CN115893494A - Method for preparing ammonium paratungstate by smelting wolframite - Google Patents
Method for preparing ammonium paratungstate by smelting wolframite Download PDFInfo
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- CN115893494A CN115893494A CN202211432542.7A CN202211432542A CN115893494A CN 115893494 A CN115893494 A CN 115893494A CN 202211432542 A CN202211432542 A CN 202211432542A CN 115893494 A CN115893494 A CN 115893494A
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- tungsten
- wolframite
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- magnesium
- ammonium paratungstate
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- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 39
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 title claims abstract description 33
- 238000003723 Smelting Methods 0.000 title claims abstract description 31
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 119
- 239000010937 tungsten Substances 0.000 claims abstract description 119
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 54
- 230000009466 transformation Effects 0.000 claims abstract description 39
- 239000011575 calcium Substances 0.000 claims abstract description 36
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 31
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 19
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004254 Ammonium phosphate Substances 0.000 claims description 9
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims description 6
- CRLHSBRULQUYOK-UHFFFAOYSA-N dioxido(dioxo)tungsten;manganese(2+) Chemical compound [Mn+2].[O-][W]([O-])(=O)=O CRLHSBRULQUYOK-UHFFFAOYSA-N 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000002411 adverse Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 238000001914 filtration Methods 0.000 description 31
- 239000007788 liquid Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 14
- 239000008399 tap water Substances 0.000 description 14
- 235000020679 tap water Nutrition 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical group [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001607 magnesium mineral Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing ammonium paratungstate by smelting wolframite, which comprises the following steps: 1) Mixing wolframite and magnesium chloride, and then carrying out high-temperature transformation reaction to obtain a tungsten-containing transformation product; 2) Soaking the tungsten-containing transformation product in water and separating the water-soluble chloride solution to obtain a solid tungsten-extracting raw material; 3) Carrying out decomposition reaction on the solid tungsten extraction raw material, water and ammonium salt to obtain a tungsten-containing solution; 4) Removing impurities from the tungsten-containing solution by using magnesium salt, and carrying out evaporative crystallization to obtain ammonium paratungstate; the method can realize the high-efficiency decomposition of the wolframite, simultaneously efficiently extract tungsten and obtain an ammonium paratungstate product, can effectively eliminate the adverse effects caused by the associated calcium and the like in the wolframite, reduces the discharge amount of waste water, and is particularly suitable for the smelting of the high-calcium wolframite.
Description
Technical Field
The invention relates to a method for smelting wolframite, in particular to a method for preparing ammonium paratungstate by smelting wolframite, belonging to the technical field of rare metal smelting.
Background
The effective component of the wolframite is FeWO 4 And MnWO 4 . Because of the characteristics of easy mining, selection and smelting, the wolframite has long been the main raw material in the tungsten smelting industry. However, as the high-quality wolframite is depleted, high-calcium wolframite, such as with calcite (CaCO) 3 ) Fluorite (CaF) 2 ) Apatite (Ca) 5 (PO 4 ) 3 (F, OH)), and even intergrown white tungsten (CaWO) 4 ) The wolframite has attracted people's attention.
In production, sodium carbonate or sodium hydroxide is often adopted to decompose wolframite to obtain a crude sodium tungstate solution, then the crude sodium tungstate solution is dephosphorized, molybdenum removal and transformation are carried out by adopting an ion exchange method, and finally an ammonium paratungstate product is obtained by adopting an evaporative crystallization method. The smelting process has the advantages of high tungsten decomposition rate, mature and stable process. However, in this process, the decomposition system contains a large amount of calcium, which is easily combined with sodium tungstate in the decomposition liquid to form calcium tungstate, resulting in a decrease in the tungsten decomposition rate. Meanwhile, the crude sodium tungstate solution in the process adopts calcium carbonate to remove phosphorus, and the generated phosphorus removal slag contains high calcium tungstate (40-60%), so that the recovery rate of metal tungsten is reduced. In addition, the sodium tungstate solution after phosphorus removal in the process is transformed by adopting an ion exchange method, so that a large amount of high-salt wastewater generated by the transformation increases the treatment cost of tungsten smelting wastewater. On the other hand, when the process is adopted to smelt the high-calcium wolframite, the alkali dosage needs to be excessive by 5 to 8 times, the decomposition temperature needs to be increased to 220 to 250 ℃ to reach a satisfactory tungsten decomposition rate, and a large amount of excessive alkali liquor is difficult to economically and effectively recover, so that the decomposition cost is increased.
