CN102021329A - Method for extracting tungsten from scheelite and producing high-quality calcined gypsum - Google Patents
Method for extracting tungsten from scheelite and producing high-quality calcined gypsum Download PDFInfo
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- CN102021329A CN102021329A CN2010106051102A CN201010605110A CN102021329A CN 102021329 A CN102021329 A CN 102021329A CN 2010106051102 A CN2010106051102 A CN 2010106051102A CN 201010605110 A CN201010605110 A CN 201010605110A CN 102021329 A CN102021329 A CN 102021329A
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Abstract
The invention provides a method for extracting tungsten from scheelite and producing high-quality calcined gypsum, comprising the following steps: adding a mixed acid of phosphoric acid and sulphuric acid to decompose scheelite; and after decomposition, adding hydrated gypsum seed crystals to finish the dewatering conversion process of dihydrate gypsum to obtain hydrated gypsum with good properties. The invention has the following advantages: the efficient atmospheric pressure leaching of scheelite is realized, the resource and energy consumption is saved, and the decomposition rate of scheelite can reach over 98%; the serious problems of Cl<-> corrosion and HCl volatilization in the traditional acid decomposition process can be overcome; the recycling of phosphoric acid is basically realized, and the leaching cost and the wastewater discharge are greatly reduced; the leaching device is simple, the operation is convenient and industrialization is easy to realize; the obtained byproduct gypsum has pure quality and can be used to produce gypsum boards, and can be used in retarder, plaster and the like produced by using cement; and due to the recrystallization process, the P2O5 content in gypsum is further reduced to below 0.5%.
Description
Technical field
The present invention relates to the extraction of rare refractory metal tungsten in the hydrometallurgy field, is a kind of method of extracting tungsten and producing the high quality plaster of Paris from sheelite specifically.
Background technology
The main resource that consumes of China's tungsten smelting at present is that wolframite (is easy to select smelting, output accounts for more than 90%), and only about 49.13 ten thousand tons of black tungsten resource basis reserves, will be totally at the several years internal consumption, add that newfound tungsten resource also is complicated white tungsten resource mostly, presented the situation that sheelite has comparative advantage (about 173.70 ten thousand tons of sheelite resource reserve, account for China's tungsten ore basis reserves 72.1%).Therefore, develop white tungsten resource replace black tungsten be China's tungsten industry STRATEGIES OF SUSTAINABLE DEVELOPMENT choosing then.
But the present domestic special sheelite treatment process that also do not form mainly is to prolong with wolframite NaOH to press the treatment technology that boils to handle sheelite (this process yields accounts for more than 80%).This technology is at high-alkalinity, and high-alkali consumption makes sheelite be able to effective decomposition under the intensified condition of High Temperature High Pressure, and slag contains WO
3Can drop to 1-3%.This has also caused this process energy consumption big, the production cost height, and shortcoming such as the subsequent handling wastewater discharge is big does not meet the demand for development of China's energy-saving and emission-reduction, low-carbon economy.
The external sheelite of handling mainly adopts the soda pressuring cooking method, and this method can stably be decomposed low-grade scheelite, and the slag tungstenic is generally at 0.x%, but reagent dosage is too big, generally will reach 3 times of theoretical amount, and domestic have laboratory study even will use 5-6 doubly.And service temperature also up to 225 ℃ about, equipment pressure reaches 20atm.
Acid decomposition is mainly handled sheelite with hydrochloric acid, and thermodynamic study shows that its reaction tendency is very high.But wolframic acid was yellow glue and is wrapped in undecomposed white tungsten surface when hydrochloric acid decomposed, and caused easily decomposing not exclusively, and the acid corrosion of hydrochloric acid and volatilization problem are serious, work under bad environment, and final a large amount of residual salts acid mother liquor is neutralized into CaCl through lime
2Solution and discharging is at present domesticly thrown aside.
