CN108754123B - A method of processing scheelite - Google Patents
A method of processing scheelite Download PDFInfo
- Publication number
- CN108754123B CN108754123B CN201810651384.1A CN201810651384A CN108754123B CN 108754123 B CN108754123 B CN 108754123B CN 201810651384 A CN201810651384 A CN 201810651384A CN 108754123 B CN108754123 B CN 108754123B
- Authority
- CN
- China
- Prior art keywords
- scheelite
- magnesium
- leaching
- handling
- magnesium salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000012545 processing Methods 0.000 title abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229940053652 fluorinse Drugs 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010937 tungsten Substances 0.000 abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 7
- 230000007704 transition Effects 0.000 abstract description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 235000011147 magnesium chloride Nutrition 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- 229910004829 CaWO4 Inorganic materials 0.000 description 5
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 5
- 229910017672 MgWO4 Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910003893 H2WO4 Inorganic materials 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- WLQXPAUZYVXSNE-UHFFFAOYSA-N [Ca].O[N+]([O-])=O Chemical compound [Ca].O[N+]([O-])=O WLQXPAUZYVXSNE-UHFFFAOYSA-N 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of method for handling scheelite, this method is to carry out high-temperature roasting processing after mixing scheelite with magnesium salts；Gained calcining, using acidic leaching or alkaline leaching, obtains wolframic acid or tungstate solution after washing；This method will be difficult to the CaWO of soda acid leaching using magnesium salts at high temperature in scheelite4It makes the transition into and is easy to the MgWO that conventional soda acid leaches4, scheelite leaching efficiency is improved, this method solves the problems, such as directly to extract tungsten difficulty from artificial schellite.
Description
Technical field
The present invention relates to a kind of processing methods of scheelite, and in particular to a kind of to utilize magnesium salts under the high temperature conditions by white tungsten
Artificial schellite is converted to the magnesium tungstate for being easy to leach in mine, realizes the method that tungsten efficiently leaches in scheelite, belongs to metallurgical technology neck
Domain.
Background technique
In nature, it has been found that tungsten ore type has more than 20, such as wolframite ((Fe, Mn) WO4), scheelite
(CaWO4), wolfram ocher (WO3·H2O), tungstenite (WS2), stolzite (PbWO4) etc..Wherein wolframite and scheelite are industrial
The primary raw material of Tungsten smelting.It is industrially main former to smelt wolframite for a long time since wolframite easily picks up and easily smelts
Material, and scheelite is seldom by as raw material.Continuous depleted with wolframite, hardly possible selects the scheelite of smelting to become Tungsten smelting
Primary raw material.The maturation method for smelting scheelite has a hydrochloric acid decomposition method, soda pressuring cooking method, due to environmental protection and cost etc., this
Two methods are eliminated substantially.Metallargist also has been working hard how research more efficiently smelts scheelite.It is close
Nian Lai has emerged in large numbers the methods of a little new smelting scheelites, as mixed acid decomposes (CN102021328A, CN102021329A,
CN104388708A, CN104404249A, CN104404275A), it mixes caustic digestion (CN102154547A).Although these methods
Relatively traditional scheelite smelting process can improve the leaching efficiency of artificial schellite to a certain extent, but not from essence
It is upper to solve the problems, such as that scheelite uses conventional acid alkali carries to take difficulty in scheelite.
Summary of the invention
It is existing processing scheelite method there are aiming at the problem that, the first purpose of this invention is to be to provide one kind
It will be difficult to the CaWO of soda acid leaching in scheelite at high temperature using magnesium salts4It makes the transition into and is easy to the MgWO that conventional soda acid leaches4, mention
The method of high scheelite leaching efficiency, this method solve the problems that tungsten difficulty is directly extracted from artificial schellite.
In order to achieve the above technical purposes, the present invention provides a kind of method for handling scheelite, this method is by white tungsten
After mine is mixed with magnesium salts, calcination process is carried out at a temperature of being placed in 500-800 DEG C；Gained calcining is soaked after washing using acidity
Out or alkaline leaching, wolframic acid or tungstate solution are obtained.
