CN116043038A - Low-grade tungsten-molybdenum ore synergistic oxidation leaching method - Google Patents
Low-grade tungsten-molybdenum ore synergistic oxidation leaching method Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 114
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 230000002195 synergetic effect Effects 0.000 title abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 81
- 239000011733 molybdenum Substances 0.000 claims abstract description 79
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 67
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000010937 tungsten Substances 0.000 claims abstract description 66
- 238000000227 grinding Methods 0.000 claims abstract description 26
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 21
- QKEIPIQRYZIKEQ-UHFFFAOYSA-N [Ca].[W].[Mo] Chemical compound [Ca].[W].[Mo] QKEIPIQRYZIKEQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000012216 screening Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000005406 washing Methods 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000010436 fluorite Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 2
- 229910021532 Calcite Inorganic materials 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000010459 dolomite Substances 0.000 claims 1
- 229910000514 dolomite Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000010450 olivine Substances 0.000 claims 1
- 229910052609 olivine Inorganic materials 0.000 claims 1
- 229910052611 pyroxene Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 16
- 239000012141 concentrate Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005188 flotation Methods 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- 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
- C22B34/34—Obtaining molybdenum
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- 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
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Abstract
The invention provides a low-grade tungsten-molybdenum ore collaborative oxidation leaching method, which belongs to the field of hydrometallurgy and comprises the following steps of: (1) Crushing, coarse grinding, screening and fine grinding the low-grade refractory tungsten-molybdenum ore to prepare fine tungsten-molybdenum ore; (2) performing process mineralogy analysis on the low-grade refractory tungsten-molybdenum ore; (3) And (3) adding a proper amount of oxidant to oxidize molybdenite, and simultaneously adding a proper amount of mixed alkali to perform synergistic wet leaching on the molybdenum-tungsten-calcium ore and scheelite. The invention can improve the oxidation rate of molybdenite, the molybdenum-tungsten ore dressing separation is difficult, the low-grade molybdenite oxidation synergistic scheelite and molybdenum-tungsten-calcium ore wet leaching technology is directly developed aiming at tungsten-molybdenum ore, the existing form of the molybdenite in the tungsten-molybdenum ore is changed, the state is converted from a indissolvable state to a soluble state, the leaching rate of the molybdenum leached by the tungsten-molybdenum ore Dan Changya is more than 83%, and the leaching rate of the tungsten is more than 45%; realizes the synergistic and efficient leaching of tungsten and molybdenum in tungsten-molybdenum ores.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a low-grade tungsten-molybdenum ore collaborative oxidation leaching method.
Background
Molybdenum is produced by using primary ore as main material, wherein the primary ore is molybdenite, and the resource of the molybdenite is gradually reduced along with the exploitation of the resource, and low-grade molybdenite is gradually the exploitation object. Molybdenite and scheelite are often accompanied by formation of tungsten molybdenum ore, and part of the molybdenite at the shallow surface is easily oxidized and easily forms a similar mineral to scheelite (molybdenum-tungsten-calcium ore). The high-calcium Gao Meigao iron high fluorite, low tungsten and molybdenum refractory tungsten and molybdenum ores have low concentrate grade and recovery rate by adopting a flotation method, and the development and utilization of the tungsten and molybdenum ores are difficult.
Aiming at low-grade and difficultly-treated tungsten-molybdenum ore, a technology of dressing before smelting is basically adopted at present, and a dressing method (CN 201110389747.7) for recovering scheelite/molybdenum oxide ore from molybdenum sulfide flotation tailings is also adopted in the dressing process, and the method comprises the steps of carrying out reselection and/or flotation desliming on the treated ore pulp by taking the molybdenum sulfide ore flotation tailings as raw materials; and adding an adjusting agent, an auxiliary inhibitor, an inhibitor and a modified fatty acid collector into the floating sulfur tailing pulp, carrying out flotation at normal temperature to recover scheelite/molybdenum oxide ore, and carrying out roughing, scavenging and concentration to obtain scheelite/molybdenum oxide concentrate. The grade WO is obtained after fine grinding, desliming, scheelite/molybdenum oxide ore floatation, primary separation, secondary scavenging and secondary concentration 3 7.49% of white tungsten/molybdenum oxide concentrate, mo3.80%, WO 3 +Mo>Recovery rate WO 10 3 65.80% and Mo67.15%. The low-grade refractory tungsten-molybdenum ore is difficult to separate and enrich tungsten-molybdenum ore only by adopting a physical beneficiation technology, so that the ideal tungsten-molybdenum grade and recovery rate cannot be obtained.