Because it is that 1: 6～1: 12 the heteropolyacid of solubility is (as [PW that tungsten can form assorted tungsten ratio with impurity such as phosphorus, arsenic, silicon
12O
40]
3-), a spot of phosphorus just can cause the dispersion and the loss of a large amount of tungsten in the hydrochloric acid decomposition course, so the hydrochloric acid decomposition technique is mainly handled higher-grade white tungsten fine ore (require impurity such as phosphorus, arsenic low).But someone anti-its road and use it specially adds small amounts of phosphoric acid to make tungsten enter solution in leaching process, thus the wolframic acid parcel when solving hydrochloric acid and decomposing and the problem of influence decomposition.(Liu Yu according to the study, Liu Qi, Lu Tiejun, outstanding big battle-axe used in ancient China. the dynamics research of several different white tungsten fine ore hydrochloric acid complexing leachings. rare metal and Wimet .1989,2:10-16), when the consumption of phosphorus is few, still yellow wolframic acid can occur, therefore need bigger excess coefficient, and the big more leaching velocity of the consumption of phosphorus be fast more.But the corrosion of hydrochloric acid and volatilization problem are still troubling, so though have the research report not see industrial application.
For corrosion and the volatilization problem that overcomes hydrochloric acid in the aforesaid method, can consider to adopt sulfuric acid to substitute hydrochloric acid, leach with the complexing that realizes tungsten.But when a large amount of sulfuric acid existed, solution was very big to the degree of supersaturation of calcium sulfate, often causes the rapid nucleation of gypsum to form a large amount of close grains and caused parcel, made that the decomposition effect is undesirable.Reported the research of leaching sheelite with sulfuric acid as United States Patent (USP) 4168296, this method is when adopting sulfuric acid to decompose, by adding phosphoric acid, calcium phosphate or rock phosphorite, decompose to improve but also need to add especially a certain amount of NaCl so that the complexing agent of phosphorus as tungsten to be provided.Describe according to this patent, for decomposing 100g grade 29.6%WO
3Tungsten ore, be made into leach liquor with 80g sulfuric acid and 300ml water, then amounting to the solution sulfuric acid concentration is 241.5g/L, adds 4gNaCl again in the strongly-acid sulphuric acid soln of this high density.At this moment the activity of HCl will be very high in the highly acid sulphuric acid soln, just is equivalent to use the hydrochloric acid of high density in fact, its volatilization problem and Cl
-Etching problem can occur again.The inventor has added 4g phosphatic rock ore deposit and has produced phosphoric acid in conjunction with tungsten for reaction, even if phosphatic rock is by pure Ca
5(PO
4)
3F calculates, and amounts to P in the solution after all decomposing
2O
5Content only is 0.3%, and the preceding phosphoric acid consumption of having mentioned generates the wolframic acid precipitation after a little while easily.The common package action of gypsum and wolframic acid has seriously hindered the carrying out of decomposing like this.Therefore, this decomposition method still needs to adopt three sections leachings just can reach higher rate of decomposition.
In fact, H.Razavizadeh had once carried out detailed experiments (Production of tungsten via leaching of scheelite with sulfuric acid.Minerals ﹠amp according to the condition of this patent; Metallurgical Processing.2006,23 (2): 67-72), find just can obtain leaching effect preferably under the situation of having added NaCl, grade is 74.7%WO
3The rate of decomposition of concentrate can reach nearly 96%, contain WO but amount to slag
3Still up to about 5%; And handle grade is 59%WO
3Concentrate the time rate of decomposition only have closely 62%, amount to slag and contain WO
3More up to about 20%! And we are by the method for this patent, use the sheelite experiment in different grades, the different places of production to find that also the rate of decomposition of one section leaching between 70-80%, is filtered also very difficult greatly.Experimental results show that also needs to leach through three sections adverse currents really, also will will regrind from the decompose slag of epimere to destroy parcel, and rate of decomposition just can reach 97-98%.
As for the mechanism of action of adding NaCl, according to document (Calcium Sulfate Dihydrate Nucleation in the Presence of Calcium and Sodium Chloride Salts.Ind.Eng.Chem.Res.2001,40,2335-2339), the existence of chlorion can increase the inductive phase of crystal of calcium sulfate greatly, thus retardance sporadic nucleation.This helps forming thick crystal certainly to a certain extent, avoids product parcel mineral and influences decomposition.But the actual sodium-chlor that adds still is difficult to the decomposition effect that reaches satisfied, and introduces Cl
-Also can bring equipment corrosion and HCl evaporable problem, can not solve the problem of wolframic acid parcel.
