CN107081220B - Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate - Google Patents
Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate Download PDFInfo
- Publication number
- CN107081220B CN107081220B CN201710325108.1A CN201710325108A CN107081220B CN 107081220 B CN107081220 B CN 107081220B CN 201710325108 A CN201710325108 A CN 201710325108A CN 107081220 B CN107081220 B CN 107081220B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- collector
- molybdenum oxide
- scheelite
- flotation
- 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.)
- Active
Links
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 62
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000005188 flotation Methods 0.000 title claims abstract description 56
- 239000012141 concentrate Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229940124639 Selective inhibitor Drugs 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 14
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 11
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 6
- 239000002274 desiccant Substances 0.000 claims abstract description 5
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 239000011733 molybdenum Substances 0.000 claims description 23
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 17
- 239000011707 mineral Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000344 soap Substances 0.000 claims description 12
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021532 Calcite Inorganic materials 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 4
- 239000004368 Modified starch Substances 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000010436 fluorite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 235000019426 modified starch Nutrition 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- -1 alkyl sulfonic acid Chemical compound 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000010428 baryte Substances 0.000 claims description 2
- 229910052601 baryte Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001648 tannin Substances 0.000 claims description 2
- 235000018553 tannin Nutrition 0.000 claims description 2
- 229920001864 tannin Polymers 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 12
- 229910052961 molybdenite Inorganic materials 0.000 description 10
- 239000003814 drug Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QKEIPIQRYZIKEQ-UHFFFAOYSA-N [Ca].[W].[Mo] Chemical compound [Ca].[W].[Mo] QKEIPIQRYZIKEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 229910001576 calcium mineral Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AWOORJZBKBDNCP-UHFFFAOYSA-N molybdenum;oxotungsten Chemical compound [Mo].[W]=O AWOORJZBKBDNCP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Lubricants (AREA)
Abstract
The invention provides a method for improving the enrichment effect of molybdenum oxide in scheelite flotation concentrate, which takes molybdenum sulfide flotation tailing slurry as a raw material to float scheelite to obtain the scheelite flotation concentrate enriched with molybdenum oxide, and comprises the following steps: step one, adding a molybdenum oxide modifier, a regulator, a selective inhibitor, a collector and a collector powerful agent into molybdenum sulfide flotation tailing pulp in sequence, and carrying out normal-temperature flotation to obtain tungsten-molybdenum mixed rough concentrate pulp; step two, concentrating the product of the step one; adding a pH regulator, a desiccants, a selective inhibitor, a collector and a collector powerful agent into the product obtained in the step two; step four, diluting the product obtained in the step three, and then performing flotation to obtain scheelite flotation concentrate enriched with molybdenum oxide; according to the invention, the molybdenum oxide modifier is added in the tailing slurry in a targeted manner to modify the surface properties of molybdenum oxide, particularly molybdenum dioxide, molybdenum trioxide and calcium molybdate resources, so that the content of molybdenum oxide in the recycled scheelite is greatly increased.
Description
Technical Field
The invention belongs to the technical field of mineral processing, relates to improvement of molybdenum oxide enrichment effect in scheelite flotation concentrate, and particularly relates to a method for improving the recovery rate of molybdenum oxide in scheelite flotation concentrate when scheelite is recovered from molybdenum sulfide flotation tailings.
Background
Molybdenum is an important rare metal and strategic reserve resource, and plays an extremely important role in the whole national economy and human health. With the continuous expansion of molybdenum resource exploitation and utilization scale, the simple and easy-to-select molybdenum ores are increasingly reduced, the selection proportion of poor, fine and high-oxidation-rate molybdenum ores is gradually increased, and for molybdenum ore dressing, a grinding and floating process using hydrocarbon oil (kerosene and diesel oil) as a collecting agent is generally adopted to recover molybdenite in the ores. The hydrocarbon oil collecting agent can only be applied to the surfaces of molybdenite particles with good natural floatability through physical adsorption, so that the floatability of the molybdenite is improved, the efficient recovery of the molybdenite is realized, and molybdenum oxide in the ore has no collecting capacity, so that the molybdenum oxide resource in the ore is lost along with tailing resources.
The recovery of molybdenum oxide belongs to a worldwide problem, the difficult selection reason is mainly that ① molybdenum oxide is subjected to certain damage to mineral lattices in the surface oxidation ore-forming process, the molybdenum oxide is easy to argillization during ore grinding, and the recovery effect is influenced, ② ore is usually associated with oxysalts of various cations with the same name, the floatability of the oxysalts is similar, and the oxysalts are difficult to separate from gangue minerals with the same name in the molybdenum oxide flotation process, so that the molybdenum oxide concentrate product has low grade, for example, the molybdenite is difficult to separate from scheelite, calcite, fluorite, apatite and the like associated in the ore.
For the tungsten-molybdenum deposit, the mineral processing process flow adopts a preferential flotation flow of firstly selecting molybdenite and floating molybdenum tailings and then selecting scheelite: in the flotation process of the scheelite, a fatty acid collecting agent is usually adopted to obtain rough concentrate containing the scheelite and other calcium minerals, and then a Peterov method is adopted to carry out concentration on the rough concentrate to obtain the scheelite concentrate. Because the fatty acid collecting agent belongs to an oxidized ore collecting agent and has a certain collecting capacity on molybdenum oxide, a small amount of molybdenum oxide is contained in the white tungsten concentrate, but because the molybdenum oxide is not recovered in a targeted manner, a large amount of molybdenum oxide resources are not reasonably recycled in tailings, and the loss and waste of the molybdenum resources are caused.
At present, researches on recovery of scheelite resources and molybdenum oxide resources from molybdenite flotation tailings of tungsten-molybdenum ore deposits have been advanced, industrial production of scheelite resources from molybdenite flotation tailings by Henan Luo-Mo group has been realized, and WO in molybdenum flotation tailings3Under the conditions that the grade is 0.07-0.1% and the molybdenum grade is about 0.025%, oleic acid soap is used as a collecting agent, and WO is obtained through one-time rough separation3Heating and concentrating the rough tungsten-molybdenum concentrate with the grade of about 1.6 percent and the molybdenum grade of about 0.16 percent to produce WO3The recovery rate of about 65 percent of tungsten-molybdenum concentrate with 25 to 30 percent of content and about 30 percent of molybdenum content with 2 percent of recovery rate,the process mainly recovers the scheelite resource and the molybdenum oxide resource in the tungsten-molybdenum bulk concentrate, and does not recover in a targeted manner, so that the recovery rate of molybdenum is very low. Zhengzhou mineral comprehensive utilization research institute of Chinese geological academy of sciences and Changsha mining and metallurgy research institute of finite liability company disclose a molybdenum-tungsten oxide ore dressing process (CN101224441) and a dressing method (CN102489407A) for recovering scheelite/molybdenum oxide ore from molybdenum sulfide flotation tailings, respectively, and the same points are that: alkali size mixing, water glass as an inhibitor and fatty acid soap (emulsification or modification) as a collector of scheelite and molybdenum oxide, wherein the difference is in a normal-temperature flotation method adopted by CN102489407A and a heating flotation method adopted by CN 101224441. However, in the two processes, only calcium tungstate ore (i.e. scheelite) and calcium molybdenum (tungsten) ore in molybdenum oxide can be recovered by using fatty acid soap as a collector, the recovery effect on molybdenum bloom and tungsten bloom is very poor, so that the molybdenum oxide and tungsten oxide resources are lost, and meanwhile, WO in tungsten-molybdenum mixed concentrate obtained by the two processes3And the molybdenum content is relatively low, and if the molybdenum is directly treated in the process (APT) for producing ammonium paratungstate from low-grade scheelite middling, the production cost is high, and the molybdenum can be used only by further treatment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for improving the enrichment effect of molybdenum oxide in scheelite flotation concentrate, and solve the technical problems of difficult recovery and serious loss of molybdenum oxide at present.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for improving the enrichment effect of molybdenum oxide in tungsten flotation concentrate is provided, the method takes molybdenum sulfide flotation tailing slurry as a raw material to float scheelite, and the scheelite is obtained by flotation, thus obtaining the scheelite flotation concentrate enriched with molybdenum oxide;
the method comprises the following steps:
step one, adding a molybdenum oxide modifier, a regulator, a selective inhibitor, a collector and a collector powerful agent into molybdenum sulfide flotation tailing pulp in sequence, and carrying out normal-temperature flotation to obtain tungsten-molybdenum mixed rough concentrate pulp;
step two, concentrating the product of the step one;
adding a pH regulator, a desiccants, a selective inhibitor, an oleic acid soap and a collector powerful agent into the product obtained in the step two;
step four, diluting the product obtained in the step three, and then performing flotation to obtain scheelite flotation concentrate enriched with molybdenum oxide;
the molybdenum oxide modifier comprises Pb2+、Fe3+、Fe2+、Al3+、Ca2+、Mg2+And Ba2+One or more elements of (a);
the selective inhibitor comprises one or more of modified water glass, phosphate, modified starch, dextrin, tannin, cellulose, tartaric acid, citric acid, oxalic acid and aminophosphoric acid.
The molybdenum oxide and the tungsten contained in the raw materials mainly exist in the forms of calcium molybdate, molybdenum dioxide, molybdenum trioxide and calcium tungstate, and the raw materials contain one or more of quartz, calcite, fluorite and barite.
The collector powerful agent comprises one or more of oxidized kerosene, oxidized diesel oil, alkyl sulfate soap and ester thereof, alkyl sulfonic acid soap and ester thereof, hydroximic acid, naphthalene and derivative thereof and alkyl ammonium bromide.
The collector comprises oleic acid and derivatives thereof.
And (4) concentrating the product obtained in the first step to more than 60%.
And in the fourth step, the dilution is below 20 percent.
In the first step, the adding amount of the molybdenum oxide modifier, the regulator, the selective inhibitor, the collector and the collector powerful agent in each ton of molybdenum sulfide flotation tailing pulp is respectively 100 g-1000 g, 500 g-2000 g, 200 g-2000 g, 100 g-500 g and 50 g-300 g.
The adding amounts of the pH regulator, the desiccants, the selective inhibitor, the collector and the collector powerful agent in the third step are respectively 100-500 g/t, 200-800 g/t, 3000-8000 g/t, 0-100 g/t and 0-50 g/t in the ratio of the product in the second step.
Compared with the prior art, the invention has the following technical effects:
(1) the invention adds molybdenum oxide modifier in tailing slurry to modify the surface property of molybdenum oxide, especially the resources of molybdenum dioxide, molybdenum trioxide and calcium molybdate, the collecting agent of the invention adopts the combined action of the collecting agent powerful agent and oleic acid soap to selectively adsorb the surface of the modified molybdenum oxide to strengthen the recovery of molybdenum oxide in the rough separation section, and combines reasonable flotation agent and flotation process, under the premise of not influencing the grade of scheelite concentrate, the total recovery rate of molybdenum can reach more than 75%, the content of molybdenum oxide in the recycled scheelite is greatly improved, and the problems of difficult recovery and serious loss of molybdenum oxide at present are solved.
(2) According to the invention, the selective inhibitor is added to reduce the adverse effect of the calcium-containing gangue minerals with good floatability on the selection, the floatation medicament plays a certain inhibiting role on the gangue minerals such as fluorite, calcite and the like in the heating and drug removal process, and meanwhile, the collecting agent is added to prevent part of scheelite and molybdenum oxide from losing along with tailings due to drug removal in the heating and drug removal process.
The present invention will be explained in further detail with reference to examples.
Detailed Description
The method takes molybdenum sulfide flotation tailing slurry after molybdenum sulfide flotation as a raw material, and performs scheelite flotation to obtain scheelite flotation concentrate enriched with molybdenum oxide. Sequentially adding a molybdenum oxide modifier, a regulator, a selective inhibitor, a collector and a collector powerful agent into molybdenum sulfide flotation tailing pulp, and performing normal-temperature flotation to obtain tungsten-molybdenum mixed rough concentrate pulp; the molybdenum oxide modifier and the molybdenum oxide mineral surface are subjected to chemical reaction to generate substances which are easy to react with the collecting agent. The regulator in the step is selected conventionally, and can refer to the mineral dressing preparation in the field, and the sodium carbonate regulator is selected in the invention. And step two, concentrating the product obtained in the step one to more than 60%, mainly aiming at reducing production energy consumption and saving the dosage of production medicaments. Adding a pH regulator, a desiccants, a selective inhibitor, a collector and a collector powerful agent into the product obtained in the step two; the pH regulator can adjust the optimal action environment of the medicament, is a conventional choice in the field, the sodium hydroxide is selected, the gangue mineral surface collecting agent can be removed by the medicament removing agent, and the calcium and magnesium ions are selected and the selective inhibitor can selectively strengthen the inhibiting effect on the gangue mineral. And step four, diluting the product obtained in the step three, and performing flotation to obtain a scheelite flotation concentrate enriched in molybdenum oxide, wherein the flotation concentration is to separate target minerals and gangue minerals, and the lower the concentration of the ore pulp is, the better the separation effect is.
In the first step of the invention, the adding amounts of the molybdenum oxide modifier, the regulator, the selective inhibitor, the collector and the collector powerful agent in each ton of molybdenum sulfide flotation tailing slurry are respectively 100 g-1000 g, 500 g-2000 g, 200 g-2000 g, 100 g-500 g and 50 g-300 g; in the third step, the addition amounts of the pH adjusting agent, the desoxidant agent, the selective inhibitor, the collector and the collector synergist in the second step are respectively 100 g/t-500 g/t, 200 g/t-800 g/t, 3000 g/t-8000 g/t, 0-100 g/t and 0-50 g/t, and specific examples of the present invention are given below by taking only a certain value in the value range of each raw material as an example.
Example 1:
the embodiment provides a method for improving the enrichment effect of molybdenum oxide in scheelite flotation concentrate, wherein molybdenite flotation tailings of a certain tungsten-molybdenum ore deposit in Henan are selected, the main tungsten minerals in the tailings are scheelite, the molybdenum minerals are mainly molybdenum oxide, the content of tungsten trioxide is 0.1%, the content of molybdenum in the molybdenum oxide is 0.02%, the grinding fineness is-200%, and the content is 65%. The method specifically comprises the following steps:
step one, sequentially adding 200g/t of lead ion molybdenum oxide modifier, 1500g/t of sodium carbonate regulator, 1000g/t of modified water glass, 20g/t of citric acid and 500g/t of modified starch as gangue inhibitor, 300g/t of oleic soap as collector, 150g/t of oxidized kerosene and 100g/t of alkyl sulfate soap as collector powerful agent into 35% molybdenite flotation tailing slurry, and performing primary roughing and three-time rough scavenging to obtain tungsten-molybdenum mixed rough concentrate;
step two, concentrating the product obtained in the step one to 65%;
and step three, heating and removing the chemicals from the product obtained in the step two, respectively adding 400g/t of sodium hydroxide as a pH regulator, 500g/t of calcium and magnesium ions as a removing agent, 5000g/t of modified water glass, 200g/t of citric acid, 1500g/t of modified starch, 20g/t of a small amount of oleic soap and 20g/t of a collecting agent powerful agent, diluting the heat-preservation ore pulp to 18% of concentration, and carrying out concentration for three times to obtain the final tungsten-molybdenum mixed concentrate, wherein the detection result is as follows, wherein the tungsten trioxide content is 30%, the total recovery rate is 81%, the molybdenum content is 5.62%, and the total recovery rate is 75.87%.
Comparative example 1:
the comparison example shows a method for floating scheelite by using molybdenum sulfide flotation tailing slurry as a raw material, which is different from the method in example 1, a molybdenum oxide modifier, a selective inhibitor and a collector powerful agent are not added in the step one of the comparison example, and scheelite flotation concentrate is obtained by direct flotation after the step one, and the detection results are as follows, and the results show that the content of tungsten trioxide is 26.67%, the total recovery rate is 67.74%, the content of molybdenum is 2.15% and the total recovery rate is 27.30%.
Claims (2)
1. A method for improving the enrichment effect of molybdenum oxide in scheelite flotation concentrate is characterized by comprising the following steps:
step one, adding a molybdenum oxide modifier, a regulator, a selective inhibitor, a collector and a collector powerful agent into molybdenum sulfide flotation tailing pulp in sequence, and carrying out normal-temperature flotation to obtain tungsten-molybdenum mixed rough concentrate pulp;
step two, concentrating the product of the step one;
adding a pH regulator, a desiccants, a selective inhibitor, a collector and a collector powerful agent into the product obtained in the step two;
step four, diluting the product obtained in the step three, and then concentrating to obtain scheelite flotation concentrate enriched with molybdenum oxide;
the molybdenum oxide modifier comprises Pb2+、Fe3+、Fe2+、Al3+、Ca2+、Mg2+And Ba2+One or more elements of (a);
the selective inhibitor comprises one or more of modified water glass, phosphate, modified starch, dextrin, tannin, cellulose, tartaric acid, citric acid, oxalic acid and aminophosphoric acid;
molybdenum oxide and tungsten contained in the molybdenum sulfide flotation tailing slurry mainly exist in the forms of calcium molybdate, molybdenum dioxide, molybdenum trioxide, calcium tungstate and tungsten bloom, and the molybdenum sulfide flotation tailing slurry contains one or more of quartz, calcite, fluorite and barite;
the tungsten mineral in the molybdenum sulfide flotation tailing slurry is scheelite, the molybdenum mineral is mainly molybdenum oxide, the content of tungsten trioxide is 0.1%, the content of molybdenum in the molybdenum oxide is 0.02%, the grinding fineness is-200%, and the content is 65%;
the collector powerful agent comprises one or more of oxidized kerosene, oxidized diesel oil, alkyl sulfate soap and ester thereof, alkyl sulfonic acid soap and ester thereof, hydroximic acid, naphthalene and derivative thereof and alkyl ammonium bromide;
the collector comprises oleic acid and derivatives thereof;
concentrating the product obtained in the first step to more than 60%;
diluting to below 20% in the fourth step;
the adding amount of the molybdenum oxide modifier, the regulator, the selective inhibitor, the collector and the collector powerful agent in each ton of molybdenum sulfide flotation tailing pulp in the step one is respectively 100 g-1000 g, 500 g-2000 g, 200 g-2000 g, 300 g-500 g and 50 g-300 g.
2. The method according to claim 1, wherein the addition amounts of the pH regulator, the desolventizing agent, the selective inhibitor, the collector and the collector synergist in the third step are respectively 100g/t to 500g/t, 200g/t to 800g/t, 3000g/t to 8000g/t, 0g/t to 100g/t and 0g/t to 50g/t in the second step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710325108.1A CN107081220B (en) | 2017-05-10 | 2017-05-10 | Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710325108.1A CN107081220B (en) | 2017-05-10 | 2017-05-10 | Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107081220A CN107081220A (en) | 2017-08-22 |
| CN107081220B true CN107081220B (en) | 2020-02-18 |
Family
ID=59612911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710325108.1A Active CN107081220B (en) | 2017-05-10 | 2017-05-10 | Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107081220B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993776A (en) * | 2018-06-22 | 2018-12-14 | 昆明理工大学 | A kind of Scheelite Flotation composite restrainer and its application method |
| CN109482362A (en) * | 2018-12-26 | 2019-03-19 | 高台县宏源矿业有限责任公司 | A kind of inhibitor and the method that calcite is separated from fluorite ore using the inhibitor |
| CN109465114B (en) * | 2019-01-09 | 2020-12-29 | 湖南有色金属研究院 | Flotation separation method for barite and dolomite |
| CN111330743A (en) * | 2020-04-09 | 2020-06-26 | 北京矿冶科技集团有限公司 | Spodumene ore flotation collector, preparation method thereof and spodumene ore dressing process for clay mineralization |
| CN114749282B (en) * | 2022-05-31 | 2024-07-16 | 西安建筑科技大学 | Calcium molybdate vulcanization flotation method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7811444B2 (en) * | 2006-06-08 | 2010-10-12 | Marathon Oil Canada Corporation | Oxidation of asphaltenes |
| CN102631976B (en) * | 2012-03-30 | 2013-10-09 | 洛阳栾川钼业集团股份有限公司 | Method for replacing lime by sodium hydroxide in scheelite heating concentration |
| CN102658241A (en) * | 2012-04-23 | 2012-09-12 | 洛阳栾川钼业集团股份有限公司 | Flotation process adopting flotation column to regrading scheelite instead of flotation machine |
| CN102671769B (en) * | 2012-05-14 | 2014-02-26 | 长沙矿冶研究院有限责任公司 | Beneficiation method for flotation and recovery of molybdenum from easy-floating gangue refractory molybdenum ore |
| CN105170335A (en) * | 2015-05-29 | 2015-12-23 | 洛阳栾川钼业集团股份有限公司 | Process for floatation of high-concentration scheelite rough concentrate |
-
2017
- 2017-05-10 CN CN201710325108.1A patent/CN107081220B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107081220A (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107081220B (en) | Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate | |
| CN104084315B (en) | Beneficiation method for separating fluorite and tungsten through flotation | |
| CN103551255B (en) | Molybdenum oxide ore flotation collecting agent and using method | |
| CN111715411B (en) | Beneficiation method for high-sulfur lead-zinc ore | |
| CN105435953A (en) | Beneficiation method for molybdenum-containing low-grade mixed copper ore | |
| CN112264197B (en) | Combined inhibitor for high-magnetic pyrite type copper-sulfur ore and beneficiation method thereof | |
| CN107971127B (en) | Beneficiation method for separating bismuth and sulfur in bismuth-sulfur concentrate | |
| CN113976307A (en) | Flotation separation method of refractory lead-zinc sulfide ore and zinc blende inhibitor thereof | |
| CN110976097B (en) | Flotation method for zinc oxide in sulfide ore tailings | |
| CN112317135B (en) | Combined inhibitor for flotation separation of copper-lead sulfide ore and application thereof | |
| CN111468302B (en) | Beneficiation inhibitor and purification method of molybdenum rough concentrate | |
| CN113856911B (en) | Beneficiation method for high-sulfur copper gold and silver ore | |
| CN111871618B (en) | Method for removing titanium minerals in high-sulfur bauxite | |
| CN113042216A (en) | Flotation separation method for carbonaceous lead sulfide zinc minerals | |
| CN113102115A (en) | Beneficiation process for zinc mineral in low-grade lead-zinc sulfide ore and inhibitor thereof | |
| CN113233426A (en) | Method for recovering sulfur from zinc oxygen pressure leaching high-sulfur slag | |
| CN110369150A (en) | A kind of high-grade lead sulfide mixed concentrate flotation separation method | |
| CN114029156A (en) | Green ore dressing process for copper, lead, zinc, gold, silver and other multi-metal complex sulfide ores | |
| CN113600345A (en) | Method for floating pyrite inhibited by lime in acid-free and ammonium-free manner | |
| CN112007760A (en) | Beneficiation method for treating high sesquioxide collophanite | |
| CN113877721B (en) | Method for deeply removing micro-fine black-white mica from granite type metal ore tailings | |
| CN109833978A (en) | A method of improving silver lead zinc ore argentalium mineral processing index | |
| CN111298977B (en) | Reagent composition for flotation of lepidolite and preparation method and application thereof | |
| CN112827640B (en) | Beneficiation method for recovering iron and sulfur from high-sulfur low-intensity magnetic separation tailings | |
| CN110496700B (en) | Method for recovering gold from high-arsenic gold-dressing tailings and application thereof |
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 |