Preferred scheme, the magnesium salts are the magnesium salts without the crystallization water.Further preferred magnesium salts include magnesium chloride and/or
Magnesium nitrate.Most preferably magnesium chloride.
More preferably scheme, the dosage of the magnesium salts are that artificial schellite in scheelite is converted to needed for magnesium salts needed for magnesium tungstate
1-8 times of theoretical molar amount.It is more preferably 3-6 times.
Preferred scheme, the temperature of the calcination process are 570-670 DEG C.
More preferably scheme, the time of the calcination process are 1-8h.It is more preferably 2-5h.
Preferred scheme, in the water-washing process, the mass ratio of calcining and water is 1:10-100.More preferably 1:40-60.Water
It washes journey and mainly washes away the complete magnesium chloride of roasting unreacted and/or magnesium nitrate and product of roasting calcium chloride and/or nitric acid
Calcium, these compounds can react generation artificial schellite with product sodium tungstate is leached in subsequent alkaline leaching process and reduce tungsten and leach
Rate.
More preferably scheme, the temperature of the washing are room temperature, washing time 1-4h.Using stirring in water-washing process
Mode.Washing time is preferably 2h.
Preferred scheme, the acidic leaching is using hydrochloric acid and/or nitric acid as acid lixiviant；The alkaline leaching is adopted
Use sodium hydroxide solution, sodium radio-phosphate,P-32 solution, Fluorinse as alkaline leaching agent.
More preferably scheme, the condition of the acidic leaching are as follows: acid lixiviant concentration is 2-10mol/L, and liquid-solid ratio is
2:1-10:1mL/g, extraction temperature are 30-80 DEG C, extraction time 1-5h.The condition of acidic leaching is preferred are as follows: acid lixiviant
Concentration is 3-6mol/L, and liquid-solid ratio 4:1-6:1mL/g, extraction temperature is 40-60 DEG C, extraction time 2-4h.
More preferably scheme, the condition that the alkali leaches are that alkaline leaching agent is 2-12mol/L, liquid-solid ratio 1:1-6:
1mL/g, extraction temperature are 60-120 DEG C, extraction time 2-8h.The condition that alkali leaches is preferably that alkaline leaching agent is 4-
6mol/L, liquid-solid ratio 2:1-4:1mL/g, extraction temperature are 70-90 DEG C, extraction time 2-4h.
Tungstenic is (with WO in scheelite of the invention3Meter) 20-70%, granularity is less than 200 μm.
Technical solution of the present invention, which is put forward for the first time, is converted to magnesium tungstate for main mine phase artificial schellite in scheelite, then realizes it
The soda acid of magnesium tungstate leaches.Be mainly based upon lot of experiments to show: magnesium tungstate is whether reacted with acid or with alkali, anti-
Big several order of magnitude of the equilibrium constant for answering the equal wolframic acid calcium of the equilibrium constant to react with acid or alkali.When such as 25 DEG C, artificial schellite and tungsten
Shown in the equilibrium constant of sour magnesium such as formula (1)-(4):
CaWO4+2OH-=Ca (OH)2+WO4 2-K=1.209 × 10-6 (1)
CaWO4+2H+=H2WO4+Ca2+K=8.721 × 103 (2)
MgWO4+2OH-=Mg (OH)2+WO4 2-K=3.451 × 105 (3)
MgWO4+2H+=H2WO4+Mg2+K=4.438 × 109 (4)
At i.e. 25 DEG C, the equilibrium constant that magnesium tungstate is reacted with alkali is up to 3.451 × 105, the equilibrium constant reacted with acid can
Up to 4.438 × 109, it is far longer than the reaction equilibrium constant (respectively 1.209 × 10 of artificial schellite and alkali or acid-6With 8.721 ×
103).Usually, if a reaction, its reaction equilibrium constant reach 104, then show that the reaction is to be very easy to progress
's.Based on this discovery, inventor, which advances an idea, is converted to magnesium tungstate for the artificial schellite in scheelite, so as to reduce scheelite
The leaching difficulty of middle tungsten, improves the leaching efficiency of tungsten.By largely testing, inventor successfully passes through high temperature solid state reaction,
By the artificial schellite Efficient Conversion in scheelite at magnesium tungstate.It, under the appropriate temperature conditions, will by selecting magnesium salts as magnesium source
Artificial schellite mineral in scheelite are thoroughly converted to magnesium tungstate, key reaction such as following formula (5)-(6).
