CN113684378A - Method for improving leaching rate of tungsten and molybdenum in scheelite containing molybdenum sulfide - Google Patents
Method for improving leaching rate of tungsten and molybdenum in scheelite containing molybdenum sulfide Download PDFInfo
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- CN113684378A CN113684378A CN202110904741.2A CN202110904741A CN113684378A CN 113684378 A CN113684378 A CN 113684378A CN 202110904741 A CN202110904741 A CN 202110904741A CN 113684378 A CN113684378 A CN 113684378A
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- leaching
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- 238000002386 leaching Methods 0.000 title claims abstract description 186
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 39
- 239000010937 tungsten Substances 0.000 title claims abstract description 39
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011733 molybdenum Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 70
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 7
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000002893 slag Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000011575 calcium Substances 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000167834 Koelreuteria Species 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 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
- C22B34/36—Obtaining tungsten
-
- 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
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
-
- 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
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- 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
-
- 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
Abstract
The invention relates to the field of rare metal smelting, in particular to a method for improving the leaching rate of tungsten and molybdenum in scheelite containing molybdenum sulfide, which comprises the steps of acid leaching, ammonia leaching, roasting, sodium hydroxide leaching and the like. The method comprises the steps of firstly, leaching molybdenum sulfide-containing scheelite with acid to obtain tungstic acid containing molybdenum sulfide, and then leaching WO in the tungstic acid with ammonia water3、MoO3Roasting the ammonia water leached residues to convert molybdenum sulfide in the ammonia water leached residues into MoO3Finally, leaching the roasted ammonia water leaching residue by using sodium hydroxide, and leaching WO in the ammonia water leaching residue3、MoO3Leaching to achieve the purpose of improving the leaching rate of tungsten and molybdenum in the scheelite containing molybdenum sulfide.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of rare metal smelting, in particular to a method for improving the leaching rate of tungsten and molybdenum in scheelite containing molybdenum sulfide.
[ background of the invention ]
Due to the influence of lanthanide contraction, the atomic radii of tungsten and molybdenum elements are very close, so that the tungsten and molybdenum elements have very similar physicochemical properties, are usually symbiotic or associated in the same mineral, and are very difficult to extract and separate. The scheelite containing molybdenum sulfide is an important tungsten-molybdenum mineral resource, the production places are mainly concentrated in regions of Henan, Shaanxi, Shanxi, Liaoning and the like, and particularly, the scheelite in the great east of the Henan Koelreuteria county is taken as a typical representative. The ore contains WO3Generally 15-35%, Mo content generally 1.5-6%, S content generally 3-10%, and complex properties and high utility value.
Researchers developed many typical processes for the utilization of scheelite containing molybdenum sulfide. Wherein the processes for realizing industrial popularization comprise a roasting-sodium carbonate high-pressure leaching process and an acid leaching-sodium hydroxide leaching process. The roasting-sodium carbonate high-pressure leaching process is used for treating the scheelite containing molybdenum sulfide, and the higher leaching rate of tungsten (in leaching slag, usually WO)3The content is controlled to be about 0.5 percent, WO3The leaching rate can reach 97 percent), but the leaching rate of molybdenum is low (in the leaching slag, the content of Mo is usually controlled to be about 0.4 percent, the leaching rate of Mo is 75 to 85 percent), the roasting amount is large, the energy consumption is high, the subsequent purification and separation processes are complex, and the cost is relatively high. Treatment of scheelite containing molybdenum sulphide by acid leaching-sodium hydroxide leaching process, WO3The leaching rate is higher, usually more than 98%, but part of Mo existing in the form of molybdenum sulfide cannot be leached, so that the leaching rate of Mo is low, and the utilization rate of valuable metals is low. Therefore, it is necessary to develop a new technology for improving the leaching rate of tungsten and molybdenum in the scheelite containing molybdenum sulfide.
Aiming at the problem of low leaching rate of tungsten and molybdenum in the scheelite containing molybdenum sulfide, the invention develops deep researchThe method comprises the steps of leaching the scheelite containing molybdenum sulfide by combining hydrochloric acid and saltpeter, leaching calcium in the form of calcium chloride, transferring molybdenum sulfide and tungsten into acid leaching residues, transferring most of tungsten into ammonia water leachate by ammonia water leaching, separating tungsten from molybdenum, and converting molybdenum sulfide into easily leachable MoO by utilizing a roasting link3And finally, leaching by using sodium hydroxide to realize the purpose of efficiently leaching tungsten and molybdenum in the scheelite containing molybdenum sulfide.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a method for improving the leaching rate of tungsten and molybdenum in scheelite containing molybdenum sulfide, which can efficiently leach tungsten and molybdenum in scheelite containing molybdenum sulfide and realize low-cost and high-efficiency gradient utilization.
The invention discloses a method for improving leaching rates of tungsten and molybdenum in scheelite containing molybdenum sulfide, which comprises the following steps:
(1) acid leaching: firstly, carrying out acid leaching on scheelite containing molybdenum sulfide, wherein the process is controlled to be that the concentration of hydrochloric acid is 10mol/L, the dosage of saltpeter is 1-3 per mill, the liquid-solid ratio is 3:1-4:1, the temperature is 90-100 ℃, the leaching time is 60-80 min, the leaching stirring speed is 60-90 r/min, the leaching is finished, filtering and hot water washing are carried out, the filtrate and washing water are collected and treated, and the filter residue enters the next treatment link;
(2) ammonia leaching: leaching tungstic acid containing molybdenum sulfide obtained in the step (1) by using ammonia water, wherein the concentration of the ammonia water is controlled to be 60-80g/L, the liquid-solid ratio is 3:1-4:1, the leaching pressure is 0.3-0.5Mpa, the leaching time is 90-120 min, the leaching stirring speed is 60-90 r/min, the leaching is finished, filtering is carried out, the filtrate enters a main tungsten smelting process, the filter residue is ammonia water leaching residue containing molybdenum sulfide, and the next treatment link is carried out;
(3) roasting: roasting the leaching residue of the ammonia water containing molybdenum sulfide obtained in the step (2), wherein the roasting temperature is controlled to be 300-500 ℃, the roasting time is controlled to be 60-120 min, roasting gas is circularly leached by liquid alkali, the leaching is also kept with the pH always larger than 13, roasting is finished, and the roasted product enters the next treatment link;
(4) leaching with sodium hydroxide: and (4) performing sodium hydroxide leaching on the obtained calcine containing tungsten and molybdenum through the step (3), wherein the leaching condition is controlled to be that the using amount of sodium hydroxide is 1.5-2.5 times of the theoretical using amount, and the solid-to-solid ratio of leaching liquid is 1: 1-1:1.5, the leaching pressure is 0.25-0.5 Mpa, the leaching time is 90-120 min, the leaching stirring speed is 60-90 r/min, the leaching is completed, the filtration and washing are carried out, the leaching residue is collected and treated, and the leaching solution is sent to a tungsten-molybdenum separation link.
Compared with the prior art, the invention has the following advantages:
converting calcium in the scheelite containing molybdenum sulfide into soluble calcium chloride for separation through acid leaching, wherein molybdenum enters acid leaching slag in the form of molybdenum sulfide and tungsten enters acid leaching slag in the form of tungstic acid, and most of the acid leaching slag is leached by ammonia water3Tungsten in the form and in minute amounts as MoO3Leaching molybdenum in the form of molybdenum, adding the molybdenum into ammonia water leaching solution, adding most of molybdenum sulfide and a very small amount of tungsten into ammonia water leaching residues, and converting the molybdenum sulfide in the ammonia water leaching residues into easily leached MoO by roasting3Finally, the sodium hydroxide is used for leaching to leach a large amount of molybdenum and a small amount of tungsten in the calcine, and the method is a method for leaching tungsten and molybdenum in the scheelite containing molybdenum sulfide with high efficiency and low cost.
[ description of the drawings ]
The following detailed description of embodiments of the invention is provided in conjunction with the appended drawings, in which:
FIG. 1 is a process flow diagram of the present invention;
[ detailed description ] embodiments
The first embodiment is as follows:
in this embodiment, the scheelite containing molybdenum sulfide is obtained from a certain tungsten concentrating mill in the south of the river by sampling, drying, sample preparation, and detection, and the detection result of the scheelite containing molybdenum sulfide is as follows: mo 2.53%, WO332.50％,Ca22.51％。
(1) Acid leaching: firstly, 600g of scheelite (dry basis) is weighed and placed in a 3000ml glass beaker for acid leaching, the process is controlled to be that the concentration of hydrochloric acid is 10mol/L, the dosage of saltpeter is 3 per mill, the liquid-solid ratio is 3:1, the temperature is 95 ℃, the leaching time is 60min, the leaching is stirredStirring at 60r/min, filtering, washing with hot water, collecting filtrate and washing water, weighing filter residue 330.72g, and measuring WO3、Mo、H20, 86.50%, 6.55% and 33.2%, respectively, and then enters the next processing step.
(2) Ammonia leaching: placing tungstic acid containing molybdenum sulfide obtained in the step (1) into a high-pressure kettle, leaching with ammonia water, controlling the ammonia water concentration to be 80g/L, the liquid-solid ratio to be 4:1, the leaching pressure to be 0.5Mpa, the leaching time to be 120min, the leaching stirring speed to be 90r/min, completing leaching, filtering, enabling the filtrate to enter a tungsten smelting main flow, weighing 50.74g of filter residues, and measuring WO (tungsten oxide)3、Mo、H20 is respectively 2.1%, 42.18% and 32.40%, and the next processing step is started.
(3) Roasting: and (3) roasting the leaching residue of the ammonia water containing molybdenum sulfide obtained in the step (2), wherein the roasting temperature is controlled to be 300 ℃, the roasting time is controlled to be 60min, and the roasted product enters the next treatment link under the condition of rich air.
(4) Leaching with sodium hydroxide: performing sodium hydroxide leaching on the obtained calcine containing tungsten and molybdenum through the step (3), controlling the leaching condition to be that the using amount of sodium hydroxide is 1.5 times of the theoretical using amount, the solid-to-solid ratio of leaching liquid is 1:1.5, the leaching pressure is 0.3Mpa, the leaching time is 120min, the leaching stirring speed is 60r/min, completing the leaching, filtering and washing, sending the leaching liquid into a tungsten-molybdenum separation link, drying leaching residues, weighing 7.21g, and measuring WO3Mo content of 1.1% and 0.48%, respectively, and calculating WO3The leaching rate of Mo is 99.95 percent and 99.77 percent.
Example two:
in this embodiment, the scheelite containing molybdenum sulfide is obtained from a certain tungsten concentrating mill in the south of the river by sampling, drying, sample preparation, and detection, and the detection result of the scheelite containing molybdenum sulfide is as follows: mo 2.53%, WO332.50％,Ca22.51％。
(1) Acid leaching: firstly, 600g of scheelite (dry basis) is weighed and placed in a 3000ml glass beaker for acid leaching, the process is controlled to be that the concentration of hydrochloric acid is 10mol/L, the dosage of the saltpeter is 1 per mill, the liquid-solid ratio is 3:1, the temperature is 95 ℃, the leaching time is 60min, the leaching stirring speed is 60r/min, the leaching is finished, the filtration is carried out,Washing with hot water, collecting filtrate and washing water, weighing filter residue 351g, and measuring WO3、Mo、H20, 85.13%, 5.71%, 36.30% respectively, and then proceed to the next processing stage.
(2) Ammonia leaching: placing tungstic acid containing molybdenum sulfide obtained in the step (1) in a high-pressure kettle, leaching with ammonia water, controlling the ammonia water concentration to be 80g/L, the liquid-solid ratio to be 4:1, the leaching pressure to be 0.5Mpa, the leaching time to be 120min, the leaching stirring speed to be 90r/min, completing leaching, filtering, enabling the filtrate to enter a tungsten smelting main flow, weighing 59.45g of filter residue, and measuring WO 783、Mo、H20 is 3.42 percent, 38.20 percent and 31.30 percent respectively, and the next treatment link is entered.
(3) Roasting: and (3) roasting the leaching residue of the ammonia water containing molybdenum sulfide obtained in the step (2), wherein the roasting temperature is controlled to be 350 ℃, the roasting time is controlled to be 60min, and the roasted product enters the next treatment link under the condition of rich air.
(4) Leaching with sodium hydroxide: performing sodium hydroxide leaching on the obtained calcine containing tungsten and molybdenum through the step (3), controlling the leaching condition to be that the using amount of sodium hydroxide is 1.5 times of the theoretical using amount, the solid-to-solid ratio of leaching solution is 1:1, the leaching pressure is 0.3Mpa, the leaching time is 120min, the leaching stirring speed is 60r/min, completing leaching, filtering and washing, sending the leaching solution into a tungsten-molybdenum separation link, drying leaching residues, weighing 9.68g, and measuring WO3Mo content of 0.87% and 0.52%, respectively, and WO was calculated3The leaching rate of Mo is 99.96 percent and 99.66 percent.
Example three:
in this embodiment, the scheelite containing molybdenum sulfide is obtained from a certain tungsten concentrating mill in the south of the river by sampling, drying, sample preparation, and detection, and the detection result of the scheelite containing molybdenum sulfide is as follows: mo 4.42%, WO322.21％,Ca25.63％。
(1) Acid leaching: firstly, 600g of scheelite (dry basis) is weighed and placed in a 3000ml glass beaker for acid leaching, the process is controlled to have the concentration of hydrochloric acid of 10mol/L, the dosage of the saltpeter is 2 per mill, the liquid-solid ratio is 4:1, the temperature is 95 ℃, the leaching time is 60min, the leaching stirring speed is 60r/min, the leaching is finished, the filtration and the hot water washing are carried out, the filtrate and the washing water are collected and treated,the residue weighed 318.10g, and was measured for WO3、Mo、H20, 73.5%, 21.11%, 38.25% respectively, and then enter the next processing stage.
(2) Ammonia leaching: placing tungstic acid containing molybdenum sulfide obtained in the step (1) into a high-pressure kettle, leaching with ammonia water, controlling the ammonia water concentration to be 80g/L, the liquid-solid ratio to be 4:1, the leaching pressure to be 0.5Mpa, the leaching time to be 120min, the leaching stirring speed to be 90r/min, completing leaching, filtering, enabling the filtrate to enter a tungsten smelting main flow, weighing 78.30g of filter residue, and measuring WO (tungsten oxide)3、Mo、H20 is 5.11%, 38.20% and 28.60% respectively, and the next processing link is entered.
(3) Roasting: and (3) roasting the leaching residue of the ammonia water containing molybdenum sulfide obtained in the step (2), wherein the roasting temperature is controlled to be 300 ℃, the roasting time is controlled to be 60min, and the roasted product enters the next treatment link under the condition of rich air.
(4) Leaching with sodium hydroxide: performing sodium hydroxide leaching on the obtained calcine containing tungsten and molybdenum through the step (3), controlling the leaching condition to be that the using amount of sodium hydroxide is 1.5 times of the theoretical using amount, the solid-to-solid ratio of leaching solution is 1:1, the leaching pressure is 0.4Mpa, the leaching time is 120min, the leaching stirring speed is 60r/min, completing leaching, filtering and washing, sending the leaching solution into a tungsten-molybdenum separation link, drying leaching residues, weighing 18.2g, and measuring WO3The Mo content is 1.2 and 0.50 percent respectively, and the WO content is calculated3The leaching rates of Mo and Mo are 99.84% and 99.65%.
Example four:
in this embodiment, the scheelite containing molybdenum sulfide is obtained from a certain tungsten concentrating mill in the south of the river by sampling, drying, sample preparation, and detection, and the detection result of the scheelite containing molybdenum sulfide is as follows: mo 4.42%, WO322.21％,Ca25.63％。
(1) Acid decomposition: firstly weighing 600g of scheelite (dry basis), placing the scheelite in a 3000ml glass beaker for acid leaching, controlling the concentration of hydrochloric acid to be 10mol/L, the dosage of saltpeter to be 1 per mill, the liquid-solid ratio to be 3:1, the temperature to be 95 ℃, the leaching time to be 60min, the leaching stirring speed to be 90r/min, completing leaching, filtering, washing with hot water, collecting and processing filtrate and washing water, weighing 328.22g of filter residues, and measuring WO3、Mo、H20 is 71.30%, 19.88% and 37.45%, respectively, and then enters the next processing step.
(2) Ammonia leaching: placing tungstic acid containing molybdenum sulfide obtained in the step (1) into a high-pressure kettle, leaching with ammonia water, controlling the ammonia water concentration to be 70g/L, the liquid-solid ratio to be 3:1, the leaching pressure to be 0.3Mpa, the leaching time to be 120min, the leaching stirring speed to be 90r/min, completing leaching, filtering, enabling the filtrate to enter a tungsten smelting main flow, weighing 89.41g of filter residue, and measuring WO (tungsten oxide)3、Mo、H20 is 8.18 percent, 35.22 percent and 30.63 percent respectively, and the next treatment link is entered.
(3) Roasting: and (3) roasting the leaching residue of the ammonia water containing molybdenum sulfide obtained in the step (2), wherein the roasting temperature is controlled to be 300 ℃, the roasting time is controlled to be 60min, and the roasted product enters the next treatment link under the condition of rich air.
(4) Leaching with sodium hydroxide: performing sodium hydroxide leaching on the obtained calcine containing tungsten and molybdenum through the step (3), controlling the leaching condition to be that the using amount of sodium hydroxide is 1.0 time of the theoretical using amount, the solid-to-solid ratio of leaching solution is 1:1, the leaching pressure is 0.3Mpa, the leaching time is 120min, the leaching stirring speed is 60r/min, completing leaching, filtering and washing, sending the leaching solution into a tungsten-molybdenum separation link, drying leaching residues, weighing 25.30g, and measuring WO3The Mo content is 1.3 and 0.66 percent respectively, and the WO content is calculated3The leaching rate of Mo is 99.75 percent and 99.37 percent.
The above description is only a preferred embodiment of the present invention, and it should be noted that a person skilled in the art can make various changes, modifications, substitutions and alterations to the embodiments without departing from the technical principles of the present invention, and such changes, modifications, substitutions and alterations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for improving the leaching rate of tungsten and molybdenum in scheelite containing molybdenum sulfide is characterized in that: comprises the following steps:
(1) acid leaching: firstly, carrying out acid leaching on scheelite containing molybdenum sulfide, wherein the process is controlled to be that the concentration of hydrochloric acid is 10mol/L, the dosage of saltpeter is 1-3 per mill, the liquid-solid ratio is 3:1-4:1, the temperature is 90-100 ℃, the leaching time is 60-80 min, the leaching stirring speed is 60-90 r/min, the leaching is finished, filtering and hot water washing are carried out, the filtrate and washing water are collected and treated, and the filter residue enters the next treatment link;
(2) ammonia leaching: leaching tungstic acid containing molybdenum sulfide obtained in the step (1) by using ammonia water, wherein the concentration of the ammonia water is controlled to be 60-80g/L, the liquid-solid ratio is 3:1-4:1, the leaching pressure is 0.3-0.5Mpa, the leaching time is 90-120 min, the leaching stirring speed is 60-90 r/min, the leaching is finished, filtering is carried out, the filtrate enters a main tungsten smelting process, the filter residue is ammonia water leaching residue containing molybdenum sulfide, and the next treatment link is carried out;
(3) roasting: roasting the leaching residue of the ammonia water containing molybdenum sulfide obtained in the step (2), wherein the roasting temperature is controlled to be 300-500 ℃, the roasting time is controlled to be 60-120 min, roasting gas is circularly leached by liquid alkali, the leaching is also kept with the pH always larger than 13, roasting is finished, and the roasted product enters the next treatment link;
(4) leaching with sodium hydroxide: and (4) performing sodium hydroxide leaching on the obtained calcine containing tungsten and molybdenum through the step (3), wherein the leaching condition is controlled to be that the using amount of sodium hydroxide is 1.5-2.5 times of the theoretical using amount, and the solid-to-solid ratio of leaching liquid is 1: 1-1:1.5, the leaching pressure is 0.25-0.5 Mpa, the leaching time is 90-120 min, the leaching stirring speed is 60-90 r/min, the leaching is completed, the filtration and washing are carried out, the leaching residue is collected and treated, and the leaching solution is sent to a tungsten-molybdenum separation link.
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| CN114956181A (en) * | 2022-05-19 | 2022-08-30 | 崇义章源钨业股份有限公司 | Method for removing potassium in scheelite by roasting waste acid liquor |
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