In the smelting process, smelting is carried out by a wet method, a combined smelting process (CN 202011630584.2) of molybdenum ore and tungsten ore discloses a combined smelting process of molybdenum concentrate and scheelite, the molybdenum concentrate is subjected to oxygen pressure leaching by a molybdenum ore leaching aid, molybdenum ore filtrate is obtained by filtering, and molybdenum ore raffinate is obtained by extracting the molybdenum ore filtrate; the molybdenum ore raffinate is used as a tungsten ore leaching agent to carry out normal pressure leaching of scheelite, and the molybdenum ore contained in the process is only molybdenum concentrate, and the molybdenum content is 40% -50%; the tungsten-containing mineral is only scheelite, the tungsten trioxide content is 40%, the leaching of the molybdenum concentrate adopts additive oxygen pressure boiling leaching, and finally the scheelite is leached out from the extract of the molybdenum concentrate. The method has relatively high requirements on the content of raw ore, and is difficult to be applied to lower-grade molybdenum concentrate, scheelite, molybdenum-tungsten-calcium ore and mixed ore of the above ores.
Therefore, under the condition that the current molybdenum resources are relatively tense, how to recover tungsten and molybdenum from low-grade tungsten and molybdenum ores difficult to float is particularly critical.
The invention comprises the following steps:
the invention aims to provide a low-grade tungsten-molybdenum ore synergistic oxidation leaching method, which utilizes the fact that molybdenite in the ore is easily oxidized, and molybdenum-tungsten-calcium ore and scheelite have strong reactivity with alkali, and can form WO with good water solubility 4 2- And MoO 4 2- Is characterized by (1). And leaching molybdenite oxidation in combination with molybdenum-tungsten-calcium ore and scheelite by a mixed alkali method.
The invention discloses a low-grade refractory tungsten-molybdenum ore oxidation synergistic mixed alkaline leaching method which comprises the following steps:
(1) Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: -200 meshes (-0.075 mm) is more than or equal to 90 percent, and the raw material fine tungsten-molybdenum ore is obtained.
(2) Placing fine tungsten-molybdenum ore into a reaction kettle, sequentially adding Na 2 CO 3 Solution of NaHCO 3 Solution KMnO 4 An oxidant, controlling the liquid-solid ratio to be 2-8, and controlling the pH value of the solution to be 9-11; stirring at 200-400 rpm for 1-5 hr at 70-90 deg.c.
(3) Directly filtering after stopping the reaction, and using Na with the same concentration as in the step (2) 2 CO 3 And NaHCO of the same concentration 3 Heating the mixed alkali solution to the same temperature as in the step (2), washing filter residues, and then adding Na 2 CO 3 And NaHCO 3 Washing the filter residue with distilled water at the same temperature to obtain leaching residue and leaching liquid.
In the step (1), the tungsten minerals in the tungsten-molybdenum ores are molybdenum-tungsten-calcium ores and scheelite, and the content of the tungsten minerals is 0.05-0.30% and 0.05-0.30% respectively; the molybdenum-containing minerals are molybdenum-tungsten-calcium ore and molybdenite, the content of which is 0.05 to 0.30 percent and 0.05 to 0.30 percent respectively; the grade of molybdenum in the tungsten-molybdenum ore after ore grinding treatment is 0.10-0.50%, the grade of tungsten is 0.05-0.50%, the grade of calcium is 20-30%, the grade of magnesium is 8-12%, the grade of iron is 3-5%, and the grade of fluorine is 3.5-5.5%.