CaWO4+MgCl2=MgWO4+CaCl2K=1.617 × 104 (5)
CaWO4+Mg(NO3)2=MgWO4+Ca(NO3)2K=7.752 × 103 (6)
After realizing transition at magnesium tungstate artificial schellite in scheelite by the above method, using conventional soda acid, mild
Under the conditions of the efficient leaching of tungsten may be implemented.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
The processing method of scheelite proposed by the present invention, using roasting-washing-leaching technology path, by by magnesium salts
It is mixed with scheelite and carries out high temperature solid state reaction, so that artificial schellite is transformed into magnesium tungstate, tungsten is extracted from magnesium tungstate, with prior art
It compares, there is following invention effect:
1. for the first time using magnesium salts as transition agent, tungsten in the scheelite under the appropriate temperature conditions successfully smelting hardly possible
Sour calcium is transformed into the magnesium tungstate for being easy leaching, substantially reduces the leaching difficulty of scheelite, improves tungsten ore leaching efficiency.
2. magnesium tungstate of the artificial schellite by generating after conversion does not need concentrated acid, solves classical acid during Ore Leaching
Method decomposes scheelite and leads to the problem of acid mist, and extraction temperature is lower (40-60 DEG C).
3. artificial schellite is through the magnesium tungstate that generates after conversion in alkali leaching process, temperature is compared with prior art when reaction
(180-220 DEG C) is low, and only 70-90 DEG C, institute's alkali needed is also low compared with prior art (1.8-2.6 times), and only 1.0-1.4 times, greatly
It reduces costs greatly, while avoiding security risk caused by high temperature and pressure.
Detailed description of the invention
[Fig. 1] is the process flow chart of the method for scheelite processing of the invention.
[Fig. 2] is the XRD diagram of scheelite and its product of roasting in the present invention.
[Fig. 3] is that the product of roasting of scheelite in the present invention uses the XRD diagram of the leached mud obtained after leaching with sodium hydroxide.
Specific embodiment
Following embodiment is intended to that the content of present invention is further described, rather than limits the guarantor of the claims in the present invention
Protect range.
Embodiment 1
Certain scheelite contains WO3: 61.72%, granularity is less than 200 μm.Mine 5g is weighed, 4 times of theoretical amount magnesium chlorides are added, is mixed
670 degree of roasting 4h of Muffle furnace are put into after closing uniformly, obtain calcining；300mL deionized water is added into calcining, after stirring at normal temperature 2h
Filtering is cleaned, obtains filter cake；The hydrochloric acid that 30mL concentration is 6mol/L is added into filter cake, 60 DEG C are filtered after reacting for 3 hours, and obtain
To wolframic acid, metal W recovery rate is 99.4%.
Control experiment: certain scheelite contains WO3: 61.72%, granularity is less than 200 μm.Mine 5g is weighed, 30mL concentration is added
For the hydrochloric acid of 6mol/L, 60 DEG C are filtered after reacting for 3 hours, and obtain wolframic acid, and metal W recovery rate is 72.3%.
Certain scheelite contains WO3: 43.89%, granularity is less than 200 μm.Mine 5g is weighed, 3 times of theoretical amount magnesium nitrates are added, is mixed
650 degree of roasting 6h of Muffle furnace are put into after closing uniformly, obtain calcining；200mL deionized water is added into calcining, after stirring at normal temperature 3h
Filtering is cleaned, obtains filter cake；Into filter cake be added 40mL concentration be 3mol/L nitric acid, 80 DEG C reaction 4 hours after filter, obtain
To wolframic acid, metal W recovery rate is 98.6%.
