CN103014343B - Process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor - Google Patents
Process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor Download PDFInfo
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- CN103014343B CN103014343B CN2013100192295A CN201310019229A CN103014343B CN 103014343 B CN103014343 B CN 103014343B CN 2013100192295 A CN2013100192295 A CN 2013100192295A CN 201310019229 A CN201310019229 A CN 201310019229A CN 103014343 B CN103014343 B CN 103014343B
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Abstract
The invention relates to the technical field of wet smelting of tungsten for production of ammonium paratungstate and particularly discloses a process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor. The process comprises the steps of: (1) generating an ammonium dodecatungstophosphate precipitate; (2) dissolving the ammonium dodecatungstophosphate precipitate obtained in the step (2) in ammonia; and (3) removing impurities from a solution obtained in the step (2), then removing molybdenum from the solution in a molybdenum removal groove, and then recycling to obtain an ammonium tungstate solution. Furthermore, the impurity removal in the step (3) includes a phosphorous removal sub-step and a magnesium removal sub-step. According to the process for recycling the ammonium tungstate from the ammonium paratungstate crystallization mother liquor, disclosed by the invention, ammonium tungstate with high purity is obtained, and the production cost is lowered efficiently.
Description
Technical field
The invention belongs to the tungsten hydrometallurgy and produce ammonium paratungstate (APT) technical field, particularly a kind of novel process that reclaims ammonium tungstate from ammonium para-tungstate crystal mother solution.
Background technology
China is tungsten reserves the abundantest country in the world.According to the data that US Geological Survey 2006 announces, China has the tungsten reserves of 1,800,000 tons, accounts for 61% of the world, and wherein sheelite approximately 70%, wolframite approximately 30%.The main technique technology of China's tungsten hydrometallurgy has: sheelite acid decomposition, basic pressure digestion-extraction, basic pressure digestion-ion-exchange.Wherein, ammonium paratungstate is the important intermediates in tungsten smelting process.Classical ammonium paratungstate production technique comprises that mainly obtaining ore decomposition, transition thick ammonium tungstate solution, thick ammonium tungstate solution removal of impurities, crystallization obtains the steps such as ammonium paratungstate and crystalline mother solution, crystalline mother solution circulation recovery.Crystalline mother solution is to produce in the ammonium para-tungstate crystal process, and its main component is the isopoly-acid of ammonium chloride and tungsten and the ammonium salt of heteropolyacid, usually contains WO
3, Cl, S, the cation impurities such as the negatively charged ion such as a small amount of P, As, Si and Ka, Na, Ca, Mg, Cu.Because containing more impurity, therefore, crystalline mother solution can not directly return to main flow and reclaim tungsten, and the tungsten in aided process recovery ammonium para-tungstate crystal mother solution must be set in existing tungsten smelting process.
Existing secondary tungsten ammonium acid crystal mother liquor reclaims the technique of tungsten, mainly comprises white tungsten precipitation technology and changes into the sodium wolframate technology.White tungsten precipitation technology precipitates into calcium wolframate by adding calcium ions reagent with wolframate radical, and discharges ammonia to improve the calcium ion concn in water body by heating, reduces the W content in water body.This method can drop to the W content in water body below 0.1g/l, but the calcium wolframate of this explained hereafter need to return to the tungsten concentrate decomposition process.Change into the technology of sodium wolframate, to add sodium hydroxide in crystalline mother solution, change into sodium wolframate, and discharge ammonia, sodium wolframate after conversion is because containing a large amount of chlorine roots, enter the D301 resin absorption after need to changing into metatungstic acid sodium with hydrochloric acid, then become not contain or the sodium wolframate of few chloride with the sodium hydroxide desorb, then enter main flow and namely enter 201 resins and reclaim.The white tungsten precipitation technology of prior art, auxiliary material consumption is many, and production cost is high, and process energy consumption is high; Change into the technology of sodium wolframate, auxiliary material consumption is many, and production cost is high.Therefore, how improving existing ammonium para-tungstate crystal mother solution and reclaim ammonium tungstate technique, is that the tungsten hydrometallurgy is produced the technical problem that ammonium paratungstate (APT) technical field is badly in need of solution.