In order to solve wolframic acid parcel problem, the present invention considers to adopt the phosphoric acid of big excess coefficient to come decompose tunstite.Because but the phosphoric acid complexing calcium ions causes the solubleness of calcium sulfate progressively to rise along with the increase of phosphoric acid concentration in the solution, greatly about P
2O
5Be about 20% reach maximum (80 ℃ the time, the 5-7 when existing times for no phosphoric acid.Even if P
2O
5Be elevated to about 40%, the 3-5 when solubleness also still can reach no phosphoric acid and exists doubly).Therefore, the degree of supersaturation of calcium sulfate also just might reduce the sporadic nucleation speed of calcium sulfate when suitable high-concentration phosphoric acid also helped reducing the tungsten ore decomposition, promoted to form thick crystalline effect thereby play; And the corrodibility of phosphoric acid is lower, also the volatilization problem as hydrochloric acid not.In the leach liquor and allocate a certain amount of SO into
4 2-Come in conjunction with calcium ion, make calcium generate phosphoric acid, obtain gypsum model (CaSO with calcium sulfate form precipitation and regeneration
4NH
2O) decompose slag.
Total reaction formula is:
12CaWO
4+H
3PO
4+12H
2SO
4+12nH
2O＝12CaSO
4·nH
2O+H
3[PW
12O
40]+12H
2O (1)
Leach liquor is after ion-exchange, solvent extraction or the ammonium salt precipitator method are extracted tungsten in the process, mends the acid of going into the to consume leaching that circulates.
This mode has been avoided the discharging of waste water, but finds to decompose the gypsum (CaSO of low quality that obtains simultaneously
4NH
2O) decompose slag is difficult to direct utilization, then causes the wasting of resources if heap is abandoned processing.For this reason, the utility value of developing this gypsum decompose slag is significant.
That be used widely in the market is the plaster of Paris (CaSO
40.5H
2O), can in the saturation steam medium, steam refining plaster stone (CaSO by autoclave
42H
2O) obtain.This plaster stone fine material of construction can be used for producing retardant, calcimine of plasterboard, manufacture of cement etc.Therefore, foothold of the present invention is exactly when adopting phosphoric acid and sulfuric acid decompose tunstite technology high efficiency extraction tungsten, and its leaching process is adjusted, and in the hope of directly obtaining utilizing the high quality plaster of Paris that is worth, improves the economic benefit and the environmental benefit of technology.
Summary of the invention
The purpose of this invention is to provide a kind of method of from sheelite, extracting tungsten and producing the high quality plaster of Paris.This method has realized the efficient decomposition of sheelite, and tungsten ore is wrapped and influences the problem of rate of decomposition in the solution decomposition course, can also directly obtain utilizing the high quality plaster of Paris that is worth, and improves the economic benefit and the environmental benefit of technology.
To achieve these goals, the measure taked of the present invention is as follows:
At first the mixing acid with dilute sulphuric acid and phosphoric acid joins in the decomposition reaction groove, control SO
4 2-Concentration is at 0.05g/ml-0.10g/ml, P
2O
5Mass content is controlled at 10%-25%, and temperature is controlled at 55-75 ℃, and liquid-solid ratio is 5: 1-8: 1ml/g, and the reaction times is 2-6h; After decomposition reaction finishes slip changed over to and add the semi-hydrated gypsum crystal seed in the crystallization reaction groove and carry out crystallization and transform, the mass ratio in semi-hydrated gypsum crystal seed/ore deposit is 1: 1000-1: 10, and temperature is controlled at 90-120 ℃, and the reaction times is 2-6h; Obtain semi-hydrated gypsum, reaction finishes the filtrate of after-filtration gained after alkali ion exchange, basic solvent extraction or the ammonium salt precipitator method are extracted tungsten, mends phosphoric acid and sulfuric acid and can return leaching to initial level.