In the step (1), 50-70% of the tungsten-molybdenum ores have a dissociation degree of more than 60%; 70-90% of molybdenite has dissociation degree more than 60%.
In the step (1), 55-75% of molybdenum-tungsten-calcium ore in the tungsten-molybdenum ore is distributed between 10-23 μm, and more than 80% of molybdenite is distributed below 10 μm.
The ore grinding in the step (1) is performed by adopting an oscillation sampling machine, and the sample preparation time is 1-5 min.
In the step (2), na 2 CO 3 The dosage of the tungsten-molybdenum ore and NaHCO is 40-100 kg/t 3 The dosage of the KMnO is 6-15 kg/t tungsten molybdenum ore 4 The dosage of the tungsten-molybdenum ore is 2.5-12.5 kg/t.
In the step (2), na 2 CO 3 The concentration is 40-100 g/L NaHCO 3 The concentration is 6-15 g/L.
In the step (3), the solid-liquid separation mode is that a vacuum filter is adopted for vacuum filtration. The consumption of the mixed alkali solution for washing the filter residue is 50-100 ml, and the consumption of the distilled water for washing the filter residue is 50-100 ml;
in the step (3), the leaching residue after filtering and washing is dried by a vacuum drying oven at the drying temperature of 60-80 ℃ until the weight is constant.
Analyzing the content of molybdenum and tungsten in the fine tungsten-molybdenum ore, the leaching slag and the leaching liquid by ICP-OES, wherein the molybdenum and tungsten in the fine tungsten-molybdenum ore and the leaching slag are respectively expressed by Mo and WO 3 The content of molybdenum and tungsten in the leaching solution is calculated according to the content of Mo and W respectively. The leaching rate is calculated according to the molybdenum and tungsten content in the leaching solution;
compared with the prior art, the low-grade tungsten-molybdenum ore synergistic oxidation leaching method has the beneficial effects that:
the low-grade tungsten-molybdenum ore collaborative oxidation leaching method can treat low-grade tungsten-molybdenum ore which cannot be beneficiated, and solves the problem that the ore cannot be utilized. The method changes the traditional technical route of selecting and then smelting tungsten-molybdenum ores, and leaches unoxidized molybdenite in the ores, synergizes scheelite and molybdenum-tungsten-calcium ore in a mixed alkali system, realizes one-step leaching of tungsten and molybdenum in low-grade tungsten-molybdenum ores, and simplifies the treatment flow; the potassium permanganate with strong oxidation is used as an oxidant of molybdenite, so that the oxidation efficiency is improved, and sodium carbonate and sodium bicarbonate are used as mixed alkali for leaching, so that the leaching rate is improved.
Drawings
Fig. 1 is a schematic flow chart of a low-grade tungsten-molybdenum ore collaborative oxidation leaching method in an embodiment of the invention.
Detailed Description
The ore in the examples of the present invention was crushed-coarsely ground-sieved-finely ground. Fine tungsten molybdenum ore particle size: the content of minus 200 meshes is more than or equal to 90 percent. Molybdenum grade is 0.10-0.50%; the tungsten grade is 0.05 to 0.50 percent.
The tungsten-containing minerals in the tungsten-molybdenum ore are molybdenum-tungsten-calcium ore and scheelite, and the mass content of the tungsten-containing minerals is 0.05 to 0.30 percent and 0.05 to 0.30 percent respectively; the molybdenum-containing minerals are molybdenum-tungsten-calcium ore and molybdenite, and the mass content of the molybdenum-containing minerals is respectively 0.05-0.30% and 0.05-0.30%.
In the embodiment of the invention, normal pressure leaching is adopted, and mechanical stirring is adopted for stirring.
In the embodiment of the invention, the fine tungsten-molybdenum ore adopts solid sample adding, na 2 CO 3 And NaHCO 3 Adding KMnO into reagent liquid prepared into concentration 4 The batch multiple charging is adopted, and the charging is all at room temperature.
The feeding sequence is that Na is firstly added 2 CO 3 Solution, then NaHCO is added 3 Solution and finally adding KMnO in batches 4 A solid.