Summary of the invention
Main purpose of the present invention is to reclaim for the ammonium para-tungstate crystal mother solution that exists in above-mentioned prior art the problem that the auxiliary material consumption of ammonium tungstate is many, production cost is high, energy consumption is large, provides a kind of ammonium para-tungstate crystal mother solution to reclaim ammonium tungstate technique.
In order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
Ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, comprises the steps:
Step (1): generate 12 ammonium tungstophosphate(AWP) precipitations
The phosphoric acid of theoretical amount 300% is added crystalline mother solution, and the rear placement 30 minutes that stirs adds hydrochloric acid under agitation condition, make pH value≤0.5, obtains 12 ammonium tungstophosphate(AWP) precipitations;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
The ammoniacal liquor of mass concentration 10%～20% is added dissolving tank, Heating temperature to 45 ℃～55 ℃, the 12 ammonium tungstophosphate(AWP) precipitations that add step (1) to obtain under agitation condition, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia at 1.25～1.35g/l, it is 25～38g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of described ammonia;
Step (3): the solution that step (2) makes, after carrying out removal of impurities, enter except the molybdenum groove except molybdenum, reclaim and obtain ammonium tungstate solution.
The contriver finds through research, causes the essence reason of defective of the ammonium tungstate recovery method of prior art to be, prior art does not find water-soluble ammonium tungstate in crystalline mother solution is all changed into the method for insoluble ammonium tungstate at low temperatures.The contriver has obtained ammonium para-tungstate crystal mother solution of the present invention and has reclaimed ammonium tungstate technique through large quantity research and screening.Aforementioned ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, utilizes 12 ammonium tungstophosphate(AWP) ((NH
4)
3PW
12O
40) solubleness is less under acidic conditions, and the fast characteristics of speed of response under low temperature, obtain suitable pH value scope by the hydrochloric acid adjustment, and screen simultaneously the consumption of phosphoric acid, can obtain 12 ammonium tungstophosphate(AWP) precipitations under cold condition, in crystalline mother solution, 90%～95% tungsten can change into 12 ammonium tungstophosphate(AWP) precipitations.Chemical equation is as follows:
12(NH
4)
2WO
4+H
3PO
4+21HCL=(NH
4)
3PW
12O
40↓+21NH
4CL+12H
2O
The 12 ammonium tungstophosphate(AWP)s precipitations that step (1) obtains are by adding ammoniacal liquor, and the add-on by screening ammoniacal liquor, can make the 12 complete ammonia of ammonium tungstophosphate(AWP) molten.Solution after the ammonia that step (2) obtains is molten through the removal of impurity, enters except after the molybdenum groove remove molybdenum, namely recyclablely carries out crystallization, directly obtains secondary tungsten ammonium sour.The described removal of impurity of step (3) can be taked this area impurities removing method commonly used.
As preferably, aforementioned ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and the described crystalline mother solution of step (1) is placed more than 16 hours after adding hydrochloric acid.Ammonium para-tungstate crystal mother solution of the present invention reclaims ammonium tungstate technique, the reaction of step (1) can be completed at low temperatures, but the time of separating out needs because of 12 ammonium tungstophosphate(AWP)s from solution fully is longer, therefore, preferred crystalline mother solution was placed 16 hours after adding hydrochloric acid, at this moment, in the solution that step (1) obtains, the residue W content only is 0.1g/l, and Precipitation is complete.
As preferably, aforementioned ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and described step (2) is controlled temperature of reaction at 60 ℃～70 ℃ after adding 12 ammonium tungstophosphate(AWP)s precipitations.
As preferably, aforementioned ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and it is 30～35g/l that the described ammoniacal liquor add-on of step (2) should make the molten rear ammonium tungstate solution free ammonia of described ammonia.By preferred ammoniacal liquor add-on, can make in the 12 molten situations completely of ammonium tungstophosphate(AWP) ammonia, further the production control cost.
As preferably, ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and the described removal of impurities of step (3) comprises dephosphorization step and demagging step; Described dephosphorization step comprises: adds magnesium chloride in the prepared solution of step (2), generates the trimagnesium phosphate precipitation, and filtering-depositing, the add-on of described magnesium chloride should make Mg content 〉=0.25g/l in filtrate; Described demagging step comprises: the filtrate that the dephosphorization step obtains enters D850, D750, D751 or D851 resin and adsorbs, to the black T of network or Acid chrome blue K indication nondiscoloration.