Described sheelite contains the WO of 30%～75% mass percent
3, granularity is not more than 100 orders.
Decompose first half at sheelite, control generates stable, thick dihydrate gypsum, does not pursue the rate of decomposition of too high tungsten ore and low excessively P
2O
5Rate of loss.
Decompose latter half at sheelite, by adjust experiment condition make the dihydrate gypsum that generates smoothly recrystallize be converted into single, stable, filtration and the good semi-hydrated gypsum of scourability, make that simultaneously undecomposed tungsten ore continues to decompose intergranular P
2O
5Loss also is released, and further improves gypsum quality.
The advantage that the present invention has is:
1. handled sheelite foreign matter of phosphor content is not strict with, and needn't establish special dephosphorization operation again in the sheelite ore dressing process, has saved the loss of dephosphorization reagent cost and tungsten;
2. after reaction finished, tungsten entered into filtrate, only need extract through simple post processing mode such as ion-exchange, solvent extraction or the ammonium salt precipitator method, had simplified operation, had reduced cost;
3. the efficient normal pressure of having realized sheelite leaches, and has saved resource and energy consumption;
4. Cl-seriously corroded problem and HCl volatilization serious problems in traditional sour decomposition technique have been overcome;
5. the material that former material is converted into product and can handles or utilize can not cause the pollution of environment;
6. leaching plant is simple, and is easy to operate, is easy to realize industrialization;
7. decompose in the recrystallize conversion process of latter half at sheelite, a small amount of undecomposed sheelite completely is able to further decomposition, and its rate of decomposition is up to more than 98%; Intergranular P2O5 loss also is released, and makes that the P2O5 loss is reduced to below 0.5% in the slag, has reduced the leaching cost; In addition, because phosphoric acid, sulfuric acid and the good molten ore deposit ability of phospho-wolframic acid mixing acid, in the recrystallize conversion process, impurity such as iron, aluminium, magnesium dissolve once more in the gypsum, and the quality of gypsum further promotes, the quality of the byproduct semi-hydrated gypsum that obtains is very pure, even can match in excellence or beauty with natural gypsum, for producing plasterboard, the retardant of manufacture of cement, calcimine etc. provide the fine raw material, production process has realized no waste sludge discharge, improves the economic benefit and the environmental benefit of this technology;
8. because excess sulfuric acid and phosphoric acid can return and recycle, actual reagent consumption sulfuric acid only for containing the theoretical equivalent of Ca amount in the mineral, has greatly reduced production cost and wastewater discharge.
Description of drawings
Fig. 1 is the XRD figure of decompose slag;
Fig. 2 is the SEM figure of decompose slag.
Embodiment
Embodiment 1
Be described further below in conjunction with embodiment, following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Sheelite (contains WO
370.6%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.03g/ml, liquid-solid ratio 6: 1ml/g, and 60 ℃ of temperature of reaction, behind the reaction times 4h, it is 94.3% that sampling analysis gets the tungsten leaching yield, filter residue contains P
2O
5Be 5.3%.Then this slip is changed over to the crystallization reaction groove and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 50g, and temperature is warming up to 110 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.6%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 8min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.1%.Filtrate is adopted primary amine groups basic extractant extraction tungsten, and the percentage extraction of tungsten is 99.5%.Phosphorus is 2.7% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in extraction process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.The decompose slag XRD figure 1 that obtains shows really be the plaster of Paris.Fig. 2 is the SEM figure of decompose slag.