After the reaction is finished, timely and thermally filtering, washing leaching residues by adopting Na with the same concentration and temperature as the above-mentioned Na 2 CO 3 And NaHCO with the same concentration and the same temperature 3 The mixed leaching solution is washed, and then distilled water with the same temperature is used for washing.
And (3) drying the leached residues after filtering and washing by adopting a vacuum drying oven, wherein the drying temperature is 60-80 ℃, and drying the leached residues until the weight is constant.
And analyzing the contents of molybdenum and tungsten in the leaching solution and leaching residues by adopting ICP-OES, and calculating the leaching rate of tungsten and molybdenum according to the contents of molybdenum and tungsten in the leaching solution.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
The flow is shown in fig. 1; crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: -200 meshes (-0.075 mm) is more than or equal to 90 percent, and the fine tungsten-molybdenum ore is prepared; molybdenum grade 0.10%, tungsten grade 0.42%, calcium grade 28.84%, magnesium grade 11.22%, iron grade 4.51%, fluorine grade 3.65%.
Placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solution (concentration 100 g/L), 20ml NaHCO 3 (concentration: 12 g/L), 0.25g KMnO was slowly added in portions 4 Adding distilled water into the solid, wherein the liquid-solid ratio is 2, 4, 6 and 8 respectively, heating the solid, controlling the reaction temperature to 90 ℃ and the reaction time to 3 hours;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by 50ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing by distillation with 50ml of the same temperature.
And (3) drying the leaching residues after filtering and washing by adopting a vacuum drying oven, wherein the drying temperature is 80 ℃, and drying the leaching residues until the weight is constant.
The contents of molybdenum and tungsten in the leaching solution and the leaching slag are analyzed by ICP-OES, the leaching rate of tungsten and molybdenum is calculated according to the contents of molybdenum and tungsten in the leaching solution, the influence of the liquid-solid ratio on the leaching rate of tungsten and molybdenum in tungsten-molybdenum ore is examined in the embodiment, test data are shown in table 1, the optimal liquid-solid ratio is 6, the leaching rate of Mo is 83.23% at the highest, and the leaching rate of W is 45.87%.
Example 2
Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: -200 meshes (-0.075 mm) is more than or equal to 90 percent, and the fine tungsten-molybdenum ore is prepared; molybdenum grade 0.15%, tungsten grade 0.50%, calcium grade 24.34%, magnesium grade 11.63%, iron grade 4.09%, fluorine grade 3.50%.
Placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solutions (concentration 40g/L, 60g/L, 80g/L, 100g/L, respectively), 20ml NaHCO 3 (concentration: 12 g/L), 0.25g KMnO was slowly added in portions 4 Adding 80ml of distilled water and the solid at the same time, wherein the liquid-solid ratio is 6, heating to raise the temperature, controlling the reaction temperature to 90 ℃ and the reaction time to 3 hours;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by 100ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing by distillation with 50ml of the same temperature.
And (3) drying the leaching residues after filtering and washing by adopting a vacuum drying oven, wherein the drying temperature is 80 ℃, and drying the leaching residues until the weight is constant.
The contents of molybdenum and tungsten in the leaching solution and the leaching residue are analyzed by ICP-OES, and the leaching rate of tungsten and molybdenum is calculated according to the contents of molybdenum and tungsten in the leaching solution, and Na is examined in the embodiment 2 CO 3 Influence of the addition on the leaching rate of tungsten and molybdenum in tungsten-molybdenum ores, test data are shown in Table 1, the best 20ml Na 2 CO 3 (concentration 80 g/L), based on the raw ore, the best Na 2 CO 3 The dosage of the ore is 80 kg/t. At this time, the leaching rate of Mo was 84.5% at the highest, and the leaching rate of W was 47.59%.
Example 3
Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: 200 mesh (-0.075 mm is more than or equal to 90%, and the fine tungsten-molybdenum ore is prepared, wherein the molybdenum grade is 0.22%, the tungsten grade is 0.38%, the calcium grade is 20.36%, the magnesium grade is 8.00%, the iron grade is 4.22%, and the fluorine grade is 4.37%.
Placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solution (concentration 80 g/L), 20ml NaHCO 3 (concentration 6g/L, 9g/L, 12g/L, 15 g/L), 0.25g KMnO was slowly added in portions 4 Adding 80ml of distilled water and the solid at the same time, wherein the liquid-solid ratio is 6, heating to raise the temperature, controlling the reaction temperature to 90 ℃ and the reaction time to 3 hours;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by 75ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing the filter residues by 75ml of distillation with the same temperature.
And (3) drying the leaching residues after filtering and washing by adopting a vacuum drying oven, wherein the drying temperature is 80 ℃, and drying the leaching residues until the weight is constant.
The contents of molybdenum and tungsten in the leaching solution and the leaching residue are analyzed by ICP-OES, and the leaching rate of tungsten and molybdenum is calculated according to the contents of molybdenum and tungsten in the leaching solution, and NaHCO is examined in the embodiment 3 Influence of the addition on the leaching rate of tungsten and molybdenum in tungsten-molybdenum ores, test data are shown in Table 1, best 20ml NaHCO 3 (concentration 9 g/L), based on raw ore, optimal NaHCO 3 The leaching rate of Mo is 85.00% at the highest and the leaching rate of W is 48.59% when the consumption of the ore is 9 kg/t.
Example 4
Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: 200 mesh (-0.075 mm is more than or equal to 90%, and the fine tungsten-molybdenum ore is prepared, wherein the molybdenum grade is 0.30%, the tungsten grade is 0.35%, the calcium grade is 25.86%, the magnesium grade is 12.00%, the iron grade is 3.00%, and the fluorine grade is 4.91%.
Placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solution (concentration 80 g/L), 20ml NaHCO 3 (concentration 9 g/L), 0.05g, 0.1g, 0.15g, 0.2g and 0.25g KMnO were slowly added in portions 4 Adding 80ml of distilled water, and heating to raise the temperature, wherein the liquid-solid ratio is 6, and the reaction temperature is controlled to 90 ℃ and the reaction time is 3 hours;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by 50ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing by 100ml of distillation with the same temperature;
the leached slag after filtering and washing is dried by a vacuum drying oven at the drying temperature of 80 ℃ until the weight is constant;
the contents of molybdenum and tungsten in the leaching solution and the leaching residue are analyzed by ICP-OES, and the leaching rate of tungsten and molybdenum is calculated according to the contents of molybdenum and tungsten in the leaching solution, and KMnO is examined in the embodiment 4 Influence of the solid addition on the leaching rate of tungsten and molybdenum in tungsten-molybdenum ores, test data are shown in Table 1, best KMnO 4 The addition amount of the solid is 0.2g, and the best KMnO is based on the raw ore 4 The consumption of the ore is 10kg/tAt this time, the leaching rate of Mo was 86.22% at the highest, and the leaching rate of W was 49.37%.
Example 5
Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: -200 meshes (-0.075 mm is more than or equal to 90%), and preparing into fine tungsten-molybdenum ore; molybdenum grade 0.43%, tungsten grade 0.05%, calcium grade 27.44%, magnesium grade 8.89%, iron grade 5.0% and fluorine grade 4.50%;
placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solution (concentration 80 g/L), 20ml NaHCO 3 (concentration 9 g/L), 0.2g KMnO was slowly added in portions 4 Adding 80ml of distilled water, heating to raise the temperature, controlling the reaction temperature to 90 ℃, and controlling the reaction time to be 1h, 2h, 3h, 4h and 5h respectively;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by 100ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing by distillation with 50ml of the same temperature;
the leached slag after filtering and washing is dried by a vacuum drying oven at the drying temperature of 80 ℃ until the weight is constant;
the contents of molybdenum and tungsten in the leaching solution and the leaching slag are analyzed by ICP-OES, the leaching rates of tungsten and molybdenum are calculated according to the contents of molybdenum and tungsten in the leaching solution, the influence of the reaction time on the leaching rates of tungsten and molybdenum in tungsten-molybdenum ores is examined in the embodiment, test data are shown in table 1, the optimal reaction time is 4 hours, the leaching rate of Mo is 87.11% at the highest, and the leaching rate of W is 50.05%.