The contriver finds by research is unexpected, D850, D750, D751 or D851 resin are applied in ammonium para-tungstate crystal mother solution reclaim the ammonium tungstate technical field, filtrate after dephosphorization is by D850, D750, D751 or D851 resin absorption, magnesium ion in adsorbent solution, play the demagging effect well.
As further preferred, ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and in the demagging step, the flow velocity that described filtrate enters described D850, D750, D751 or D851 resin is 5～20cm/min.
As further preferred, ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and in the demagging step, the flow velocity that described filtrate enters the D850 of institute, D750, D751 or D851 resin is 10～12cm/min.
As preferably, ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and in the demagging step, the aspect ratio of described D850, D750, D751 or D851 resin absorbing column is 3:1～7:1.
As further preferred, ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and in the demagging step, described D850, D750, D751 or D851 resin absorbing column aspect ratio are 4:1～5:1.
The contriver has obtained flow velocity and the aspect ratio processing parameter of demagging step of the present invention by great many of experiments and screening.Find through research, flow velocity is too fast, can cause because of solution and resin too shortly duration of contact, and magnesium absorption is thorough and do not make in solution magnesium higher; Flow velocity is excessively slow, can cause unit production of resins ability to reduce.The adsorption column aspect ratio is excessive, pushes bad resin because of expansion in the time of can causing resin regeneration, and aspect ratio is too small, can cause the too small production efficiency that affects of the capacity that penetrates, and increases production difficulty.The present invention is by flow velocity and aspect ratio that screening obtains, and the ammonium tungstate solution purity that obtains is high, and production cost is effectively controlled.
As preferably, ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, and in step (3) dephosphorization step, the add-on of described magnesium chloride should make that in filtrate, Mg content is 0.25～0.35g/l.
Compared with prior art, the invention has the beneficial effects as follows:
One, technique of the present invention reclaims the ammonium tungstate solution that obtains and can the direct evaporation crystallization obtain APT-0 level product, and technical process is short, does not take the main flow equipment capacity.
Two, the present invention by utilize 12 ammonium tungstophosphate(AWP)s in solubleness under acidic conditions fast characteristics of speed of response under less and low temperature, obtain suitable pH value scope by the hydrochloric acid adjustment, and screen simultaneously the consumption of phosphoric acid, can obtain 12 ammonium tungstophosphate(AWP) throw outs under cold condition, and, removal of impurities molten by ammonia, except molybdenum obtains ammonium tungstate solution, production cost is effectively reduced.Specific as follows:
(1) cost of supplementary product relatively.
1, prior art consumes sodium hydroxide, consumes by 0.5 ton of/ton APT, and price is by 3300 yuan/tons of sodium hydroxide, and its expense is 0.5 * 3300=1650 yuan/ton of APT.
Ammonium chloride is made with extra care in prior art consumption, consumes by 0.75 ton of/ton APT, and price is by 2400 yuan/tons of refining ammonium chlorides, and its expense is 0.75 * 2400=1800 yuan/ton of APT.
Prior art consumes ammoniacal liquor, consumes by 0.7 ton of/ton APT, and price is by 1100 yuan/tons of ammoniacal liquor, and its expense is 0.7 * 1100=770 yuan/ton of APT.
2, the present invention consumes ammoniacal liquor, consumes by 1.1 tons of/ton APT, and price is by 1100 yuan/tons of ammoniacal liquor, and its expense is 1.1 * 1100=1210 yuan/ton of APT.
The present invention consumes phosphoric acid, consumes by 0.093 ton of/ton APT, and price is by 5000 yuan/tons of phosphoric acid, and its expense is 0.093 * 5000=465 yuan/ton of APT.
The present invention consumes hydrochloric acid: consume by 3.5 tons of/ton APT, price is by 400 yuan/tons of hydrochloric acid, and its expense is 3.5 * 400=1400 yuan/ton of APT.
3, the present invention saves the auxiliary material expense and is: (1650+1800+770)-(1210+465+1400)=1145 yuan/tons of APT.
(2) energy consumption relatively.
1, prior art consumption mark coal consumes by 2 tons of/ton APT, and price is by 600 yuan/tons of mark coals, and its expense is 2 * 600=1200 yuan/ton of APT.