Embodiment 2
Sheelite (contains WO
370.6%) 1kg, preparation P
2O
5Content is 25% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.05g/ml, liquid-solid ratio 5: 1ml/g, 55 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 100g, and temperature is warming up to 120 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.8%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 15min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.3%.Filtrate is adopted secondary amine basic extractant extraction tungsten, and the percentage extraction of tungsten is 99.1%.Phosphorus is 2.5% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in extraction process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 3
Sheelite (contains WO
370.6%) 1kg, preparation P
2O
5Content is 10% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.02g/ml, liquid-solid ratio 8: 1ml/g, 75 ℃ of temperature of reaction, reaction times 3h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 1g, and temperature is warming up to 100 ℃, and the crystallization transformation time is 4h, and the tungsten leaching yield is 99.5%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 12min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.2%.Filtrate is adopted tertiary amine groups basic extractant extraction tungsten, and the percentage extraction of tungsten is 99.3%.Phosphorus is 2.8% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in extraction process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 4
Sheelite (contains WO
370.6%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.025g/ml, liquid-solid ratio 5: 1ml/g, 70 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 20g, and temperature is warming up to 90 ℃, and the crystallization transformation time is 2h, and the tungsten leaching yield is 99.3%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 30min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.6%.Filtrate is adopted quaternary amine base basic extractant extraction tungsten, and the percentage extraction of tungsten is 98.9%.Phosphorus is 2.6% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in extraction process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 5
Sheelite (contains WO
365.7%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.03g/ml, liquid-solid ratio 6: 1ml/g, 60 ℃ of temperature of reaction, reaction times 4h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 50g, and temperature is warming up to 110 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.6%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 8min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.12%.Filtrate is adopted the absorption of quaternary amine base anionite-exchange resin, and the adsorption rate of tungsten is 99.2%.Phosphorus is 3.7% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 6
Sheelite (contains WO
365.7%) 1kg, preparation P
2O
5Content is 25% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.05g/ml, liquid-solid ratio 5: 1ml/g, 55 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 10g, and temperature is warming up to 120 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.4%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 15min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.3%.Filtrate is adopted the absorption of primary amine groups anionite-exchange resin, and the adsorption rate of tungsten is 98.9%.Phosphorus is 3.5% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 7
Sheelite (contains WO
365.7%) 1kg, preparation P
2O
5Content is 10% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.02g/ml, liquid-solid ratio 8: 1ml/g, 75 ℃ of temperature of reaction, reaction times 3h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 1g, and temperature is warming up to 120 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.0%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 12min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.2%.Filtrate is adopted the absorption of secondary amine anionite-exchange resin, and the adsorption rate of tungsten is 99.2%.Phosphorus is 3.8% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 8
Sheelite (contains WO
365.7%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.04g/ml, liquid-solid ratio 5: 1ml/g, 70 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 20g, and temperature is warming up to 90 ℃, and the crystallization transformation time is 2h, and the tungsten leaching yield is 99.1%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 30min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.5%.Filtrate is adopted the absorption of tertiary amine groups anionite-exchange resin, and the adsorption rate of tungsten is 98.7%.Phosphorus is 3.4% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 9
Sheelite (contains WO
345.9%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.03g/ml, liquid-solid ratio 6: 1ml/g, 60 ℃ of temperature of reaction, reaction times 4h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 50g, and temperature is warming up to 110 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.3%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 8min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.10%.Filtrate is adopted the absorption of quaternary phosphonium base anionite-exchange resin, and the adsorption rate of tungsten is 98.7%.Phosphorus is 3.5% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Sheelite (contains WO
345.9%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.02g/ml, liquid-solid ratio 5: 1ml/g, 70 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 10g, and temperature is warming up to 90 ℃, and the crystallization transformation time is 2h, and the tungsten leaching yield is 99.0%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 30min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.6%.Filtrate is adopted the absorption of uncle's sulfonium base anionite-exchange resin, and the adsorption rate of tungsten is 98.6%.Phosphorus is 3.3% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 11
Sheelite (contains WO