In conclusion, the alkali decomposition → calcium carbonate dephosphorization → ion exchange process is adopted in the existing industrial wolframite smelting process, and the following problems exist: firstly, because of the existence of calcium in the system, calcium tungstate is generated in the decomposition liquid and the phosphorus-removing slag of the crude sodium tungstate solution contains a large amount of calcium tungstate. Secondly, the ion exchange method produces a large amount of high-salinity wastewater, which causes the increase of wastewater treatment cost. Thirdly, a large amount of excess alkali liquor is difficult to recover when the high-calcium wolframite is treated, so that the production cost is increased. Therefore, a tungsten ore smelting process which can eliminate the adverse effect of calcium and reduce the discharge of waste water simultaneously is needed, so that the comprehensive utilization rate of tungsten resources in China is improved and the sustainable development of the tungsten industry is stabilized.
Disclosure of Invention
Aiming at the defects of the method for smelting the wolframite in the prior art, the invention aims to provide the method for smelting the wolframite to prepare the ammonium paratungstate, which can realize the high-efficiency decomposition of the wolframite, efficiently extract tungsten and obtain an ammonium paratungstate product at the same time, can effectively eliminate the adverse effect caused by calcium and the like in the wolframite, reduces the discharge amount of waste water, and is particularly suitable for smelting the high-calcium wolframite.
In order to achieve the technical purpose, the invention provides a method for preparing ammonium paratungstate by smelting wolframite, which comprises the following steps: 1) Mixing wolframite and magnesium chloride, and then carrying out high-temperature transformation reaction to obtain a tungsten-containing transformation product; 2) Soaking the tungsten-containing transformation product in water and separating the water-soluble chlorine salt solution to obtain a solid tungsten-extracting raw material; 3) Carrying out decomposition reaction on the solid tungsten extraction raw material, water and ammonium salt to obtain a tungsten-containing solution; 4) And removing impurities from the tungsten-containing solution by using magnesium salt, and carrying out evaporative crystallization to obtain the ammonium paratungstate.
The key point of the technical scheme of the invention is that the high-temperature transformation reaction is carried out on the wolframite by utilizing the magnesium chloride, and in the high-temperature transformation process, the magnesium chloride can promote FeWO in the wolframite 4 And MnWO 4 Even with accompanying CaWO 4 All converted into monoclinic MgWO with single component 4 (equations (1) to (3)), and the monoclinic magnesium tungstate is a relative tetragonal tungstate (e.g., caWO) 4 Etc.) have higher reactivity and also have monoclinic system FeWO 4 And MnWO 4 The activity is far lower than that of monoclinic MgWO 4 Monoclinic MgWO 4 Can be decomposed by ammonium salt under mild conditions, and the magnesium chloride can also replace iron, manganese, calcium and the like in the wolframite to be converted into soluble chloride, so that the tungsten-extracting raw material with high purity can be obtained by water soaking, and the tungsten-extracting raw material is decomposed by the ammonium salt, so that tungsten can be efficiently extracted to obtain an ammonium tungstate solution ((reaction formulas (4) - (6))).
FeWO 4(s) +MgCl 2(s) ＝MgWO 4(s) +FeCl 2(s) (1)
MnWO 4(s) +MgCl 2(s) ＝MgWO 4(s) +MnCl 2(s) (2)
CaWO 4(s) +MgCl 2(s) ＝MgWO 4(s) +CaCl 2(s) (3)
MgWO 4(s) +(NH 4 ) 3 PO 4(aq) ＝NH 4 MgPO 4(s) +(NH 4 ) 2 WO 4(aq) (4)
MgWO 4(s) +2NH 4 F (aq) ＝MgF 2(s) +(NH 4 ) 2 WO 4(aq) (5)
MgWO 4(s) +(NH 4 ) 2 CO 3(aq) ＝MgCO 3(s) +(NH 4 ) 2 WO 4(aq) (6)
As a preferable scheme, the amount of the magnesium chloride is 1 to 4 times of the theoretical molar amount of the magnesium chloride required for converting all tungstate including iron tungstate and/or manganese tungstate and/or calcium tungstate in the wolframite into magnesium tungstate. The dosage of the magnesium chloride is 1.5 to 2 times of the theoretical molar amount of the magnesium chloride required by converting all tungstates containing iron tungstate and/or manganese tungstate and/or calcium tungstate in the wolframite into magnesium tungstate. If the dosage of the magnesium chloride is too low, the conversion of the wolframite is incomplete, and if the dosage of the magnesium chloride is too high, the conversion efficiency of the wolframite is not obviously increased any more, but the magnesium chloride is wasted.
