CN102690949A - Method of purifying ammonium tungstate solution - Google Patents
Method of purifying ammonium tungstate solution Download PDFInfo
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- CN102690949A CN102690949A CN201210164500XA CN201210164500A CN102690949A CN 102690949 A CN102690949 A CN 102690949A CN 201210164500X A CN201210164500X A CN 201210164500XA CN 201210164500 A CN201210164500 A CN 201210164500A CN 102690949 A CN102690949 A CN 102690949A
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- ammonium tungstate
- tungstate solution
- ammonium
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- dephosphorization
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Abstract
The invention provides a method of purifying ammonium tungstate solution. The method comprises the following steps of contacting the ammonium tungstate solution and magnesium salt so as to remove phosphorus in a form of magnesium ammonium phosphate sediments. By utilizing the method, the phosphorus in the ammonium tungstate solution can be effectively removed.
Description
Technical field
The invention belongs to the wolframite field of smelting.More specifically, the present invention relates to a kind of ammonium tungstate solution purifying method.
Background technology
Existing tungsten smelting technology mainly adopts alkali decomposition → calcium salt dephosphorization → anionresin → ammonium tungstate solution sulfuration removal of impurities → evaporative crystallization to produce APT technology, and wherein alkali decomposes back Na
2WO
4The solution phosphorus concentration is 0.5~1g/l, and the concentration of phosphorus is still about 0.2g/l in the ammonium tungstate solution that calcium salt dephosphorization-anionresin obtains.
Thereby the purification means to ammonium tungstate solution still remain to be improved at present.
Summary of the invention
The present invention is intended to one of solve the problems of the technologies described above at least.
The present invention is based on contriver's following discovery and accomplishes: Na
2WO
4Solution directly can be removed the phosphorus more than 90% through IX without the calcium salt dephosphorization, and the phosphorus concentration of resulting ammonium tungstate solution (does not comprise 0) yet about 0-3g/l.Therefore the calcium salt dephosphorization does not have substantial phosphor-removing effect, and this technology can directly be cancelled.In addition, there are many drawbacks in the calcium salt dephosphorization process, removes WO in the phosphorus slag
3Content up to 30 weight %, must it be returned the soda boiling pot in the production and recycle, this has consumed a large amount of raw and auxiliary materials, production cost obviously raises.In addition, the contriver is through discovering: containing phosphorus concentration and be the ammonium tungstate solution that (does not comprise 0) about 0-3g/l, to produce the APT phosphorus content through evaporative crystallization be 13ppm, can't satisfy country " 0 " grade standard (P≤7ppm).Therefore the desorbed solution after the IX needs further dephosphorization.The contriver finds, through adopting the alternative calcium salt of magnesium salts, can remove in the ammonium tungstate solution effectively the phosphorus that is contained.
In one aspect of the invention, the present invention proposes and a kind ofly can effectively remove institute's phosphorated method in the ammonium tungstate solution.According to embodiments of the invention, this method comprises: ammonium tungstate solution is contacted with magnesium salts, so that remove dephosphorization with the form of magnesium ammonium phosphate sediment.The contriver finds, through ammonium tungstate solution is contacted with magnesium salts, following reaction can take place:
Mg
2++NH
4 ++PO
4 3-+6H
2O→MgNH
4PO
4·6H
2O↓
Magnesium ammonium phosphate (Mg (the NH that reaction generates
4) PO
46H
2O) the resolution of precipitate degree is less, K
SP (MgNH4PO4)=2.5 * 10
-13In the time of 20 ℃, its solubleness is 0.052%.Thus, can make the phosphorus that is comprised in the ammonium tungstate solution with magnesium ammonium phosphate (Mg (NH through ammonium tungstate solution is contacted with magnesium salts
4) PO
46H
2O) sedimentary form is removed.
In this article, broad understanding should be done in the term that is adopted " contact ", can be anyly can make the phosphorus in magnesium salts and the ammonium tungstate solution that the form of above-mentioned chemical reaction can take place; For example; According to one embodiment of present invention, can be that magnesium salts is joined in the ammonium tungstate solution, and under agitation condition, mix; Can improve the efficient of reaction thus, and then improve dephosphorization efficiency by using.