332.0%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.03g/ml, liquid-solid ratio 6: 1ml/g, 60 ℃ of temperature of reaction, reaction times 4h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 50g, and temperature is warming up to 110 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.2%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 8min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.10%.Filtrate is adopted the absorption of guanidine radicals anionite-exchange resin, and the adsorption rate of tungsten is 98.7%.Phosphorus is 3.7% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in ion exchange process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 12
Sheelite (contains WO
332.0%) 1kg, preparation P
2O
5Content is 25% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.05g/ml, liquid-solid ratio 5: 1ml/g, 55 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 100g, and temperature is warming up to 120 ℃, and the crystallization transformation time is 2h, and the tungsten leaching yield is 98.5%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 15min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.35%.Filtrate is adopted ammonium sulfate precipitation method precipitation tungsten, and the deposition rate of tungsten is 97.6%.Phosphorus is 1.7% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in precipitation process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 13
Sheelite (contains WO
332.0%) 1kg, preparation P
2O
5Content is 10% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.02g/ml, liquid-solid ratio 8: 1ml/g, 75 ℃ of temperature of reaction, reaction times 3h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 10g, and temperature is warming up to 100 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.3%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 12min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.28%.Filtrate is adopted monoammonium sulfate precipitator method precipitation tungsten, and the deposition rate of tungsten is 96.7%.Phosphorus is 1.5% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in precipitation process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 14
Sheelite (contains WO
332.0%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.04g/ml, liquid-solid ratio 5: 1ml/g, 70 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 20g, and temperature is warming up to 90 ℃, and the crystallization transformation time is 2h, and the tungsten leaching yield is 98.9%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 30min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.5%.Filtrate is adopted ammonium phosphate precipitator method precipitation tungsten, and the deposition rate of tungsten is 96.6%.Phosphorus is 1.3% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in precipitation process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 15
Sheelite (contains WO
310.8%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.03g/ml, liquid-solid ratio 6: 1ml/g, 60 ℃ of temperature of reaction, reaction times 4h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 50g, and temperature is warming up to 110 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.2%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 8min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.20%.Filtrate is adopted monoammonium phosphate precipitator method precipitation tungsten, and the deposition rate of tungsten is 96.0%.Phosphorus is 1.2% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in precipitation process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 16
Sheelite (contains WO
310.8%) 1kg, preparation P
2O
5Content is 25% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.05g/ml, liquid-solid ratio 5: 1ml/g, 55 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 10g, and temperature is warming up to 120 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 99.1%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 15min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.35%.Filtrate is adopted diammonium phosphate precipitator method precipitation tungsten, and the deposition rate of tungsten is 96.2%.Phosphorus is 1.4% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in precipitation process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Embodiment 17
Sheelite (contains WO
310.8%) 1kg, preparation P
2O
5Content is 15% phosphoric acid solution, calls in sulfuric acid then, controls SO in the process
4 2-Concentration stabilize is at 0.02g/ml, liquid-solid ratio 5: 1ml/g, 70 ℃ of temperature of reaction, reaction times 2h.Change slip over to the crystallization reaction groove after decomposition reaction finishes and carry out the crystallization conversion, semi-hydrated gypsum crystal seed add-on is 100g, and temperature is warming up to 105 ℃, and the crystallization transformation time is 6h, and the tungsten leaching yield is 98.2%.Filtering slip employing specification is the B of 200mm, and the filtration required time is 30min, adopts the pure water washing leaching cake then three times, and each water loss is 300ml, and filter cake contains P after washing
2O
5Reduce to 0.48%.Filtrate is adopted ammonia precipitation process method precipitation tungsten, and the deposition rate of tungsten is 95.6%.Phosphorus is 1.2% with phosphorus heteropoly tungstic acid form loss and entrainment loss total amount in precipitation process, and mother liquor is mended to return behind the phosphoric acid of loss and the sulfuric acid and soaked the ore deposit.
Claims (2)
1. method of extracting tungsten and produce the high quality plaster of Paris from sheelite, it is characterized in that: at first the mixing acid with dilute sulphuric acid and phosphoric acid joins in the decomposition reaction groove, control SO
4 2-Concentration is at 0.05g/ml～0.10g/ml, P
2O
5Mass content is controlled at 10%～25%, temperature is controlled at 55～75 ℃, liquid-solid ratio is 5: 1-8: 1ml/g, reaction times is 2～6h, after decomposition reaction finishes slip changed over to and add the semi-hydrated gypsum crystal seed in the crystallization reaction groove and carry out crystallization and transform, the mass ratio in semi-hydrated gypsum crystal seed/ore deposit is 1: 1000～1: 10, and temperature is controlled at 90～120 ℃, and the reaction times is 2～6h; Obtain semi-hydrated gypsum, reaction finishes the filtrate of after-filtration gained after alkali ion exchange, basic solvent extraction or the ammonium salt precipitator method are extracted tungsten, mends phosphoric acid and sulfuric acid and can return leaching to initial level.