As a preferred embodiment, the conditions of the high temperature transformation reaction are as follows: the temperature is 500-700 ℃, and the time is 5-240 min. The temperature of the high-temperature transformation reaction is more preferably 550 to 600 ℃ and the most preferably 30 to 60min. If the temperature of the high-temperature transformation reaction is too low, incomplete transformation of the wolframite can be caused; if the temperature of the high-temperature transformation reaction is too high, the tungsten-containing transformation product is hardened and is difficult to loosen, so that the subsequent water soaking and tungsten extraction processes are not facilitated.
As a preferred scheme, the water soaking conditions are as follows: and (3) the liquid-solid ratio is 2-5mL, the mixture is statically soaked at room temperature, and the soaking end point is that all tungsten-containing transformation products are loose. Under the optimized leaching condition, the separation and removal of soluble chlorine salt in the tungsten-containing transformation product can be realized, and the soluble chlorine salt mainly comprises an excessive chlorinating agent and generated products of ferric chloride, manganese chloride, calcium chloride and the like. The water adopted in the water soaking process is tap water and/or neutral water for production circulation.
In a preferred embodiment, in the decomposition of the tungsten extraction raw material, the ammonium salt includes at least one of ammonium phosphate, ammonium carbonate and ammonium fluoride. Most preferred is ammonium phosphate. The water is tap water.
As a more preferable scheme, the dosage of the ammonium salt is the WO in the solid tungsten extraction raw material 3 All conversion to WO 4 2- 1 to 6 times the theoretical molar amount of the desired ammonium salt. Further preferred amounts of ammonium salt are 2 to 4 times the amount.
As a preferred embodiment, the decomposition reaction conditions are: the temperature is 100-180 ℃, the liquid-solid ratio of water to the solid tungsten extraction raw material is 2-10mL, and the time is 1-4 hours. Further preferably, the temperature is 100-140 ℃, the liquid-solid ratio of water to the solid tungsten extraction raw material is 3-6 mL. Monoclinic FeWO contained in wolframite if it is not subjected to high-temperature transformation of magnesium chloride 4 And MnWO 4 Or a tetragonal system associated therewith CaWO 4 Almost all of which are difficult to decompose directly by ammonium salts, and after converting the tungstate in the wolframite to magnesium tungstate of monoclinic system, it is possible to decompose by ammonium salts at temperatures below 150 c without the aid of acids and bases, which is unexpected.
As a preferable embodiment, the magnesium salt includes at least one of magnesium carbonate, magnesium hydroxide, and magnesium oxide. Magnesium oxide is most preferred.
As a preferable scheme, the condition for removing impurities is as follows: the temperature is 20-80 ℃, the time is 0.5-3 h, and the dosage of the magnesium salt is 2-4 times of the molar dosage of the magnesium salt required by converting all phosphate radicals in the tungsten-containing solution into magnesium phosphate precipitate. Further preferred temperature is 40 to 60 ℃. A more preferred time is 1 to 2 hours. The amount of magnesium salt is more preferably 2 to 3 times the molar amount of magnesium salt required for converting all phosphate in the tungsten-containing solution into magnesium phosphate precipitate.
As a preferable scheme, the particle size of the wolframite is less than or equal to 250 mu m, the content of Ca in percentage by mass is more than or equal to 10 percent, and the WO is 3 The mass percentage content is more than or equal to 20 percent.
As a preferable scheme, in the evaporation crystallization process, a steam heating or electric heating mode is adopted; the time for the evaporative crystallization is a time when the pH value of the solution is lowered to 5.5 to 7.0, and more preferably a time when the pH value is lowered to 6.0 to 6.5.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the invention adopts the technical route of transformation, water soaking, ammonium salt decomposition, magnesium salt impurity removal and evaporative crystallization to realize the smelting preparation of ammonium paratungstate from wolframite. Firstly, through mixing magnesium chloride and wolframite and then carrying out high-temperature transformation reaction, different tungstate minerals in the wolframite, including monoclinic system iron tungstate and manganese tungstate which are difficult to be decomposed by ammonium salt, even intergrowth tetragonal system calcium tungstate, can be completely converted into the same monoclinic system magnesium tungstate mineral, and the monoclinic system magnesium tungstate mineral has higher reaction activity, can adopt ammonium salt decomposition to extract tungsten under milder conditions, and directly prepare an ammonium tungstate solution; secondly, magnesium salt is adopted for dephosphorization; finally evaporating and crystallizing to obtain the ammonium paratungstate product. Compared with the existing industrial wolframite smelting process, the method has the following excellent effects:
1. the invention successfully transforms different types of tungstate minerals which are difficult to be decomposed by ammonium salt into the same monoclinic system tungstate magnesium mineral which has high reaction activity and is easy to be decomposed by ammonium salt at lower temperature under the condition of using magnesium chloride, thereby solving the problem that tungsten can not be simultaneously, economically and efficiently extracted from iron tungstate, manganese tungstate and calcium tungstate in the prior industry.
2. The main component of the tungsten-containing transformation product is monoclinic magnesium tungstate mineral with single component, calcium does not exist in an ammonium salt decomposition reaction system, and the problem of reduction of tungsten decomposition rate caused by the existence of calcium in the existing tungsten ore alkali decomposition is solved.
3. The decomposition solution of the tungsten-containing transformation product adopts magnesium salt to remove phosphorus, and calcium tungstate is not found in the obtained phosphorus removal slag, so that the problem of tungsten loss caused by calcium in the traditional phosphorus removal of tungstate solution is solved.
4. The tungsten-containing transformation product has lower decomposition reaction temperature which is only 100-140 ℃ lower than that of the existing tungsten ore alkali decomposition process (160-180 ℃), reduces the decomposition energy consumption and avoids the potential safety hazard of high temperature and high pressure.
5. The tungsten-containing transformation product is decomposed by adopting ammonium salt, the obtained decomposition liquid is ammonium tungstate solution, the step that the traditional tungsten ore decomposition liquid sodium tungstate needs to be transformed into ammonium tungstate by an ion exchange method is omitted, the production flow is shortened, and the discharge amount of smelting wastewater is greatly reduced.
Drawings
FIG. 1 is a process flow chart of the method for preparing ammonium paratungstate by smelting wolframite.
FIG. 2 is an XRD pattern of the wolframite and the products of the high temperature transformation reaction of wolframite and magnesium chloride in examples 1 and 2 of the present invention; from the results shown in fig. 2, it can be seen that iron tungstate, manganese tungstate and calcium tungstate in the wolframite can be all successfully converted into magnesium tungstate with high reactivity regardless of whether scheelite is associated in the wolframite, which indicates that the wolframite is feasible to be subjected to magnesium chloride transformation reaction.
FIG. 3 is an XRD pattern of a transformation reaction product of wolframite and a decomposition slag obtained by decomposing the transformation product with ammonium phosphate in example 1 of the present invention; from the results shown in fig. 3, it is understood that the main phase in the transformation product of wolframite is magnesium tungstate, and the main phase in the ammonium phosphate decomposition slag of the transformation product is magnesium ammonium phosphate, and the phase of magnesium tungstate has disappeared, indicating that the magnesium tungstate has a good decomposition effect by the ammonium phosphate decomposition.
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Certain wolframite (Fe, mn) WO 4 Associated with scheelite CaWO 4 The granularity is less than or equal to 250 mu m, and the content of Ca is as follows: 13.64% of WO 3 :45.29 percent, weighing 100g of the tungsten ore, adding 2 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 600 ℃ for 40min to obtain a tungsten-containing transformation product; adding 200mL of tap water into the transformed matter, statically soaking for 10min at normal temperature, filtering, and cleaning to obtain a tungsten extraction raw material; adding 300mL of tap water and 2 times of the tap water into the tungsten extracting raw materialReacting the theoretical amount of ammonium phosphate at 120 ℃ for 2 hours, and filtering to obtain a tungsten-containing solution; adding 2 times of theoretical amount of magnesium carbonate into the tungsten-containing solution, reacting for 1 hour at 50 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.3, and filtering to obtain an ammonium paratungstate product, wherein the tungsten recovery rate is 98.2%.
Comparative example 1
Certain wolframite (Fe, mn) WO 4 Associated with scheelite CaWO 4 The granularity is less than or equal to 250 mu m, and the content of Ca is as follows: 13.64% of WO 3 :45.29 percent, weighing 100g of the tungsten ore, adding 300mL of tap water and 2 times of theoretical amount of ammonium phosphate, reacting for 2 hours at 120 ℃, and filtering to obtain a tungsten-containing solution; adding 2 times of theoretical amount of magnesium carbonate into the tungsten-containing solution, reacting for 1 hour at 50 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.3, and filtering to obtain an ammonium paratungstate product, wherein the recovery rate of tungsten is 14.65%.
Example 2
Certain wolframite (Fe, mn) WO 4 The granularity is less than or equal to 250 mu m, and the Ca content is as follows: 15.32% of WO 3 :38.74 percent, weighing 100g of the tungsten ore, adding 3 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 650 ℃ for 60min to obtain a tungsten-containing transformed substance; adding 300mL of neutral water for production circulation into the transformed substance, soaking at normal temperature for 30min, filtering, and cleaning to obtain a tungsten-extracting raw material; adding 400mL of tap water and 3 times of theoretical amount of ammonium carbonate into the tungsten extracting raw material, reacting for 1 hour at 100 ℃, and filtering to obtain a tungsten-containing solution; adding 1 time of theoretical amount of magnesium hydroxide into the tungsten-containing solution, reacting for 2 hours at 40 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.5, and filtering to obtain an ammonium paratungstate product, wherein the recovery rate of tungsten is 96.7%.
Example 3
Certain wolframite (Fe, mn) WO 4 The granularity is less than or equal to 250 mu m, and the content of Ca is as follows: 11.32% of a compound containing WO 3 :29.82 percent, weighing 100g of the tungsten ore, adding 4 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 700 ℃ for 60min to obtain a tungsten-containing transformed substance; adding 400mL of tap water into the transformed material, soaking at normal temperature for 60min, filtering, and washingCleaning to obtain a tungsten extracting raw material; adding 400mL of tap water and 2 times of theoretical amount of ammonium fluoride into the tungsten extracting raw material, reacting for 2 hours at 110 ℃, and filtering to obtain a tungsten-containing solution; adding magnesium oxide with 3 times of theoretical amount into the tungsten-containing solution, reacting for 3 hours at 70 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.0, and filtering to obtain an ammonium paratungstate product, wherein the recovery rate of tungsten is 97.1%.
Example 4
Certain wolframite (Fe, mn) WO 4 The granularity is less than or equal to 250 mu m, and the content of Ca is as follows: 18.16% by weight of WO 3 :33.64 percent, weighing 100g of the tungsten ore, adding 3 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 600 ℃ for 40min to obtain a tungsten-containing transformed substance; adding 500mL of neutral water for production circulation into the transformed substance, soaking for 30min at normal temperature, filtering, and cleaning to obtain a tungsten-extracting raw material; adding 500mL of tap water and 2 times of theoretical amount of ammonium phosphate into the tungsten extracting raw material, reacting for 3 hours at 130 ℃, and filtering to obtain a tungsten-containing solution; adding 1 time of theoretical amount of magnesium carbonate into the tungsten-containing solution, reacting for 2 hours at 40 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.7, and filtering to obtain an ammonium paratungstate product, wherein the recovery rate of tungsten is 96.2%.
Example 5
Certain wolframite (Fe, mn) WO 4 The granularity is less than or equal to 250 mu m, and the content of Ca is as follows: 13.58% by weight of a compound containing WO 3 :41.36 percent, weighing 100g of the tungsten ore, adding 2 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 630 ℃ for 30min to obtain a tungsten-containing transformation product; adding 300mL of neutral water for production cycle into the transformed substance, soaking at normal temperature for 20min, filtering, and cleaning to obtain a tungsten extraction raw material; adding 500mL of tap water and 2 times of theoretical amount of ammonium carbonate into the tungsten extraction raw material, reacting for 2 hours at 120 ℃, and filtering to obtain a tungsten-containing solution; adding 2 times of theoretical amount of magnesium hydroxide into the tungsten-containing solution, reacting for 3 hours at 80 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.8, and filtering to obtain an ammonium paratungstate product, wherein the tungsten recovery rate is 95.4%.
Example 6
Certain wolframite (Fe, mn) WO 4 The granularity is less than or equal to 250 mu m, and the Ca content is as follows: 16.58% by weight of a compound containing WO 3 :23.87 percent, weighing 100g of the tungsten ore, adding 4 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 680 ℃ for 50min to obtain a tungsten-containing transformed substance; adding 500mL of tap water into the transformed matter, soaking for 30min at normal temperature, filtering, and cleaning to obtain a tungsten extraction raw material; adding 400mL of tap water and 1 time of theoretical amount of ammonium fluoride into the tungsten extraction raw material, reacting at 140 ℃ for 1 hour, and filtering to obtain a tungsten-containing solution; adding magnesium oxide with 3 times of theoretical amount into the tungsten-containing solution, reacting for 2 hours at 70 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.3, and filtering to obtain an ammonium paratungstate product, wherein the recovery rate of tungsten is 94.6%.
Example 7
Certain wolframite (Fe, mn) WO 4 The granularity is less than or equal to 250 mu m, and the Ca content is as follows: 20.45% and contains WO 3 :38.94 percent, weighing 100g of the tungsten ore, adding 3 times of theoretical amount of magnesium chloride, uniformly mixing, and carrying out heat preservation reaction at 700 ℃ for 40min to obtain a tungsten-containing transformation product; adding 400mL of neutral water for production circulation into the transformed substance, soaking for 50min at normal temperature, filtering, and cleaning to obtain a tungsten-extracting raw material; adding 500mL of tap water and 5 times of theoretical amount of ammonium fluoride into the tungsten extracting raw material, reacting for 1 hour at 110 ℃, and filtering to obtain a tungsten-containing solution; adding 3 times of theoretical amount of magnesium carbonate into the tungsten-containing solution, reacting for 2 hours at 60 ℃, and filtering to obtain tungsten-containing purified liquid; heating and evaporating the tungsten-containing purified liquid in a water bath until the pH value of the solution is 6.6, and filtering to obtain an ammonium paratungstate product, wherein the recovery rate of tungsten is 95.1%.
Claims (10)
1. A method for preparing ammonium paratungstate by smelting wolframite is characterized by comprising the following steps: comprises the following steps:
1) Mixing wolframite and magnesium chloride, and then carrying out high-temperature transformation reaction to obtain a tungsten-containing transformation product;
2) Soaking the tungsten-containing transformation product in water and separating the water-soluble chloride solution to obtain a solid tungsten-extracting raw material;
3) Carrying out decomposition reaction on the solid tungsten extraction raw material, water and ammonium salt to obtain a tungsten-containing solution;
4) And removing impurities from the tungsten-containing solution by using magnesium salt, and carrying out evaporative crystallization to obtain the ammonium paratungstate.
2. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1, characterized by comprising the following steps: the dosage of the magnesium chloride is 1 to 4 times of the theoretical molar quantity of the magnesium chloride required by converting all tungstate containing iron tungstate and/or manganese tungstate and/or calcium tungstate in the wolframite into the magnesium tungstate.
3. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1 or 2, characterized by comprising the following steps: the conditions of the high-temperature transformation reaction are as follows: the temperature is 500-700 ℃, and the time is 5-240 min.
4. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1, characterized by comprising the following steps: the water soaking conditions are as follows: and (3) the liquid-solid ratio is 2-5mL, the mixture is statically soaked at room temperature, and the soaking end point is that all tungsten-containing transformation products are loose.
5. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1, characterized in that: the ammonium salt comprises at least one of ammonium phosphate, ammonium carbonate and ammonium fluoride.
6. The method for preparing ammonium paratungstate by smelting of wolframite according to claim 1 or 5, characterized in that: the dosage of the ammonium salt is WO in the solid tungsten extraction raw material 3 All conversion to WO 4 2- 1 to 6 times the theoretical molar amount of the desired ammonium salt.
7. The method for preparing ammonium paratungstate by smelting of wolframite according to claim 1 or 5, characterized in that: the conditions of the decomposition reaction are as follows: the temperature is 100-180 ℃, the liquid-solid ratio of water to the solid tungsten extraction raw material is 2-10mL, and the time is 1-4 hours.
8. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1, characterized in that: the magnesium salt comprises at least one of magnesium carbonate, magnesium hydroxide and magnesium oxide.
9. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1 or 8, characterized by comprising the following steps: the impurity removal conditions are as follows: the temperature is 20-80 ℃, the time is 0.5-3 h, and the dosage of the magnesium salt is 2-4 times of the molar dosage of the magnesium salt required for converting all phosphate radicals in the tungsten-containing solution into magnesium phosphate precipitate.
10. The method for preparing ammonium paratungstate by smelting wolframite according to claim 1, characterized in that: the particle size of the wolframite is less than or equal to 250 mu m, the content of Ca in percentage by mass is more than or equal to 10 percent, and the content of WO 3 The mass percentage content is more than or equal to 20 percent.
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