described in certain density sodium salt, concentration is theoretical gauge, not less than theoretical amount；
Preferably, step 2) described in liquid-solid ratio be 2:1～6:1, preferably 3:1～5:1, more preferably 3:1；
Preferably, step 2) described in temperature be 10～50 DEG C, preferably 15～35 DEG C；
Preferably, step 2) described in response time be 0.5～5h, preferably 1～3h；
Preferably, step 3) described in ammonium salt be ammonium sulfate, ammonia, ammonium carbonate, ammonium hydrogen carbonate, preferably ammonium sulfate；
Preferably, step 3) described in temperature be 50～80 DEG C, preferably 60～70 DEG C.
The present invention uses sulphuric acid to decompose wolframite (mainly with FeWO4Meter), react such as formula (1), by the WO in wolframite3With H2SO4 Form precipitation, ferrum, manganese etc. enter solution；Process in leaching adds ammonium salt or sodium salt, wolframic acid is converted into tungstates, to add carbonic acid As a example by ammonium, reaction is such as formula (2)；Adding ammonium salt in the sulphuric acid filtrate with ferrous sulfate, obtain Ferrous ammonium sulfate crystal, filtrate fills into sulphuric acid Rear return process wolframite ammonium sulfate is as a example by adding ammonium sulfate, and reaction is such as formula (3).
H2SO4+FeWO4=FeSO4+H2WO4 (1)
H2WO4+(NH4)2CO3=(NH4)2WO4+H2O+CO2 (2)
FeSO4+(NH4)2SO4+6H2O=(NH4)2SO4·FeSO4·6H2O (3)
According to the present invention, compared with prior art, the invention have the advantages that
(1) employing sulfuric acid treatment wolframite of the present invention, solves and overcomes Cl-seriously corroded and HCl in tradition hydrochloric acid decomposition technique and wave Question is inscribed；
(2) adjuvant that the present invention uses is common ammonium salt and sodium salt, is conveniently easy to get, it is easy to large-scale production；
(3) present invention is during dissolution obtains ammonium tungstate solution, carries out at normal temperatures, it is easy to produce, energy-saving and cost-reducing and its resolution ratio can Reach more than 98.5%；
(4) present invention is during dissolution obtains sodium tungstate solution, carries out at normal temperatures, it is easy to produce, and the consumption of sodium salt is theoretical amount Time, slag tungstenic is less than 4%, largely reduces the consumption of sodium salt, alleviates the processing load of follow-up sodium salt；
(5) present invention achieves the comprehensive utilization of material, the ferrous sulfate that transition, filtrate produced in processing can be used for extracting sulfuric acid ferrous ammonium, Non-pollutant discharge, environmental friendliness；
(6) equipment is simple, easy to operate, it is easy to industrial applications.
(7) combination of " wolframite transition " and " material dissolution transition " two steps in the present invention, not only can realize normal pressure operation and effectively reduce Energy consumption, and total overall reaction process does not all have rigors to reaction unit, it is simple to implement industrialization.
(8) present invention can process the low-grade wolframite of high impurity, black tungsten flotation tailing, Scheelite-Wolframite Mixed Mine.
(9) tungsten recovery rate of the present invention is stable more than 98%, and up to more than 99.5% during the higher scheelite of process, and supplies consumption is few, Economy is strong.
Accompanying drawing explanation
Fig. 1 is the structural principle schematic diagram of the system being prepared tungstate solution by sulfuric acid treatment wolframite according to the present invention.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.The only help of described embodiment understands the present invention, and it is right to be not construed as The concrete restriction of the present invention.Without departing under the technology of the present invention state of mind, according to ordinary skill knowledge and customary means, make each Plant and replace and change, all should be included within the scope of the invention.