2. method according to claim 1 is characterized in that: described sheelite contains the WO3 of 30%～75% mass percent, and granularity is not more than 100 orders.
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| CN2010106051102A CN102021329B (en) | 2010-12-24 | 2010-12-24 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| PCT/CN2011/001895 WO2012083583A1 (en) | 2010-12-24 | 2011-11-11 | Method for extracting tungsten from scheelite |
| DE112011104540.9T DE112011104540B4 (en) | 2010-12-24 | 2011-11-11 | Process for extracting tungsten from scheelite |
| RU2013125145/02A RU2532767C1 (en) | 2010-12-24 | 2011-11-11 | Method of extracting tungsten from scheelite |
| CA2815708A CA2815708C (en) | 2010-12-24 | 2011-11-11 | Method for extracting tungsten from scheelite |
| US13/794,844 US8771617B2 (en) | 2010-12-24 | 2013-03-12 | Method for extracting tungsten from scheelite |
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| CN2010106051102A CN102021329B (en) | 2010-12-24 | 2010-12-24 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
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| CN102021329B CN102021329B (en) | 2012-03-21 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012083583A1 (en) * | 2010-12-24 | 2012-06-28 | 中南大学 | Method for extracting tungsten from scheelite |
| CN103014343A (en) * | 2013-01-18 | 2013-04-03 | 成都西顿硬质合金有限公司 | Process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor |
| RU2496896C1 (en) * | 2012-10-10 | 2013-10-27 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | Development method of scheelite concentrates |
| CN103871256A (en) * | 2014-03-19 | 2014-06-18 | 同济大学 | Intersection passage control method achieving left turning through exit lanes |
| RU2571244C1 (en) * | 2014-09-02 | 2015-12-20 | Андрей Вилорьевич Доронин | Method for obtaining pure tungstic acid |
| CN105463217A (en) * | 2015-11-25 | 2016-04-06 | 中南大学 | Treatment method for high-phosphorus high-molybdenum complex scheelite |
| CN106282608A (en) * | 2016-08-29 | 2017-01-04 | 中南大学 | A kind of method decomposing Scheelite-Wolframite Mixed Mine |
| RU2610187C1 (en) * | 2015-12-03 | 2017-02-08 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of alkaline development of scheelite concentrates |
| CN106636681A (en) * | 2016-11-23 | 2017-05-10 | 江西稀有金属钨业控股集团有限公司 | Tungsten-contained raw ore pretreatment system for realizing green metallurgy |
| CN108642278A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that mixture of sulfuric phosphoric acid pressurization decomposes wolframite or Scheelite-Wolframite Mixed Mine to extract tungsten |
| CN108642308A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that high tin tungsten ore is decomposed in mixture of sulfuric phosphoric acid pressurization |
| CN108642307A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that wolframite or Scheelite-Wolframite Mixed Mine extraction tungsten are decomposed in hydrochloric acid-phosphoric acid pressurization |
| CN108707765A (en) * | 2018-04-13 | 2018-10-26 | 中南大学 | A kind of method that scheelite is decomposed in the pressurization of phosphorus sulphur nitration mixture |
| CN110093511A (en) * | 2019-05-29 | 2019-08-06 | 湖南长宏新能源材料有限责任公司 | A kind of totally-enclosed technique for handling hazardous waste-tungsten slag and recycling valuable metal |
| CN111517354A (en) * | 2020-04-07 | 2020-08-11 | 厦门钨业股份有限公司 | Method for preparing high-quality gypsum production raw material from scheelite smelting slag |
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| WO2012083583A1 (en) * | 2010-12-24 | 2012-06-28 | 中南大学 | Method for extracting tungsten from scheelite |
| RU2496896C1 (en) * | 2012-10-10 | 2013-10-27 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | Development method of scheelite concentrates |
| CN103014343A (en) * | 2013-01-18 | 2013-04-03 | 成都西顿硬质合金有限公司 | Process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor |
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