2, the present invention consumes the energy and is almost 0.
3, the present invention saves energy expenditure and is: 1200-0=1200 yuan/ton of APT.
(3) adopt the present invention, but the whole industry cost saving whole year is calculated.
At present, the industry is produced about 100000 tons of APT per year, produces mother liquor by 10% (folding APT), reclaims APT by mother liquor and reaches 100000 * 10%=10000 ton, but adopt the present invention's cost saving to add up to: (1145+1200) * ten thousand yuan of 10000=2345.
Embodiment
Below in conjunction with embodiment, foregoing invention content of the present invention is described in further detail.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Not breaking away from the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1 the present embodiment is that ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique
Comprise the steps:
Step (1): generate 12 ammonium tungstophosphate(AWP) precipitations
Crystalline mother solution 500l (WO
3: 30g/l), the phosphatase 11 .7 ㎏ (85 phosphoric acid) of theoretical amount 300% is added, the rear placement 30 minutes that stirs adds hydrochloric acid 60l under agitation condition, make pH value=0.5, obtains 12 ammonium tungstophosphate(AWP)s precipitations, places 12 hours;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
The ammoniacal liquor 37l of mass concentration 10% is added dissolving tank, Heating temperature to 45 ℃, add the 12 ammonium tungstophosphate(AWP) precipitations that step (1) obtains (to starch with 13 l water furnishings under agitation condition, conveniently to add), control temperature of reaction at 60 ℃, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia 1.30, it is 30g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of ammonia;
Step (3): add magnesium chloride (MgCl in the solution that step (2) makes
2.7H
2O) 1.306 ㎏ generate magnesium ammonium phosphate sediment (MgNH
4PO
4), only put filtering-depositing after 30 minutes, the add-on of magnesium chloride should make that in filtrate, Mg content is 0.25g/l; The filtrate that the dephosphorization step obtains enters the D850 resin and adsorbs, and D850 resin aspect ratio is 4:1, and flow velocity is 10cm/min, to the black T indication of network nondiscoloration, stops resin absorption, and solution enters except the molybdenum groove except molybdenum, reclaims and obtains ammonium tungstate solution.
After testing, in ammonium tungstate solution, phosphorus content drops to 0.0010g/l, and ammonium tungstate solution is after conventional method produces APT, and reclaiming the APT product purity that obtains after testing is APT-0.Detection method: the phosphorus molybdenum blue spectrophotometric method is surveyed phosphorus; The EDTA volumetry is surveyed calcium magnesium.
Embodiment 2 the present embodiment are that ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique
Comprise the steps:
Step (1): generate 12 ammonium tungstophosphate(AWP) precipitations
Crystalline mother solution 500l (WO
3: 30g/l), phosphoric acid (85 phosphoric acid) 1.7 ㎏ of theoretical amount 300% are added, the rear placement 30 minutes that stirs adds hydrochloric acid 80l under agitation condition, make pH value=0.3, obtains 12 ammonium tungstophosphate(AWP)s precipitations, places 16 hours;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
The ammoniacal liquor 37L of mass concentration 10% is added dissolving tank, Heating temperature to 55 ℃, add the 12 ammonium tungstophosphate(AWP) precipitations that step (1) obtains (to add 7 l water furnishing slurries under agitation condition, conveniently add), control temperature of reaction at 70 ℃, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia 1.32, it is 38g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of ammonia;
Step (3): add magnesium chloride (MgCl in the solution that step (2) makes
2.7H
2O) 1.34 ㎏ generate magnesium ammonium phosphate sediment (MgNH
4PO
4), filtering-depositing, the add-on of magnesium chloride should make that in filtrate, Mg content is 0.34g/l; The filtrate that the dephosphorization step obtains enters the D750 resin and adsorbs, and D750 resin aspect ratio is 5:1, and flow velocity is 12cm/min, to Acid chrome blue K indication nondiscoloration, stops resin absorption, and solution enters except the molybdenum groove except molybdenum, reclaims and obtains ammonium tungstate solution.
After testing, in ammonium tungstate solution, phosphorus content has dropped to 0.0008g/l, and ammonium tungstate solution is after conventional method produces APT, and reclaiming the APT product purity that obtains after testing is APT-0.Detection method is with embodiment 1.