Example 6
Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: 200 meshes (-0.075 mm is more than or equal to 90 percent) to prepare fine tungsten-molybdenum ore, wherein the molybdenum grade is 0.50 percent, the tungsten grade is 0.35 percent, the calcium grade is 21.52 percent, the magnesium grade is 9.93 percent, the iron grade is 4.2 percent, and the fluorine grade is 5.5 percent;
placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solution (concentration 80 g/L), 20ml NaHCO 3 (concentration 9 g/L), 0.2g KMnO was slowly added in portions 4 Solid, at the same time supplementAdding 80ml distilled water, wherein the liquid-solid ratio is 6, heating to raise the temperature, controlling the reaction temperature to be 70 ℃, 75 ℃,80 ℃, 85 ℃ and 90 ℃ respectively, and controlling the reaction time to be 4 hours;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by using 100ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing by distillation with 100ml of the same temperature;
the leached slag after filtering and washing is dried by a vacuum drying oven at the drying temperature of 80 ℃ until the weight is constant;
the contents of molybdenum and tungsten in the leaching solution and the leaching slag are analyzed by ICP-OES, the leaching rates of tungsten and molybdenum are calculated according to the contents of molybdenum and tungsten in the leaching solution, the influence of the reaction temperature on the leaching rates of tungsten and molybdenum in tungsten-molybdenum ores is examined in the embodiment, test data are shown in table 1, the optimal reaction temperature is 85 ℃, the leaching rate of Mo is 87.15% at the maximum, and the leaching rate of W is 51.59%.
Example 7
Crushing, coarse grinding, screening and fine grinding tungsten-molybdenum ore to reach the granularity: -200 meshes (-0.075 mm accounts for more than or equal to 90 percent) to prepare fine tungsten-molybdenum ore, wherein the molybdenum grade is 0.30 percent, the tungsten grade is 0.35 percent, the calcium grade is 26 percent, the magnesium grade is 9 percent, the iron grade is 4.4 percent, and the fluorine grade is 5.2 percent;
placing 20g of fine tungsten-molybdenum ore into a reaction kettle, starting stirring, adjusting the stirring speed to 250rpm, and sequentially adding 20ml of Na 2 CO 3 Solution (concentration 80 g/L), 20ml NaHCO 3 (concentration 9 g/L), 0.2g KMnO was slowly added in portions 4 Adding 80ml of distilled water, heating to raise the temperature, controlling the reaction temperature to 85 ℃ and controlling the reaction time to 4 hours, wherein the liquid-solid ratio is 6;
after stopping the reaction, filtering in vacuum while the reaction is hot, washing filter residues by using 100ml of mixed alkali solution with the same concentration and the same temperature as the reaction system, and then washing by distillation with 100ml of the same temperature;
the leached slag after filtering and washing is dried by a vacuum drying oven at the drying temperature of 80 ℃ until the weight is constant;
the contents of molybdenum and tungsten in the leaching solution and leaching residues are analyzed by ICP-OES, and the leaching rates of tungsten and molybdenum are calculated according to the contents of molybdenum and tungsten in the leaching solution, and the leaching rates of tungsten and molybdenum under the optimal condition of influencing factors are examined in the embodiment, wherein the leaching rate of Mo is 87.79% at most and the leaching rate of W is 51.87% under the optimal reaction condition.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and enhancements can be made by those skilled in the art without departing from the principles of the present invention and are also contemplated as falling within the scope of the present invention.