According to embodiments of the invention, the type that can use method of the present invention to carry out the ammonium tungstate of dephosphorization does not receive special restriction, as long as foregoing reaction can take place phosphorus wherein.According to embodiments of the invention, can adopt the ammonium tungstate solution that is produced in the industrial production ammonium paratungstate.According to embodiments of the invention, the ammonium tungstate solution that can adopt can contain the WO of 350g/l at the most
3, preferably contain the WO about 230g/l
3, randomly, ammonium tungstate solution contains the phosphorus that (does not comprise 0) about 0-3g/l, for example can contain the phosphorus of 0.2g/l.Thus, can remove the phosphorus in the ammonium tungstate solution effectively through above-mentioned reaction.
According to embodiments of the invention, the type that can be used to carry out the magnesium salts of purifying treatment does not receive special restriction, as long as can mg ion be provided for reaction system.According to instances more of the present invention, the magnesium salts that can be used for purifying treatment is be selected from magnesium basic carbonate, sal epsom, Natural manganese dioxide, magnesiumcarbonate, Marinco H at least a.It will be understood by those skilled in the art that and promptly can adopt independent a kind of magnesium salts, also can adopt the combination with arbitrary proportion of multiple magnesium salts.According to embodiments of the invention, the consumption that is used to purify the magnesium salts of ammonium tungstate solution does not receive special restriction.According to embodiments of the invention, the amount of the magnesium salts that is adopted is 1~1.4 times of theoretical value.Here employed term " theoretical amount " refers to, and calculates according to chemical reaction equation, removes all phosphorus in the solution, the amount of needed magnesium salts.For example, when adopting magnesiumcarbonate, for the phosphorous 0.2g/L of 200ml, contain WO
3The ammonium tungstate solution of 210g/L, the amount of the magnesiumcarbonate of theoretical amount are 0.1088g.The contriver finds, Mg in solution
2+And NH
4 +When superfluous, magnesium ammonium phosphate (Mg (NH
4) PO
46H
2O) the resolution of precipitate degree can significantly reduce, thus, and through adopting excessive magnesium salts, further dephosphorization effectively.
In addition, according to embodiments of the invention, the condition that ammonium tungstate solution and magnesium salts react does not receive special restriction.Based on instantiation of the present invention, under pH value 8-11, preferably, ammonium tungstate solution is contacted with magnesium salts pH value 9 times, for example sodium tungstate solution is mixed with magnesium salts.According to embodiments of the invention, ammonium tungstate solution and magnesium salts reaction 1-5 hour, preferred 120 minutes.Thus, can further improve the reaction efficiency of ammonium tungstate and magnesium salts, and then improve the dephosphorization efficiency by using that purifies ammonium tungstate solution.
In addition, according to embodiments of the invention, with ammonium tungstate solution with before magnesium salts contacts, at first ammonium tungstate mixes with ammonium sulfide solution.Through in reaction system, adding ammonium sulfide, with the MOO in the solution
4 2-Be sulfided into and be prone to by Cu
2+The MOS that catches
4 2-, can remove in the ammonium tungstate solution for example molybdenum of other impurity effectively through adding copper-bath again, react and be:
MoS
4 2-+CuSO
4(aq)→CuMoS
4(s)+SO
4 2-
Unnecessary (NH
4)
2S can with unnecessary CuSO
4Reaction generates the CuS throw out, makes the Cu in the solution
2+, S
2-Can be inexcessive, and can not influence follow-up cationic exchange technology, its technological principle is:
CuSO
4+(NH
4)
2S=CuS(s)+(NH
4)
2SO
4(aq)
And the contriver is surprised to find, and adds the reaction that ammonium sulfide and copper sulfate do not influence phosphorus in magnesium salts and the ammonium tungstate solution, thus, carries out simultaneously with dephosphorization with except that the reaction of other impurity, significantly improves the efficient that purifies ammonium tungstate solution.
According to embodiments of the invention, the amount of ammonium sulfide is the 1%-3.5% of ammonium tungstate solution volume.Thus, can further improve the efficient that purifies ammonium tungstate solution.