Embodiment 3
Certain scheelite contains WO3: 26.45%, granularity is less than 200 μm.Mine 5g is weighed, 6 times of theoretical amount magnesium nitrates are added, is mixed
670 degree of roasting 8h of Muffle furnace are put into after closing uniformly, obtain calcining；400mL deionized water is added into calcining, after stirring at normal temperature 3h
Filtering is cleaned, obtains filter cake；Into filter cake be added 40mL concentration be 8mol/L hydrochloric acid, 30 DEG C reaction 5 hours after filter, obtain
To wolframic acid, metal W recovery rate is 98.2%.
Embodiment 4
Certain scheelite contains WO3: 61.72%, granularity is less than 200 μm.Mine 5g is weighed, 4 times of theoretical amount magnesium chlorides are added, is mixed
670 degree of roasting 6h of Muffle furnace are put into after closing uniformly, obtain calcining；300mL deionized water is added into calcining, after stirring at normal temperature 2h
Filtering is cleaned, obtains filter cake；Into filter cake be added 40mL concentration be 4mol/L sodium hydroxide, 100 DEG C reaction 3 hours after mistake
Filter, obtains sodium tungstate, and metal W recovery rate is 99.8%.
Control experiment: certain scheelite contains WO3: 61.72%, granularity is less than 200 μm.Mine 5g is weighed, 40mL concentration is added
For the sodium hydroxide of 4mol/L, 100 DEG C are filtered after reacting for 3 hours, and obtain sodium tungstate, and metal W recovery rate is 13.7%.
Embodiment 5
Certain scheelite contains WO3: 61.72%, granularity is less than 200 μm.Mine 5g is weighed, 6 times of theoretical amount magnesium chlorides are added, is mixed
600 degree of roasting 8h of Muffle furnace are put into after closing uniformly, obtain calcining；300mL deionized water is added into calcining, after stirring at normal temperature 2h
Filtering is cleaned, obtains filter cake；Into filter cake be added 30mL concentration be 8mol/L sodium phosphate, 80 DEG C reaction 5 hours after filter,
Sodium tungstate is obtained, metal W recovery rate is 99.6%.
Embodiment 6
Certain scheelite contains WO3: 43.89%, granularity is less than 200 μm.Mine 5g is weighed, 6 times of theoretical amount magnesium nitrates are added, is mixed
670 degree of roasting 6h of Muffle furnace are put into after closing uniformly, obtain calcining；400mL deionized water is added into calcining, after stirring at normal temperature 4h
Filtering is cleaned, obtains filter cake；The sodium fluoride that 25mL concentration is 6mol/L is added into filter cake, 80 DEG C are filtered after reacting for 3 hours,
Sodium tungstate is obtained, metal W recovery rate is 99.7%.
Embodiment 7
Certain scheelite contains WO3: 43.89%, granularity is less than 200 μm.Mine 5g is weighed, 6 times of theoretical amount magnesium nitrates are added, is mixed
670 degree of roasting 6h of Muffle furnace are put into after closing uniformly, obtain calcining；400mL deionized water is added into calcining, after stirring at normal temperature 4h
Filtering is cleaned, obtains filter cake；Into filter cake be added 45mL concentration be 8mol/L sodium fluoride, 80 DEG C reaction 5 hours after filter,
Ammonium tungstate is obtained, metal W recovery rate is 99.3%.
Embodiment 8
Certain scheelite contains WO3: 61.72%, granularity is less than 200 μm.Mine 5g is weighed, 6 times of theoretical amount magnesium nitrates are added, is mixed
600 degree of roasting 8h of Muffle furnace are put into after closing uniformly, obtain calcining；300mL deionized water is added into calcining, after stirring at normal temperature 2h
Filtering is cleaned, obtains filter cake；Into filter cake be added 30mL concentration be 5mol/L sodium hydroxide, 100 DEG C reaction 3 hours after mistake
Filter, obtains sodium tungstate, and metal W recovery rate is 99.2%.