Embodiment 3 the present embodiment are that ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique
Comprise the steps:
Step (1): generate 12 ammonium tungstophosphate(AWP) precipitations
Crystalline mother solution 500l (WO
3: 30g/l), phosphoric acid (85 phosphoric acid) 1.7 ㎏ of theoretical amount 300% are added, the rear placement 30 minutes that stirs adds hydrochloric acid 60l under agitation condition, make pH value=0.5, obtains 12 ammonium tungstophosphate(AWP)s precipitations, places 16 hours;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
Ammoniacal liquor 37 l of mass concentration 10% are added dissolving tank, Heating temperature to 50 ℃, the 12 ammonium tungstophosphate(AWP) precipitations (adding 10 l water furnishing slurries) that add step (1) to obtain under agitation condition, control temperature of reaction at 65 ℃, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia 1.3, it is 32g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of ammonia;
Step (3): add magnesium chloride Mg Cl in the solution that step (2) makes
2.7H
2O) 1.35 ㎏ generate the trimagnesium phosphate precipitation, filtering-depositing, and the add-on of magnesium chloride should make that in filtrate, Mg content is 0.35g/l; The filtrate that the dephosphorization step obtains enters the D851 resin and adsorbs, and D851 resin aspect ratio is 4:1, and flow velocity is 10cm/min, to the black T indication of network nondiscoloration, stops resin absorption, and solution enters except the molybdenum groove except molybdenum, reclaims and obtains ammonium tungstate solution.
After testing, the ammonium tungstate solution phosphorus content drops to 0.0008g/l, and ammonium tungstate solution is after conventional method produces APT, and reclaiming the APT product purity that obtains after testing is APT-0.Detection method is with embodiment 1.
Embodiment 4 the present embodiment are that ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique
Comprise the steps:
Step (1): generate 12 ammonium tungstophosphate(AWP) precipitations
Crystalline mother solution 500l (WO
3: 30g/l), phosphoric acid (85 phosphoric acid) 1.7 ㎏ of theoretical amount 300% are added, the rear placement 30 minutes that stirs adds hydrochloric acid 60l under agitation condition, make pH value=0.5, obtains 12 ammonium tungstophosphate(AWP)s precipitations, places 16 hours;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
The ammoniacal liquor 32.7L of mass concentration 10% is added dissolving tank, Heating temperature to 50 ℃, the 12 ammonium tungstophosphate(AWP) precipitations (adding 10.2L water furnishing slurry) that add step (1) to obtain under agitation condition, control temperature of reaction at 65 ℃, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia at 1.35g/l, it is 25g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of ammonia;
Step (3): add magnesium chloride Mg Cl in the solution that step (2) makes
2.7H
2O) 1.33 ㎏ generate the trimagnesium phosphate precipitation, filtering-depositing, and the add-on of magnesium chloride should make that in filtrate, Mg content is 0.35g/l; The filtrate that the dephosphorization step obtains enters the D751 resin and adsorbs, and D751 resin aspect ratio is 3:1, and flow velocity is 5cm/min, to the black T indication of network nondiscoloration, stops resin absorption, and solution enters except the molybdenum groove except molybdenum, reclaims and obtains ammonium tungstate solution.
After testing, the ammonium tungstate solution phosphorus content drops to 0.0008g/l, and ammonium tungstate solution is after conventional method produces APT, and reclaiming the APT product purity that obtains after testing is APT-0.Detection method is with embodiment 1.
Embodiment 5 the present embodiment are that ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique
Comprise the steps:
Step (1): with embodiment 3;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
The ammoniacal liquor 21.5L of mass concentration 20% is added dissolving tank, Heating temperature to 50 ℃, the 12 ammonium tungstophosphate(AWP) precipitations (adding 38.5L water furnishing slurry) that add step (1) to obtain under agitation condition, control temperature of reaction at 65 ℃, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia at 1.25g/l, it is 35g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of ammonia;
Step (3): add magnesium chloride Mg Cl in the solution that step (2) makes
2.7H
2O) 1.38 ㎏ generate the trimagnesium phosphate precipitation, filtering-depositing, and the add-on of magnesium chloride should make that in filtrate, Mg content is 0.35g/l; The filtrate that the dephosphorization step obtains enters the D751 resin and adsorbs, and D751 resin aspect ratio is 7:1, and flow velocity is 20cm/min, to the black T indication of network nondiscoloration, stops resin absorption, and solution enters except the molybdenum groove except molybdenum, reclaims and obtains ammonium tungstate solution.