Include as it is shown in figure 1, prepared the system of tungstate solution by sulfuric acid treatment wolframite:
Wolframite device 10 transition, it has isomerization container 11 and filter 12 transition, and it is molten that this isomerization container 11 has sulphuric acid Liquid entrance 13, wolframite entrance 14 and isomerization liquid outlet 15, this, filter 12 had isomerization liquid entrance 16, filter transition transition Liquid outlet 17 and material outlet 18 transition；
Make the transition material dissolving device 20, and it has mixing reactor 21 and dissolution filter 22, and this mixing reactor 21 has material transition Entrance 23, ammonium salt or sodium salt solution entrance 24 and dissolution taphole 25, this dissolution filter 22 has dissolution solution inlet 26, filtering residue Outlet 27, ammonium tungstate solution or sodium tungstate solution outlet 28；And
Transition filtrate processing means 30, it has filtrate crystallisation container 31 and crystal filter 32 transition, this transition filtrate crystallisation container 31 Having ammonium salt and add entrance 33, material inlet 36 transition and liquid to be filtered outlet 37, this crystal filter 32 has liquid to be filtered entrance 38, Ferrous ammonium sulfate crystal outlet 34 and crystalline mother solution outlet 35, crystalline mother solution outlet 35 connects with sulfuric acid solution entrance 13.
Transition, material outlet 18 was the outlet of wolframic acid filter cake.
Particularly, wolframite device 10 transition also includes:
H 2 so 4 concentration controller 1, its range is at least with H2SO4Quality meter H2SO4＞ 400g/L, preferably 500～700g/L；
Wolframite liquid-solid ratio controller 2 transition, its range is at least 2:1～10:1, preferably 5:2～5:1, more preferably 3:1；
Wolframite temperature controller 3 transition, its range is at least temperature ＞ 70 DEG C, preferably 70～100 DEG C, more preferably 90～100 DEG C；
Wolframite isomerization time controller 4, its range is at least ＞ 3h, preferably 3～10h, more preferably 5～8h；And/or,
Wolframite Task-size Controlling device 5, its range is at least not more than 100 μm, preferably ＜ 30 μm.
Transition, material dissolving device 20 also included:
Ammonium salt consistency controller 6, its range is at least concentration with theoretical gauge excess ＞ 50g/L, preferably excess ＞ 100g/L, or sodium salt solution Consistency controller 6, its range is at least theoretical gauge that concentration consumes with wolframic acid filter cake not less than theoretical amount；
Make the transition material dissolution liquid-solid ratio controller 7, and its range is at least 2:1～6:1, preferably 3:1～5:1, more preferably 3:1；
Make the transition material leaching temperature controller 8, and its range is at least 10～50 DEG C, preferably 15～35 DEG C；And/or,
Make the transition material dissolution response time controller 9, and its range is at least 0.5～5h, preferably 1～3h.
Transition, filtrate processing means 30 also included:
Transition, filtrate processed ammonium salt theoretical amount controller 51, and ammonium salt is selected from ammonium sulfate, ammonia, ammonium carbonate, ammonium hydrogen carbonate, preferably sulfuric acid ammonium；
Make the transition filtrate treatment temperature controller 52, and its range is at least 50～80 DEG C, preferably 55-80 DEG C, more preferably 60～70 DEG C；And/or, Pressure controller 53.
Described wolframite entrance 14 is Scheelite-Wolframite Mixed Mine entrance；
Described wolframite entrance 14 has containing WO3Mass percent controller 19, its range is at least 10%～75%, preferably ＞ 40%.
Described ammonium salt solution entrance 24 is that ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate, ammonium phosphate etc. are containing energy and Ca2+ Form the ammonium salt solution entrance of the anion of settlement, preferably sal volatile entrance；
Described sodium salt solution entrance 24 is that sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., sodium silicate, sodium phosphate etc. are containing energy and Ca2+ Form the sodium salt solution entrance of the anion of settlement, preferably sodium carbonate entrance.
Ammonium tungstate solution outlet 28, purification are sequentially communicated with crystallisation vessel 41, crystal filter 42 and separator 43, this crystal filter 42 have APT solid outlet 44 and crystalline mother solution outlet 45；Crystalline mother solution outlet 45 connects with the second sulfuric acid solution entrance 46, this point Having wolframic acid outlet 47 and heavy tungsten mother liquor outlet 48 from device 43, wolframic acid outlet 47 connects with material dissolving device 20 transition, heavy tungsten mother solution Outlet 48 and CaCO3Add entrance 49,45-95 DEG C of reaction temperature controller 54, time controller 55, material dissolving device 20 transition even Logical.