According to embodiments of the invention, after the ammonium tungstate solution that obtains through the dephosphorization removal of impurities, can resulting ammonium tungstate be used to prepare ammonium paratungstate.For example, according to specific examples of the present invention, can the ammonium tungstate solution that pass through the dephosphorization removal of impurities be carried out evaporative crystallization, so that obtain ammonium paratungstate.In addition, according to specific examples of the present invention, before the ammonium tungstate solution that will pass through dephosphorization carried out evaporative crystallization, the ammonium tungstate solution that will pass through dephosphorization carries out cationic exchange to be handled.Thus, the phosphorus content of resulting ammonium paratungstate (APT) significantly reduces.According to embodiments of the invention, can be reduced to below the 0.004g/l through purifying the ammonium tungstate solution phosphorus concentration that obtains, again through cationic exchange technology, the phosphorus content of the ammonium paratungstate that evaporative crystallization obtains can reach below the 5ppm.Thus, utilize method, cancelled calcium salt dephosphorization process, shortened process in the production, reduced production costs, improve the tungsten smelting recovery according to the embodiment of the invention, thus the method for deep phosphorous removal removal of impurities under a kind of ammonium tungstate vulcanization system that provides.
Positively effect according to the method for the purification ammonium tungstate of the embodiment of the invention:
Based on embodiments of the invention, cancelled calcium salt dephosphorization process in the existing technology, with dephosphorization process with the sulfuration impurity removal process merge to one the step carry out, not only shortened technological process, reduced production cost, simplified operation, and improved production efficiency.
According to embodiments of the invention, resultingly remove that tungstic oxide content is lower than 1% in the phosphorus slag, remove in the phosphorus slag 30% W content much smaller than calcium salt, improved the tungsten metal recovery rate greatly.
According to embodiments of the invention, adopt the magnesium salts deep phosphorous removal, phosphorus content can be reduced to 0.004g/L in the solution, and the APT impurity content that the present invention produces is lower than GB " 0 " level article APT.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize through practice of the present invention.
Embodiment
Describe embodiments of the invention below in detail, need to prove, these embodiment only are for the present invention is described, and scope of the present invention are not made any restriction.The all material that in the following example, is adopted all is commonly used in the industry, is commercially available getting.
Raw material: the ammonium tungstate solution in the industrial production, analytical pure magnesium basic carbonate, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5, Natural manganese dioxide, magnesiumcarbonate, Marinco H, magnesium chloride, industrial ammonium sulfide.
Equipment: DF-1 heat collecting type constant temperature blender with magnetic force, 500ml glass Erlenmeyer flask, 200ml ceramic cup.
Analytical procedure: tungsten adopts the thiocyanate-absorbance method, and phosphorus adopts the yellow spectrophotometry of phosphorus molybdenum.The ammonium tungstate solution that the present invention adopts all comes from industrial production, P=0.22g/l wherein, WO
3=230g/l.
Embodiment 1
Under the normal temperature, get 300ml and contain WO
3Concentration is 230g/l; The ammonium tungstate solution that contains phosphorus concentration and be 0.22g/l is in the 500ml beaker; The industrial ammonium sulfide solution that adds the 1%-3.5% of ammonium tungstate solution volume stirs; The magnesium basic carbonate, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5, Natural manganese dioxide, magnesiumcarbonate, the Marinco H that in said mixture, add 1~1.4 times of theoretical amount respectively carry out deep phosphorous removal (for magnesium basic carbonate, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5, Natural manganese dioxide, magnesiumcarbonate, Marinco H; The magnesium salts consumption of 1 times of theoretical amount is respectively: 0.2069g, 0.5245g, 0.0858g, 0.1795g, 0.1235g), the pH value=9-10 of reaction soln, dephosphorization reaction times 120min; After above-mentioned experimental implementation and analysis, experimental result is as follows:
One, the magnesium basic carbonate of 1~1.4 times of theoretical multiple is seen shown in the table 1 influence of vulcanization system ammonium tungstate solution dephosphorization.Wherein the weight of the magnesium basic carbonate of 1 times of theoretical amount is 0.2069g.
Table 1 magnesium basic carbonate consumption is to the influence of vulcanization system ammonium tungstate solution deep phosphorous removal
The theoretical multiple of magnesium basic carbonate | 1 | 1.1 | 1.2 | 1.3 | 1.4 |
Initial p concentration, g/L | 0.22 | ||||
Residue P concentration, g/L | 0.012 | 0.004 | 0 | 0 | 0 |
Final WO 3: P ratio | 2.5×10 4 | 7.5×10 4 | ∞ | ∞ | ∞ |
Dephosphorizing rate, % | 94.55 | 98.18 | 100 | 100 | 100 |
Research shows: under the vulcanization system, at high WO
3In the ammonium tungstate solution of concentration, low phosphorus concentration, along with the increase of magnesium basic carbonate consumption, phosphoric residue concentration reduces gradually in the solution.When the theoretical multiple of magnesium basic carbonate was 1 times, the phosphorus concentration in the solution was reduced to 0.012g/L from 0.22g/L, WO
3: P is 2.5 * 10
4, dephosphorizing rate 94.55% reaches the dephosphorization standard.
Two, the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 of 1~1.4 times of theoretical multiple is seen shown in the table 2 influence of vulcanization system ammonium tungstate solution dephosphorization.Wherein the weight of the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 of 1 times of theoretical amount is 0.5246g.
Table 2 MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 consumption is to the influence of vulcanization system ammonium tungstate solution deep phosphorous removal
The theoretical multiple of MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 | 1 | 1.1 | 1.2 | 1.3 | 1.4 |
Initial p concentration, g/L | 0.22 | ||||
Residue P concentration, g/L | 0.014 | 0.006 | 0.004 | 0.006 | 0.007 |
Final WO 3: P ratio | 2.14×10 4 | 5.0×10 4 | 7.5×10 4 | 5.0×10 4 | 4.29×10 4 |
Dephosphorizing rate, % | 93.64 | 97.27 | 98.18 | 97.27 | 96.82 |
Research shows: under the vulcanization system, at high WO
3In the ammonium tungstate solution of concentration, low phosphorus concentration, along with the increase of MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 consumption, phosphoric residue concentration reduces gradually in the solution.When the theoretical multiple of MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 was 1 times, the phosphorus concentration in the solution was reduced to 0.014g/L from 0.22g/L, WO
3: P is 2.14 * 10
4, dephosphorizing rate 93.64% reaches the dephosphorization standard.
Three, the Natural manganese dioxide of 1~1.4 times of theoretical multiple is seen shown in the table 3 influence of vulcanization system ammonium tungstate solution dephosphorization.Wherein the magnesian weight of 1 times of theoretical amount is 0.0858g.
Table 3 Natural manganese dioxide consumption is to the influence of vulcanization system ammonium tungstate solution deep phosphorous removal
Magnesian theoretical multiple | 1 | 1.1 | 1.2 | 1.3 | 1.4 |
Initial p concentration, g/L | 0.22 | ||||
Residue P concentration, g/L | 0.059 | 0.016 | 0.009 | 0.006 | 0.004 |
Final WO 3: P ratio | 5.08×10 3 | 1.88×10 4 | 3.33×10 4 | 5.0×10 4 | 7.5×10 4 |
Dephosphorizing rate, % | 73.18 | 92.73 | 95.91 | 97.27 | 98.18 |
Research shows: under the vulcanization system, at high WO
3In the ammonium tungstate solution of concentration, low phosphorus concentration, along with the increase of Natural manganese dioxide consumption, phosphoric residue concentration reduces gradually in the solution.When the theoretical multiple of Natural manganese dioxide was 1.1 times, the phosphorus concentration in the solution was reduced to 0.016g/L from 0.22g/L, WO
3: P is 1.88 * 10
4, dephosphorizing rate 92.73% reaches the dephosphorization standard.
Four, the magnesiumcarbonate of 1~1.4 times of theoretical multiple is seen shown in the table 4 influence of vulcanization system ammonium tungstate solution dephosphorization.Wherein the weight of the magnesiumcarbonate of 1 times of theoretical amount is 0.1795g.
Table 4 magnesiumcarbonate consumption is to the influence of vulcanization system ammonium tungstate solution deep phosphorous removal
The theoretical multiple of magnesiumcarbonate | 1 | 1.1 | 1.2 | 1.3 | 1.4 |
Initial p concentration, g/L | 0.22 | ||||
Residue P concentration, g/L | 0.12 | 0.10 | 0.074 | 0.045 | 0.022 |
Final WO 3: P ratio | 2.5×10 3 | 3.0×10 3 | 4.05×10 3 | 6.67×10 3 | 1.36×10 4 |
Dephosphorizing rate, % | 45.45 | 54.55 | 66.36 | 79.55 | 90 |
Research shows: under the vulcanization system, at high WO
3In the ammonium tungstate solution of concentration, low phosphorus concentration, along with the increase of magnesiumcarbonate consumption, phosphoric residue concentration reduces gradually in the solution.When the theoretical multiple of magnesiumcarbonate was 1.4 times, the phosphorus concentration in the solution was reduced to 0.022g/L from 0.22g/L, WO
3: P is 1.36 * 10
4, dephosphorizing rate 90% reaches the dephosphorization standard.
Five, the Marinco H of 1~1.4 times of theoretical multiple is seen shown in the table 5 influence of vulcanization system ammonium tungstate solution dephosphorization.Wherein the weight of the Marinco H of 1 times of theoretical amount is 0.1235g.
Table 5 Marinco H consumption is to the influence of vulcanization system ammonium tungstate solution deep phosphorous removal
Research shows: under the vulcanization system, at high WO
3In the ammonium tungstate solution of concentration, low phosphorus concentration, along with the increase of Marinco H consumption, phosphoric residue concentration is constant basically in the solution.When the theoretical multiple of Marinco H was 1 times, the phosphorus in the solution was removed rate 43.64%, continues to strengthen the consumption of Marinco H, and dephosphorizing rate raises little.Therefore the Marinco H phosphor-removing effect is not good.
Embodiment 2
Get the 300ml ammonium tungstate solution in the 500ml beaker; Add the industrial ammonium sulfide of 1 times of theoretical amount, the magnesiumcarbonate of 1 times of theoretical amount respectively, pH=9.0 in the solution, reaction is 2 hours under the room temperature; The ammonium tungstate solution phosphorus concentration that filtration obtains is 0.10g/L, and the clearance of phosphorus is 54.55%.
Embodiment 3
Get the 300ml ammonium tungstate solution in the 500ml beaker; Add the industrial ammonium sulfide of 1 times of theoretical amount, the light magnesium oxide of 1.1 times of theoretical amount respectively, pH=9.0 in the solution, reaction is 2 hours under the room temperature; The ammonium tungstate solution phosphorus concentration that filtration obtains is 0.016g/L, and the clearance of phosphorus is 92.73%.
Embodiment 4
Get the 300ml ammonium tungstate solution in the 500ml beaker; Add the industrial ammonium sulfide of 1 times of theoretical amount, the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 of 1.2 times of theoretical amount respectively, pH=9.5 in the solution, reaction is 2 hours under the room temperature; The ammonium tungstate solution phosphorus concentration that filtration obtains is 0.006g/L, and the clearance of phosphorus is 97.27%.
Embodiment 5
Get the 300ml ammonium tungstate solution in the 500ml beaker; Add the industrial ammonium sulfide of 1 times of theoretical amount, the magnesium basic carbonate of 1.1 times of theoretical amount respectively, pH=10 in the solution, reaction is 2 hours under the room temperature; The ammonium tungstate solution phosphorus concentration that filtration obtains is 0.004g/L, and the clearance of phosphorus is 98.18%.
Embodiment 6
Adopt resulting ammonium tungstate solution in " embodiment 5 ", the APT that obtains through cationic exchange → evaporative crystallization technique is " 0 " level GB product.Its major impurity is as shown in table 6.
Table 6APT major impurity element and the contrast of " 0 " level GB
Element | K | Na | P | Ca | Cu | Mg | Mo |
0 grade of GB | 10 | 10 | 7 | 10 | 3 | 5 | 20 |
APT | 6 | 3 | <5 | <5 | <1 | <3 | 8 |
Embodiment 7
Adopt resulting ammonium tungstate solution in " embodiment 5 ", not through cationic exchange, but directly carry out the APT that evaporative crystallization technique obtains, wherein the part element exceeds the regulation of " 0 " level GB product.Its major impurity is as shown in table 7.