After testing, the ammonium tungstate solution phosphorus content drops to 0.0008g/l, and ammonium tungstate solution is after conventional method produces APT, and reclaiming the APT product purity that obtains after testing is APT-0.Detection method is with embodiment 1.
Test example
1 test example of test example is about in step of the present invention (1), and the screening study of phosphoric acid and hydrochloric acid consumption (pH value) is partly made a summary.
Test is divided into 5 groups, and phosphoric acid and hydrochloric acid consumption, pH value see Table 1, and all the other steps are with the step (1) of embodiment 3, and test-results sees Table 1.In solution, the detection method of residue W content is the thiocyanate-content comparison.
Table 1. 12 ammonium tungstophosphate(AWP) precipitator method testing datas
(5L solution, WO
3: 30g/l)
| ? | 1 | 2 | 3 | 4 | 5 |
| Phosphoric acid consumption (unit: g) | 34 | 10 | 300%(17) | 20 | 15 |
| Hydrochloric acid consumption (ml) | 100 | 30 | 60 | 40 | 80 |
| The pH value | 0 | 1.0 | 0.5 | 0.8 | 0.3 |
| Remain W content (g/l) in solution | 0.1 | 7.5 | 0.2 | 3.3 | 1.8 |
By as seen from Table 1, phosphoric acid consumption, hydrochloric acid consumption and 12 ammonium tungstophosphate(AWP) precipitin reaction yields are closely related, relatively waste when the phosphoric acid consumption is too much and the precipitation yield be there is no more contributions, and when very few, the tungsten precipitation not exclusively; When the hydrochloric acid consumption is too much, waste is arranged also, cause the too high tungsten precipitation of pH value when very few not exclusively.Obtain through screening, the phosphoric acid consumption is 300% of crystalline mother solution theoretical amount, hydrochloric acid adjustment pH value≤0.5 o'clock, and 12 ammonium tungstophosphate(AWP) precipitin reaction are complete.
2 test examples of test example are about in step of the present invention (3), the research of solution flow rate and aspect ratio screening summary.
Test is divided into 7 groups, and by the filtrate that embodiment 3 dephosphorization steps obtain, every group of 10l enters the D850 resin and adsorb, and D850 resin aspect ratio and flow velocity see Table 2, and all the other steps are with embodiment 3.Test-results sees Table 2. ammonium tungstate method for detecting purity: EDTA analyzing purity magnesium.
Table 2. resin adsorption method demagging testing data
| ? | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Flow velocity (cm/min) | 20 | 30 | 2 | 10 | 5 | 20 | 5 |
| Aspect ratio | 8:1 | 7:1 | 3:1 | 5：1 | 6：1 | 4：1 | 2:1 |
| Ammonium tungstate purity (Mg:g/l) | 0.0015 | 0.05 | Trace | Trace | Trace | Trace | 0.02 |
By as seen from Table 2, aspect ratio, flow velocity and ammonium tungstate purity are closely related, when too small or flow velocity is too fast when aspect ratio, all will affect the purity of ammonium tungstate, when excessive or flow velocity is too small when aspect ratio, will affect production efficiency and production capacity.Obtain through screening, aspect ratio is in 3:1～7:1 scope, and flow velocity is when 5～20cm/min scope, especially aspect ratio is in 4:1～5:1 scope, and flow velocity is when 10～12cm/min scope, and the ammonium tungstate purity that obtains is best, and can not affect production efficiency, or affect production capacity.
Claims (10)
1. ammonium para-tungstate crystal mother solution reclaims ammonium tungstate technique, it is characterized in that, comprises the steps:
Step (1): generate 12 ammonium tungstophosphate(AWP) precipitations
The phosphoric acid of theoretical amount 300% is added crystalline mother solution, and the rear placement 30 minutes that stirs adds hydrochloric acid under agitation condition, make pH value≤0.5, obtains 12 ammonium tungstophosphate(AWP) precipitations;
Step (2): 12 ammonium tungstophosphate(AWP) precipitation ammonia are molten
The ammoniacal liquor of mass concentration 10%～20% is added dissolving tank, Heating temperature to 45 ℃～55 ℃, the 12 ammonium tungstophosphate(AWP) precipitations that add step (1) to obtain under agitation condition, make the described 12 molten rear ammonium tungstate solution proportions of ammonium tungstophosphate(AWP) precipitation ammonia at 1.25～1.35g/l, it is 25～38g/l that the add-on of described ammoniacal liquor should make the molten rear ammonium tungstate solution free ammonia of described ammonia;
Step (3): the solution that step (2) makes, after carrying out removal of impurities, enter except the molybdenum groove except molybdenum, reclaim and obtain ammonium tungstate solution.