TABLE 1
Claims (10)
1. The collaborative oxidation leaching method for the low-grade tungsten-molybdenum ore is characterized by comprising the following steps of:
(1) Crushing, coarse grinding, screening and fine grinding the tungsten-molybdenum ore to the granularity of-200 meshes (-0.075 mm) of more than or equal to 90 percent to obtain raw material fine tungsten-molybdenum ore;
(2) Placing the fine tungsten-molybdenum ore into a reaction kettle, and sequentially adding Na 2 CO 3 Solution of NaHCO 3 Solution KMnO 4 An oxidizing agent, heating and stirring;
(3) Directly filtering after stopping the reaction, firstly using Na with the same concentration and the same temperature as the reaction system in the step (2) 2 CO 3 And NaHCO 3 Washing the filter residue by mixing the alkali solution, and washing the filter residue by distilled water with the same temperature as the reaction system in the step (2) to obtain leaching residue and leaching liquid.
2. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein the low-grade tungsten-molybdenum ore belongs to high-calcium Gao Meigao iron high fluorite and low-tungsten-molybdenum refractory tungsten-molybdenum ore, wherein the partial oxidation of molybdenite in the ore and scheelite form a similar mineral (molybdenum-tungsten-calcium ore), and the fluorite grade is 8% -12%; the nonmetallic minerals are mainly pyroxene, olivine, dolomite and calcite; the tungsten-containing minerals in the tungsten-molybdenum ore are molybdenum-tungsten-calcium ore and scheelite, and the mass content of the tungsten-molybdenum ore is 0.05-0.30% and 0.05-0.30% respectively; the molybdenum-containing minerals are molybdenum-tungsten-calcium ore and molybdenite, and the mass content of the molybdenum-containing minerals is respectively 0.05-0.30% and 0.05-0.30%.
3. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein in the step (1), the grade of molybdenum in the tungsten-molybdenum ore after ore grinding treatment is 0.10-0.50%, the grade of tungsten is 0.05-0.50%, the grade of calcium is 20-30%, the grade of magnesium is 8-12%, the grade of iron is 3-5%, and the grade of fluorine is 3.5-5.5%.
4. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein in the step (1), 50-70% of molybdenum-tungsten-calcium ore in the tungsten-molybdenum ore has dissociation degree of more than 60%; 70-90% of molybdenite has dissociation degree more than 60%.
5. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein in the step (1), 55-75% of molybdenum-tungsten-calcium ore in the tungsten-molybdenum ore is distributed between 10-23 μm, and more than 80% of molybdenite is distributed below 10 μm.
6. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein ore grinding in the step (1) is fine grinding by adopting an oscillation sampling machine, and the sampling time is 1-5 min.
7. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein the stirring in the step (2) is specifically that the stirring speed is 200-400 rpm, the reaction time is 1-5 h, and the reaction temperature is 70-90 ℃; the Na is 2 CO 3 The dosage of the tungsten-molybdenum ore and NaHCO is 40-100 kg/t 3 The dosage of the KMnO is 6-15 kg/t tungsten molybdenum ore 4 The dosage of the tungsten-molybdenum ore is 2.5-12.5 kg/t.
8. The method for collaborative oxidative leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein the steps of(2) In Na (Na) 2 CO 3 The concentration is 40-100 g/L NaHCO 3 The concentration is 6-15 g/L; controlling the liquid-solid ratio to be 2-8 and controlling the pH value to be 9-11.
9. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein the filtering in the step (3) is specifically filtering by a vacuum filter; the consumption of the mixed alkali solution for washing the filter residue is 50-100 ml, and the consumption of the distilled water for washing the filter residue is 50-100 ml; and (3) drying the leached residues after filtering and washing by adopting a vacuum drying oven, wherein the drying temperature is 60-80 ℃, and drying the leached residues to constant weight.
10. The method for collaborative oxidation leaching of low-grade tungsten-molybdenum ore according to claim 1, wherein the content of molybdenum and tungsten in the fine tungsten-molybdenum ore, the leaching residue and the leaching liquid is analyzed by ICP-OES, and the content of molybdenum and tungsten in the fine tungsten-molybdenum ore and the leaching residue are expressed as Mo and WO respectively 3 And calculating leaching rate according to the content of molybdenum and tungsten in the leaching solution and the content of molybdenum and tungsten in the leaching solution by the content of Mo and W in the leaching solution.
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