Second sulfuric acid solution entrance 46 has sulfuric acid solution addition controller 56, and its range is at least the theoretical gauge with ammonium tungstate consumption not Less than theoretical amount.
Transition, filtrate processing means 30 had stirring paddle, and such as, stirring paddle can be folding paper or Bu Lumajinshi, helical-ribbon type.
Stirring paddle has mixing speed controller 57, and its range is at least 50-80 rev/min, preferably 60-65 rev/min.
Embodiment 1:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 10min, granularity ＜ 30 μm；Join Concentration processed is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 2:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 10min, granularity ＜ 30 μm；Join Concentration processed is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reaction 2h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 3:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜ 20 μm；Join Concentration processed is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 95 DEG C, response time 7h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 150g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 25 DEG C, reacts 1h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 4:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜ 20 μm；Join Concentration processed is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 95 DEG C, response time 7h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 25 DEG C, reaction 1h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 4% in filtering residue.
Embodiment 5:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 200g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 35 DEG C, reacts 3h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 6:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 35 DEG C, reaction 3h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 7:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 40 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 8:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 40 DEG C, reaction 2h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 2% in filtering residue.
Embodiment 9:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 1:1 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 10:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 1:1 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reaction 2h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 11:
Certain Scheelite-Wolframite Mixed Mine (WO3Weight/mass percentage composition is 56%), Scheelite-Wolframite Mixed Mine and water 1:1 are in vibromill wet grinding 10min, granularity ＜ 30 μm；Compound concentration is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, the response time 8h, is filtrated to get material transition, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 12:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:2 are in vibromill wet grinding 10min, granularity ＜ 30 μm；Join Concentration processed is the sulfuric acid solution of 700g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 100 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reaction 2h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 13:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1.3 are in vibromill wet grinding 20min, granularity ＜ 20 μm； Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 95 DEG C, response time 7h, filter To material transition, its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 150g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 25 DEG C, reacts 1h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 14:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1.2 are in vibromill wet grinding 20min, granularity ＜ 20 μm； Compound concentration is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 95 DEG C, response time 7h, filter To material transition, its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 25 DEG C, reaction 1h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 4% in filtering residue.
Embodiment 15:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 4h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 200g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 35 DEG C, reacts 3h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 16:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1.1 are in vibromill wet grinding 15min, granularity ＜ 25 μm； Compound concentration is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, filter To material transition, its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 35 DEG C, reaction 3h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.
Embodiment 17:
Certain wolframite (WO3Weight/mass percentage composition is 56%), wolframite and water 1:1 are in vibromill wet grinding 20min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 500g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 40 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 18:
Certain scheelite (WO3Weight/mass percentage composition is 56%), scheelite and water 1:1 are in vibromill wet grinding 20min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 300g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 3:1, temperature 105 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 50 DEG C, reaction 6h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 2% in filtering residue.
Embodiment 19:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 2:5 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 350g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is finally the sal volatile of theoretical amount excess 100g/L, containing 5%NH3·H2O, by molten for above-mentioned material addition transition Liquid, liquid-solid ratio is 3:1, and temperature is 60 DEG C, reacts 2h, is filtrated to get ammonium tungstate solution, slag tungstenic ＜ 1% in filtering residue.
Embodiment 20:
Certain black and white tungsten ore (WO3Weight/mass percentage composition is 60%), tungsten ore and water 1:1 are in vibromill wet grinding 15min, granularity ＜ 25 μm；Join Concentration processed is the sulfuric acid solution of 400g/L；Mineral aggregate is mixed with solution, liquid-solid ratio 5:1, temperature 90 DEG C, response time 8h, be filtrated to get Make the transition material, and its X-ray diffraction analysis result shows, present in grog, thing does not contains CaWO mutually4。
Compound concentration is the sodium carbonate liquor of theoretical amount, and by above-mentioned material addition transition solution, liquid-solid ratio is 3:1, and temperature is 30 DEG C, reaction 2h, is filtrated to get sodium tungstate solution, slag tungstenic ＜ 3% in filtering residue.

Claims (10)

1. the preparation method of a tungstate solution, it is characterised in that comprise the following steps:
Make wolframite make the transition, carry out normal pressure or reaction under high pressure, obtain make the transition filtrate and material transition, to overcome in tradition hydrochloric acid decomposition technique Cl-Seriously corroded and HCl volatilization problems；
Making filtrate transition be comprehensively utilized, solid phase can be used for producing side-product, and non-pollutant discharge, and liquid phase circulation is to participating in wolframite Transition；
Make material dissolution transition, use the adjuvant being conveniently easy to get and being prone to large-scale production, operation under normal pressure or high pressure, obtain tungstate solution.
Method the most according to claim 1, it is characterised in that comprise the following steps:
1) wolframite transition: the sulfuric acid solution of preparation certain mass concentration, suitable liquid-solid ratio and temperature are controlled, by the black tungsten of certain particle size Ore deposit adds and carries out isomerization in this sulfuric acid solution, after reaction terminates, filters, and obtains make the transition filtrate and material i.e. wolframic acid filter cake transition；
2) material dissolution transition: prepare certain density ammonium salt or sodium salt solution, control suitable liquid-solid ratio and temperature, by thing above-mentioned transition Material and this ammonium salt or sodium salt solution hybrid reaction, after reaction certain time, filter, obtain ammonium tungstate solution or sodium tungstate solution (filtering residue master Wanting composition is stone-like pulse, such as silicon dioxide, calcium mineral, and remaining concrete composition is relevant with wolframite raw material used, if containing valuable constituent, Can recycle further)；
3) transition, filtrate processed: adds the ammonium salt of theoretical amount to transition in filtrate, makes (NH in solution4)2SO4With FeSO4At a certain temperature React and occur that epitaxial, standing are cooled to Ferrous ammonium sulfate crystal and are fully crystallized precipitation, filtration under diminished pressure to solution surface, obtain Ferrous ammonium sulfate brilliant Body, after filling into sulphuric acid, returns wolframite transformation process in crystalline mother solution.
Method the most according to claim 2, it is characterised in that
Use sulfuric acid treatment wolframite；
The solid phase that described solid phase can be used for producing in side-product is ferrous sulfate, and side-product is Ferrous ammonium sulfate；
Described tungstate solution is ammonium tungstate solution or sodium tungstate solution；
Described adjuvant is common ammonium salt and sodium salt；And/or,
Transition, material was wolframic acid filter cake,
When wolframite makes the transition, the sulfuric acid solution of preparation certain mass concentration, control suitable liquid-solid ratio and temperature, by the wolframite of certain particle size Add and this sulfuric acid solution carries out isomerization, after reaction terminates, by being filtrated to get filtrate transition and material transition, wherein,
Described wolframite can also be Scheelite-Wolframite Mixed Mine, containing WO3Mass percent is 10%～75% (preferably WO3Mass percent For ＞ 40%)；
Described certain mass concentration is with H2SO4Quality meter, H2SO4＞ 400g/L, preferably 500～700g/L；
Described suitable liquid-solid ratio is 2:1～10:1, preferably 5:2～5:1, more preferably 3:1；
Described suitable temperature is ＞ 70 DEG C, preferably 70～100 DEG C, more preferably 90～100 DEG C；,
The wolframite isomerization time is ＞ 3h, preferably 3～10h, more preferably 5～8h；And/or
Described certain particle size is not more than 100 μm, the most described certain particle size ＜ 30 μm.
Method the most according to claim 2, it is characterised in that when making that transition, filtrate was comprehensively utilized, added in filtrate to transition The ammonium salt of theoretical amount, makes (NH in solution4)2SO4With FeSO4React at a certain temperature, to solution surface, epitaxial occurs, stand and be cooled to sulfur Acid ferrous ammonium crystal is fully crystallized precipitation, filtration under diminished pressure, obtains Ferrous ammonium sulfate crystal, after filling into sulphuric acid, returns wolframite in crystalline mother solution Transformation process, wherein,
Described ammonium salt is ammonium sulfate, ammonia, ammonium carbonate, ammonium hydrogen carbonate, preferably sulfuric acid ammonium；And/or,
Described uniform temperature is 50～80 DEG C, preferably 60～70 DEG C.
Method the most according to claim 2, it is characterised in that when making material dissolution transition, prepare certain density ammonium salt or sodium salt Solution, controls suitable liquid-solid ratio and temperature, by above-mentioned transition material with this ammonium salt or sodium salt solution hybrid reaction, after reaction certain time, By obtaining filtering ammonium tungstate solution or sodium tungstate solution, wherein,
Described ammonium salt is that ammonium carbonate, ammonium hydrogen carbonate, ammonium fluoride, ammonium oxalate, ammonium silicate, ammonium phosphate etc. are containing energy and Ca2+It is stable heavy to be formed The ammonium salt of the anion formed sediment, preferably ammonium carbonate；
Described certain density ammonium salt, its concentration, with theoretical gauge, excess ＞ 50g/L, is preferably excess ＞ 100g/L；
Described sodium salt is that sodium carbonate, sodium bicarbonate, sodium fluoride, Disodium oxalate., sodium silicate, sodium phosphate etc. are containing energy and Ca2+It is stable heavy to be formed The sodium salt of the anion formed sediment, preferably sodium carbonate；
Described certain density sodium salt, the theoretical gauge that its concentration consumes with wolframic acid filter cake, not less than theoretical amount；
The most suitable described liquid-solid ratio is 2:1～6:1, preferably 3:1～5:1, more preferably 3:1；
Described suitable temperature is 10～50 DEG C, preferably 15～35 DEG C；And/or,
Described reaction certain time is 0.5～5h, preferably 1～3h.
Method the most according to claim 5, it is characterised in that the process step of described ammonium tungstate solution is as follows:
1) ammonium tungstate solution purified, crystallize, obtain APT solid and crystalline mother solution；
2) adding sulfuric acid solution in crystalline mother solution, isolated wolframic acid and heavy tungsten mother solution, wolframic acid returns described material dissolution transition step；
3) heavy tungsten mother solution will add CaCO3, after 45-95 DEG C of reaction certain time (more than 0.5 hour, preferably 1.5～2.5 hours), Filter, obtain returning liquid containing ammonium, return liquid containing ammonium and return described material dissolution transition step.
Method the most according to claim 6, it is characterised in that
Step 2) in, contained ammonium tungstate reacts generation wolframic acid precipitation to sulfuric acid solution with crystalline mother solution, and the addition of sulfuric acid solution disappears with ammonium tungstate The theoretical gauge of consumption, not less than theoretical amount.
Method the most according to claim 6, it is characterised in that
Step 3) in, reaction temperature is 55-80 DEG C, preferably 60-70 DEG C.
Method the most according to claim 6, it is characterised in that
Step 3) in, it being stirred with stirring paddle during reaction, stirring paddle is folding paper or Bu Lumajinshi, helical-ribbon type.
Method the most according to claim 9, it is characterised in that
The mixing speed of stirring paddle is 50-80 rev/min, preferably 60-65 rev/min.
CN201610341860.0A 2016-05-20 2016-05-20 Method for preparing tungstate solution by treating wolframite with sulfuric acid Pending CN105905947A (en)

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CN114477288A (en) * 2021-12-16 2022-05-13 中南大学 Comprehensive utilization and treatment method for wolframite resources
CN115893494A (en) * 2022-11-16 2023-04-04 江西理工大学 Method for preparing ammonium paratungstate by smelting wolframite

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CN114477288A (en) * 2021-12-16 2022-05-13 中南大学 Comprehensive utilization and treatment method for wolframite resources
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CN115893494A (en) * 2022-11-16 2023-04-04 江西理工大学 Method for preparing ammonium paratungstate by smelting wolframite

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