2. ammonium para-tungstate crystal mother solution according to claim 1 reclaims ammonium tungstate technique, it is characterized in that, the described crystalline mother solution of step (1) is placed more than 16 hours after adding hydrochloric acid.
3. ammonium para-tungstate crystal mother solution according to claim 1 reclaims ammonium tungstate technique, it is characterized in that, described step (2) is controlled temperature of reaction at 60 ℃～70 ℃ after adding 12 ammonium tungstophosphate(AWP) precipitations.
4. ammonium para-tungstate crystal mother solution according to claim 1 reclaims ammonium tungstate technique, it is characterized in that, it is 30～35g/l that the described ammoniacal liquor add-on of step (2) should make the molten rear ammonium tungstate solution free ammonia of described ammonia.
5. ammonium para-tungstate crystal mother solution according to claim 1 reclaims ammonium tungstate technique, it is characterized in that, the described removal of impurities of step (3) comprises dephosphorization step and demagging step; Described dephosphorization step comprises: adds magnesium chloride in the prepared solution of step (2), generates the trimagnesium phosphate precipitation, and filtering-depositing, the add-on of described magnesium chloride should make Mg content 〉=0.25g/l in filtrate; Described demagging step comprises: the filtrate that the dephosphorization step obtains enters D850, D750, D751 or D851 resin and adsorbs, to the black T of network or Acid chrome blue K indication nondiscoloration.
6. ammonium para-tungstate crystal mother solution according to claim 5 reclaims ammonium tungstate technique, it is characterized in that, in the demagging step, the flow velocity that described filtrate enters described D850, D750, D751 or D851 resin is 5～20cm/min.
7. ammonium para-tungstate crystal mother solution according to claim 6 reclaims ammonium tungstate technique, it is characterized in that, in the demagging step, the flow velocity that described filtrate enters described D850, D750, D751 or D851 resin is 10～12cm/min.
8. ammonium para-tungstate crystal mother solution according to claim 5 reclaims ammonium tungstate technique, it is characterized in that, in the demagging step, the aspect ratio of described D850, D750, D751 or D851 resin absorbing column is 3:1～7:1.
9. ammonium para-tungstate crystal mother solution according to claim 8 reclaims ammonium tungstate technique, it is characterized in that, in the demagging step, described D850, D750, D751 or D851 resin absorbing column aspect ratio are 4:1～5:1.
10. ammonium para-tungstate crystal mother solution according to claim 5 reclaims ammonium tungstate technique, it is characterized in that, in step (3) dephosphorization step, the add-on of described magnesium chloride should make that in filtrate, Mg content is 0.25～0.35g/l.
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| CN108640155B (en) * | 2018-07-23 | 2020-03-17 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for solving product ammonium paratungstate yellow spot by accurately titrating industrial ammonium tungstate solution |
| CN109402397B (en) * | 2018-11-05 | 2020-04-07 | 中南大学 | Method for preparing ammonium phosphotungstate by utilizing molybdenum-removing slag from tungsten smelting |
| CN110015694B (en) * | 2019-04-30 | 2022-03-04 | 江西理工大学 | Purifying agent for purifying ammonium paratungstate and method for purifying ammonium paratungstate |
| CN111283211A (en) * | 2020-02-26 | 2020-06-16 | 厦门虹鹭钨钼工业有限公司 | Preparation method of high-purity tungsten powder |
| CN114672672B (en) * | 2022-04-18 | 2024-04-16 | 江西钨业股份有限公司 | Method for recovering tungstic acid from tungsten-containing solution |
| CN115679128B (en) * | 2022-11-08 | 2024-04-16 | 厦门钨业股份有限公司 | Method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag |
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