Claims (10)
1. a kind of method for handling scheelite, it is characterised in that: after mixing scheelite with magnesium salts, be placed in 500-800 DEG C of temperature
Lower carry out calcination process；Gained calcining, using acidic leaching or alkaline leaching, obtains wolframic acid or tungstates is molten after washing
Liquid；The magnesium salts is magnesium chloride and/or magnesium nitrate.
2. a kind of method for handling scheelite according to claim 1, it is characterised in that: the magnesium salts is without the crystallization water
Magnesium salts.
3. a kind of method for handling scheelite according to claim 1 or 2, it is characterised in that: the dosage of the magnesium salts is
Artificial schellite in scheelite is converted to 1-8 times of theoretical molar amount needed for magnesium salts needed for magnesium tungstate.
4. a kind of method for handling scheelite according to claim 1 or 2, it is characterised in that: the temperature of the calcination process
Degree is 570-670 DEG C.
5. a kind of method for handling scheelite according to claim 4, it is characterised in that: the time of the calcination process is
1-8h。
6. a kind of method for handling scheelite according to claim 1, it is characterised in that: in the water-washing process, calcining
Mass ratio with water is 1:10-100.
7. a kind of method for handling scheelite according to claim 1, it is characterised in that: the temperature of the washing is room
Temperature, washing time 1-4h.
8. a kind of method for handling scheelite according to claim 1, it is characterised in that: the acidic leaching uses hydrochloric acid
And/or nitric acid is as acid lixiviant；The alkaline leaching is made using sodium hydroxide solution, sodium radio-phosphate,P-32 solution, Fluorinse
For alkaline leaching agent.
9. a kind of method for handling scheelite according to claim 8, it is characterised in that: the condition of the acidic leaching
Are as follows: acid lixiviant concentration is 2-10mol/L, and liquid-solid ratio 2:1-10:1mL/g, extraction temperature is 30-80 DEG C, extraction time
For 1-5h.
10. a kind of method for handling scheelite according to claim 8, it is characterised in that: the condition that the alkali leaches is,
Alkaline leaching agent is 2-12mol/L, and liquid-solid ratio 1:1-6:1mL/g, extraction temperature is 60-120 DEG C, extraction time 2-8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810651384.1A CN108754123B (en) | 2018-06-22 | 2018-06-22 | A method of processing scheelite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810651384.1A CN108754123B (en) | 2018-06-22 | 2018-06-22 | A method of processing scheelite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108754123A CN108754123A (en) | 2018-11-06 |
| CN108754123B true CN108754123B (en) | 2019-10-15 |
Family
ID=63976352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810651384.1A Expired - Fee Related CN108754123B (en) | 2018-06-22 | 2018-06-22 | A method of processing scheelite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108754123B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280769B (en) * | 2018-11-30 | 2020-12-04 | 贵州轻工职业技术学院 | Method for extracting tungsten-containing mineral by microwave and application |
| CN109439929B (en) * | 2018-12-17 | 2020-07-28 | 江西理工大学 | Method for decomposing wolframite and wolframite mixed ore by alkaline system |
| CN109439930B (en) * | 2018-12-18 | 2020-07-28 | 赣州海创钨业有限公司 | Method for decomposing medium-low grade scheelite |
| JP7206009B2 (en) * | 2019-02-25 | 2023-01-17 | 三菱マテリアル株式会社 | How to recover tungsten |
| CN110643808B (en) * | 2019-11-07 | 2021-06-22 | 赣州有色冶金研究所有限公司 | Method for extracting tungsten from low-grade wolframite |
| CN111020234A (en) * | 2019-12-27 | 2020-04-17 | 厦门钨业股份有限公司 | Method for preparing APT (ammonium paratungstate) by utilizing tungsten-containing waste |
| CN110980809A (en) * | 2019-12-27 | 2020-04-10 | 厦门钨业股份有限公司 | Method for preparing ammonium metatungstate by utilizing tungsten-containing waste |
| CN111020235A (en) * | 2019-12-27 | 2020-04-17 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