Table 7APT major impurity element and the contrast of " 0 " level GB
Element | K | Na | P | Ca | Cu | Mg | Mo |
0 grade of GB | 10 | 10 | 7 | 10 | 3 | 5 | 20 |
APT | 6 | 3 | 18 | 15 | 5 | 3 | 10 |
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means the concrete characteristic, structure, material or the characteristics that combine this embodiment or example to describe and is contained at least one embodiment of the present invention or the example.In this manual, the schematic statement to above-mentioned term not necessarily refers to identical embodiment or example.And concrete characteristic, structure, material or the characteristics of description can combine with suitable manner in any one or more embodiment or example.
Although illustrated and described embodiments of the invention; Those having ordinary skill in the art will appreciate that: under the situation that does not break away from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited claim and equivalent thereof.
Claims (10)
1. the method that ammonium tungstate solution purifies is characterized in that, comprising:
Ammonium tungstate solution is contacted with magnesium salts, so that remove dephosphorization with the form of magnesium ammonium phosphate sediment.
2. method according to claim 1 is characterized in that, said ammonium tungstate solution contains the WO of 350g/l at the most
3, preferably contain the WO of 230g/l
3
3. method according to claim 1 is characterized in that, said ammonium tungstate solution contains the phosphorus below the 3g/l.
4. method according to claim 1 is characterized in that, said magnesium salts is be selected from magnesium basic carbonate, sal epsom, Natural manganese dioxide, magnesiumcarbonate, Marinco H at least a.
5. method according to claim 1 is characterized in that, the amount of said magnesium salts is 1~1.4 times of theoretical value.
6. method according to claim 1 is characterized in that, under pH value 8-11, preferably pH value 9 times, said ammonium tungstate solution is contacted with said magnesium salts.
7. method according to claim 1 is characterized in that, said ammonium tungstate solution and the reaction of said magnesium salts 1-5 hour, preferred 120 minutes.
8. method according to claim 1 is characterized in that, said ammonium tungstate solution with before said magnesium salts contacts, is mixed said ammonium tungstate solution with ammonium sulfide, and the amount of preferred said ammonium sulfide is the 1%-3.5% of said ammonium tungstate solution volume.
9. method according to claim 1 is characterized in that, further comprises the ammonium tungstate solution through dephosphorization is carried out evaporative crystallization, so that obtain ammonium paratungstate.
10. method according to claim 9 is characterized in that, before said ammonium tungstate solution through dephosphorization is carried out evaporative crystallization, said ammonium tungstate solution through dephosphorization is carried out cationic exchange handle.
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CN104817115A (en) * | 2015-04-15 | 2015-08-05 | 赣州海创钨业有限公司 | Method for removing micro-phosphorus in ammonium tungstate solution |
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CN109368699A (en) * | 2018-12-19 | 2019-02-22 | 金堆城钼业股份有限公司 | The minimizing technology of magnesium in a kind of ammonium dimolybdate production technology |
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CN104973628A (en) * | 2015-06-30 | 2015-10-14 | 崇义章源钨业股份有限公司 | Method used for purifying sodium tungstate solution |
CN108773856A (en) * | 2018-09-10 | 2018-11-09 | 江钨世泰科钨品有限公司 | A kind of purification technique of purification sodium tungstate solution |
CN109368699A (en) * | 2018-12-19 | 2019-02-22 | 金堆城钼业股份有限公司 | The minimizing technology of magnesium in a kind of ammonium dimolybdate production technology |
CN112877540A (en) * | 2021-01-13 | 2021-06-01 | 厦门钨业股份有限公司 | Tungsten-molybdenum analysis method for tungsten smelting |
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CN113603143A (en) * | 2021-08-18 | 2021-11-05 | 崇义章源钨业股份有限公司 | Method for preparing ammonium paratungstate by removing molybdenum through one-step ammonia solution dephosphorization of tungstic acid |
CN113943871A (en) * | 2021-10-21 | 2022-01-18 | 崇义章源钨业股份有限公司 | Method for treating magnesium ammonium phosphate slag containing tungsten |
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