| CN111057880A (en) * | 2019-12-27 | 2020-04-24 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
| CN111057881B (en) * | 2019-12-31 | 2022-07-12 | 湖北绿钨资源循环有限公司 | Method for recovering tungsten from purification slag |
| CN113106248B (en) * | 2021-03-01 | 2022-09-30 | 崇义章源钨业股份有限公司 | Tungsten mineral transformation pretreatment method |
| CN113234921A (en) * | 2021-05-10 | 2021-08-10 | 贵州轻工职业技术学院 | Method for extracting tungsten and fluorine from fluorine-containing tungsten ore and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177944C (en) * | 2002-11-15 | 2004-12-01 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN102011017A (en) * | 2010-11-19 | 2011-04-13 | 中南大学 | Method for extracting tungsten by decomposing tungsten minerals |
| CN104313361B (en) * | 2014-10-16 | 2016-11-23 | 中国科学院过程工程研究所 | A kind of Leaching of Vanadium from Vanadium slag containing chromium and the process of coproduction chromium-base alloy |
| CN105112691A (en) * | 2015-10-10 | 2015-12-02 | 江西理工大学 | Method for extracting tungsten from tungsten minerals through alkaline decomposition |
| CN106011504B (en) * | 2016-07-05 | 2018-01-02 | 江西理工大学 | A kind of method for decomposing scheelite |
-
2018
- 2018-06-22 CN CN201810651384.1A patent/CN108754123B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN108754123A (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108754123B (en) | A method of processing scheelite | |
| CN103361486B (en) | Method for extracting high purity scandium oxide and titanium from waste acid solution containing scandium and titanium | |
| CN107032400B (en) | TiCl4The method that purification tailings alkali is soaked standby high-purity vanadium oxide | |
| WO2015176429A1 (en) | Method for extracting vanadium by leaching vanadium-containing raw material fired clinkers with ammonium bicarbonate solution | |
| CN102127654B (en) | Method for decomposing chromium-containing vanadium slag by using sodium hydroxide molten salt | |
| CN106282608B (en) | A method of decomposing Scheelite-Wolframite Mixed Mine | |
| CN106929696A (en) | TiCl4Refine method of the tailings ammonium soak for high-purity vanadium oxide | |
| CN105087934B (en) | The recovery method of useless fluorescent powder middle rare earth metal | |
| CN102121068A (en) | Method for preparing vanadium pentoxide | |
| CN110042226A (en) | A method of plus iron low temperature concentrated sulfuric acid roasting decomposes high-grade mixed rare earth concentrates | |
| CN110004309A (en) | The method of soda acid combined extracting tungsten from tungsten mineral | |
| CN108384960B (en) | A kind of synchronous method for extracting tungsten slag with tungsten, aluminium, sodium and iron in red mud | |
| CN107619941A (en) | The method that vanadium and chromium are separated from vanadium chromium slag | |
| Zhao et al. | Precipitation of vanadium from Bayer liquor with lime | |
| CN102127656A (en) | Method for decomposing vanadium slag by liquid phase oxidation | |
| CN106987732A (en) | A kind of method for separating and recovering vanadium chromium | |
| CN105603220A (en) | Method for extracting vanadium and chromium step by step and removing aluminum and silicon from alkaline aqueous solution | |
| CN109055724A (en) | The method of vanadium and chromium is extracted from chrome alum mine/slag | |
| CN101607721B (en) | Method for preparing highly pure magnesium hydroxide and magnesium hexa-silicate by using olivine tailing mine | |
| CN108531718A (en) | A method of producing chrome green using tailings in vanadium extraction | |
| CN109811122A (en) | The extracting method of rare earth oxide | |
| Xu et al. | The effect of iron sources on caustic and alumina recovery from synthetic bayer DSP (sodalite) | |
| JP6317864B2 (en) | Method for treating tungsten-containing material | |
| CN106011465B (en) | A kind of method that high pressure leaches Baotou rare earth ore deposit | |
| CN109019687A (en) | A method of vanadic anhydride and chrome green are prepared using chromium type high vanadium slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191015 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |