CN117654783A - Mineral separation method for generating Pickering emulsion by using ultrafine particles as surfactant - Google Patents
Mineral separation method for generating Pickering emulsion by using ultrafine particles as surfactant Download PDFInfo
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- CN117654783A CN117654783A CN202311690310.6A CN202311690310A CN117654783A CN 117654783 A CN117654783 A CN 117654783A CN 202311690310 A CN202311690310 A CN 202311690310A CN 117654783 A CN117654783 A CN 117654783A
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- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 96
- 239000011707 mineral Substances 0.000 title claims abstract description 96
- 239000000839 emulsion Substances 0.000 title claims abstract description 45
- 239000011882 ultra-fine particle Substances 0.000 title claims abstract description 31
- 238000000926 separation method Methods 0.000 title claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 73
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000012141 concentrate Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000003814 drug Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000005476 size effect Effects 0.000 abstract description 2
- 238000005188 flotation Methods 0.000 description 15
- 238000011084 recovery Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- 230000002776 aggregation Effects 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000002367 phosphate rock Substances 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 4
- 230000005501 phase interface Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000012840 feeding operation Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000003415 peat 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
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011593 sulfur 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
- B03D3/00—Differential sedimentation
-
- 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
-
- 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
- Colloid Chemistry (AREA)
Abstract
The invention belongs to the technical field of ultrafine particle mineral separation, and particularly relates to a mineral separation method for generating Pickering emulsion by taking ultrafine particles as a surfactant. Firstly, preparing ultrafine particle minerals into suspension slurry, then adding a dispersing agent and a collecting agent for stirring, and then adding an oil phase for stirring and pulping to obtain Pickering emulsion; after the Pickering emulsion is kept stand and stable, collecting cream-like liquid drops which float on the top of the slurry and contain ultrafine grain mineral, and separating the cream-like liquid drops from deposited tailings; and centrifuging the creamy liquid drops, and demulsifying and separating to obtain the required concentrate. The method fully utilizes the size effect of the ultrafine particle minerals, breaks through thinking and makes use of the surface activity of the ultrafine particles as a surfactant to prepare the Pickering emulsion, thereby converting the disadvantage of fine granularity into advantages, and sorting the ultrafine particle minerals in a mode of forming the Pickering emulsion, and has the advantages of simple operation, high sorting efficiency, low medicine consumption, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of ultrafine particle mineral separation, and particularly relates to a mineral separation method for generating Pickering emulsion by taking ultrafine particles as a surfactant.
Background
With the gradual exhaustion of high-quality easily-processed ores and the increasing global demand for ores, ores are becoming lean, thin and hybridized, and low-quality minerals become main sources of mineral resources for a long time in the future. Low quality mineral resources commonly present ultra-fine grain sorting challenges, such as molybdenum, titanium, iron, copper, rare earth, graphite, etc. embedded in ultra-fine grain form of tens of microns.
Flotation is considered one of the most cost-effective methods of fine-grained mineral separation. However, the momentum of the superfine ore particles in the flotation ore pulp is small, the collision probability with bubbles is small, and the flotation recovery rate is low; in addition, because the specific surface area of the ultra-fine mineral particles is increased, non-selective agglomeration between gangue mineral particles and useful mineral particles is easy to cause, the action between the medicament and the minerals is influenced, high medicament consumption is caused, and the production cost is greatly increased. Therefore, a large amount of valuable ultrafine minerals cannot be effectively separated into discarded tailings, so that not only is the resource wasted, but also the ecological environment is threatened.
In order to improve the flotation effect of ultra-fine useful minerals, patent CN101722111A, CN103056033a and the like disclose an improved peat flotation reagent, which is proposed to enhance the reagent dispersibility by emulsifying the reagent, thereby reducing the reagent consumption. However, the flotation reagent has poor stability after emulsification treatment, is not easy to store and breaks emulsion to cause the failure of the emulsification and separation functions, and can not solve the problem of low efficiency of superfine particle flotation and mineralization. In addition, the oil agglomeration and separation are adopted by the scholars, the oil bridge strengthening agglomeration effect is formed among the hydrophobically modified ultrafine particles by taking nonpolar oil as bridging liquid, the apparent particle size of the ultrafine particles is increased, and then separation is carried out by screening or fractional flotation and other methods, but the oil phase cannot be recovered, and the oil consumption is high and reaches tens or even hundreds of kg/t. Some scholars propose to add surfactant in the oil agglomeration sorting process, emulsify the oil phase, improve the oil phase dispersibility, although can reduce the oil consumption, the oil phase still can not effectively recycle, and the oil consumption still is greater than 10kg/t, still has great distance from practical application.
In conclusion, the separation of the ultrafine mineral is a worldwide difficult problem which is very troublesome to solve, and the method for improving the efficient recovery of the ultrafine mineral is provided as soon as possible, so that the method has great significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a mineral separation method for generating Pickering emulsion by using ultrafine particles as a surfactant.
The invention adopts the technical scheme that:
the mineral separation method for generating Pickering emulsion by taking ultrafine particles as a surfactant, wherein the Pickering emulsion is formed by taking ultrafine particles as the surfactant and selectively adsorbing the ultrafine particles at an oil-water interface by utilizing the surface activity of the ultrafine particles, and comprises the following steps:
step 1: adding water into the ultrafine mineral to perform primary stirring and size mixing to obtain suspension sizing agent;
step 2: adding a required dispersing agent matched with the separated ultrafine particle minerals and a collecting agent into the suspension slurry, and carrying out secondary stirring and slurry mixing;
step 3: continuously adding the oil phase to perform stirring and pulping for the third time to obtain Pickering emulsion;
step 4: after the Pickering emulsion is kept stand and stable, collecting cream-like liquid drops which float on the top of the slurry and contain ultrafine grain mineral, and separating the cream-like liquid drops from tailings deposited on the bottom of the slurry;
step 5: and centrifuging the creamy liquid drops, and demulsifying and separating to obtain an oil phase and required concentrate.
Preferably, the ultrafine grain mineral is an ultrafine grain mineral with a mass ratio of not more than 80% and not more than 38 μm.
Preferably, in the suspension slurry, the mass ratio of the ultrafine mineral to the water is 1 (18-22).
Preferably, in the step 2, the addition of the dispersing agent and the collecting agent satisfies that the superfine minerals in the slurry are uniformly dispersed after the second stirring and size mixing, and the contact angle of the target minerals is 75-110 degrees.
Preferably, the dispersing agent is water glass and/or sodium hexametaphosphate, and is used for keeping the superfine particle minerals in a dispersed state and preventing aggregation of the superfine particle minerals. The type and the amount of the collector are adjusted according to different mineral compositions, and the type and the amount of the collector need to enable the contact angle of the target mineral (concentrate) to be between 75 and 110 degrees so as to ensure that the superfine particles of the target mineral (concentrate) have enough surface activity and can be selectively adsorbed on an oil-water interface to play a role of the surfactant.
Preferably, in the step 2, the method further comprises a pH adjuster, wherein the pH adjuster is any one or more than two of lime, sodium carbonate and sulfuric acid, and the pH adjuster is added to maximize the difference of adsorption amounts of the target minerals (concentrate) and the non-target minerals (tailings) at an oil-water interface.
Preferably, in the step 3, the oil phase is any one or a combination of more than one of linear alkane, branched alkane and cycloalkane, and the addition mass of the oil phase accounts for 1/(9-12) of the mass of the water added in the step 1.
Preferably, the stirring rotation speeds of the first stirring and size mixing, the second stirring and size mixing and the third stirring and size mixing are 1000-2000 rpm, and the stirring time is 3-25 min.
Preferably, the slurry and the tailings remain in the step 4 to obtain an aqueous phase, and the aqueous phase and the oil phase in the step 5 are returned to the step 1 and the step 3 for recycling.
The present invention also provides a system for implementing a mineral separation process for forming pickering emulsions with ultrafine particles as defined in claim 1 as a surfactant.
The invention has the beneficial effects that:
the valuable components of the ultrafine particle minerals are generally embedded in the form of particles of tens of micrometers, and when the ultrafine particle minerals are treated by the traditional beneficiation method, the granularity is fine, so that the invention breaks through the thinking setting, fully utilizes the size effect of the ultrafine particle minerals, utilizes the surface activity of the ultrafine particles as a surfactant, and is used for preparing Pickering emulsion, thereby converting the disadvantage of fine granularity into advantages.
The Pickering emulsion is adopted to selectively separate the ultrafine particle minerals, and the wettability of the ultrafine particle minerals is adjusted to enable the ultrafine particle minerals to selectively adhere to the surface of oil drops to form the Pickering emulsion, so that the target minerals and gangue minerals can be effectively separated.
The oil phase and the water phase can be recycled. The water phase and the oil phase participate in the formation of the Pickering emulsion, and can be easily separated from concentrate and tailings after standing and centrifugal operation, so that the water phase and the oil phase can be recycled, and the method is economical and environment-friendly.
The invention effectively utilizes the activity of the hydrophobically modified ultrafine grain mineral at the oil-water phase interface, realizes the separation of ultrafine grain mineral by forming Pickering emulsion, and has the advantages of simple operation, high separation efficiency, low medicine consumption, environmental protection and the like.
Drawings
FIG. 1 is a schematic flow chart of the present invention;
FIG. 2 is a schematic diagram of a conventional flotation circuit in example 1;
FIG. 3 is a schematic diagram of a conventional flotation circuit in example 2;
FIG. 4 is a schematic diagram of a conventional flotation circuit in example 3;
fig. 5 is a schematic diagram of a device system according to the present invention.
The meaning of the reference numerals in the figures is as follows:
10-stirring device 11-first stirring barrel 12-second stirring barrel 13-third stirring barrel
20-water tank 30-medicine box 40-oil tank 50-Pickering emulsion sorting device
60-centrifugal device 61-second pump 62-second recovery conduit
70-filtration device 71-first pump body 72-first recovery conduit
Detailed Description
The technical scheme of the invention is described in more detail below with reference to examples.
Example 1
The method is used for separating and recovering certain superfine molybdenum ore in Henan, wherein useful minerals in the target superfine molybdenum ore are molybdenite, and metal minerals are pyrite, chalcopyrite and hematite. Gangue minerals mainly comprise chlorite, quartz, muscovite, etc. The concentration of the superfine molybdenum ore is lower, about 5 percent, the granularity is finer, and the content of minus 38 mu m is more than 85 percent. Molybdenum in the ultrafine grain molybdenum ore is 0.699%, copper is 0.020%, and iron is 0.07%.
The method comprises the following steps:
s0. sieving molybdenum ore to obtain superfine ore with a mass content of-38 μm of more than 90%;
s1, mixing 80g of screened ultrafine mineral with 1600g of water, stirring and pulping for the first time, wherein the stirring speed is 1000rpm, and the stirring time is 3min, so that ultrafine mineral aggregates are crushed, dispersed and homogenized into suspension slurry;
s2, adding dispersant water glass (280 g.t) -1 ) Yellow drug of collector (450 g.t) -1 ) pH regulator sodium carbonate (300 g.t) -1 ) Stirring and sizing for the second time, wherein the pH value of the suspension sizing agent is 10, the stirring rotating speed is 1000rpm, and the stirring time is 5min, so that the superfine mineral particles are fully dispersed and the surface hydrophobicity of the target mineral is improved;
s3, continuing adding kerosene (180 g) as an oil phase to perform stirring and sizing for the third time, wherein the stirring speed is 1500rpm, the stirring time is 20min, and the hydrophobically modified ultrafine grain mineral is selectively adsorbed on an oil-water phase interface to form Pickering emulsion;
s4, after the Pickering emulsion is kept stand and stable, collecting cream-like liquid drops which float at the top of the slurry and contain ultrafine grain mineral, and separating the cream-like liquid drops from tailings deposited at the bottom of the slurry;
s5, centrifuging the creamy liquid drops, demulsifying and separating to obtain an oil phase and concentrate, filtering the residual slurry and tailings in the step 4 to obtain a water phase, and returning the water phase and the oil phase to the step S1 and the step S3 for recycling.
Referring to fig. 2, the ultrafine molybdenum ore is also subjected to oil agglomeration and separation, and the dosage of the agents in each stage is shown in the following table:
the concentrate in the Pickering emulsion sorting flow is detected, the molybdenum concentrate grade is 30.669%, the recovery rate is 67.44%, the molybdenum concentrate grade of the conventional oil agglomeration sorting is 28.669%, the recovery rate is 65.44%, and the Pickering emulsion sorting flow obtains higher concentrate grade and recovery rate, and meanwhile the oil phase is effectively recycled.
Example 2
The method is used for separating and recovering ultrafine ilmenite of Sichuan, and the valuable components which can be recovered and utilized in the raw ore are iron, titanium, sulfur and the like, wherein TiO 2 The grade is 6.32%, mFe is 1.43%, S content is 0.49%, and the main recovered target mineral is ilmenite. The ilmenite embedded particle size is typically an ultrafine size fraction of-0.038 mm.
The method comprises the following steps:
s0. sieving molybdenum ore to ultrafine particle mineral content of-38 μm of more than 85%;
s1, mixing 360g of screened ultrafine mineral with 6500g of water, stirring and pulping for the first time, wherein the stirring speed is 1200rpm, and the stirring time is 4min, so that ultrafine mineral aggregates are crushed, dispersed and homogenized into suspension slurry;
s2, adding dispersant water glass (500 g.t) -1 ) Collector sodium oleate (300 g.t) -1 ) pH regulator sulfuric acid (800 g.t) -1 ) Stirring and sizing for the second time, wherein the stirring rotation speed is 1200rpm, and stirringStirring for 7min to fully disperse the superfine mineral and improve the surface hydrophobicity of the target mineral;
s3, continuing adding diesel oil (700 g) as an oil phase to perform stirring and sizing for the third time, wherein the stirring speed is 1800rpm, the stirring time is 20min, and the hydrophobically modified ultrafine grain mineral is selectively adsorbed on an oil-water phase interface to form Pickering emulsion;
s4, after the Pickering emulsion is kept stand and stable, collecting cream-like liquid drops which float at the top of the slurry and contain ultrafine grain mineral, and separating the cream-like liquid drops from tailings deposited at the bottom of the slurry;
s5, centrifuging the creamy liquid drops, demulsifying and separating to obtain an oil phase and concentrate, filtering the residual slurry and tailings in the step 4 to obtain a water phase, and returning the water phase and the oil phase to the step S1 and the step S3 for recycling.
Referring to fig. 3, the ultrafine ilmenite was also subjected to oil agglomeration classification, carefully selected for a feed operation condition: adding 3600g of water and fully mixing with the roughing concentrate for 4min; carefully selecting secondary ore feeding operation conditions: 1800g of water and materials are added and fully mixed for 3min; selecting three ore feeding operation conditions: 900g of water and the material were added and thoroughly mixed for 3min. The dosage of the medicament in each stage is shown in the following table:
the concentrate in the Pickering emulsion sorting flow is detected, the titanium grade of the titanium concentrate is 48.667%, the recovery rate is 67.44%, the titanium grade of the titanium concentrate subjected to conventional oil agglomeration sorting is 47.20%, the recovery rate is 63.56%, and the Pickering emulsion sorting flow obtains higher concentrate grade and recovery rate, and meanwhile the oil phase is effectively recycled.
Example 3
The method is used for separating and recovering superfine phosphorite in Guizhou, and the raw ore consists of fluorapatite, dolomite and quartz, wherein the useful mineral is fluorphosphateThe limestone and gangue minerals are dolomite and a small amount of quartz. P in raw ore 2 O 5 Grade is 1.67%, mgO content is 7.63%, siO 2 The content is only 42.58%, which indicates that the ore belongs to low-grade phosphate ore.
The method comprises the following steps:
s0. the phosphorite is subjected to ore grinding process treatment, ore is fully dissociated, and then the phosphorite is screened to ultrafine grain mineral content of-38 mu m accounting for more than 90 percent;
s1, mixing 350g of screened ultrafine mineral with 7000g of water, stirring and pulping for the first time, wherein the stirring speed is 1300rpm, and the stirring time is 3min, so that ultrafine mineral aggregates are crushed, dispersed and homogenized into suspension slurry;
s2, adding dispersant water glass (150 g.t) -1 ) pH regulator sulfuric acid (1200 g.t) -1 ) Collector fatty amine (60 g.t) -1 ) Stirring and sizing for the second time, wherein the stirring rotating speed is 1300rpm, so that the superfine mineral is fully dispersed and the surface hydrophobicity of the target mineral is improved;
s3, continuously adding oxidized kerosene (500 g.t) -1 ) Stirring and pulping for the third time as an oil phase, wherein the stirring speed is 1700rpm, the stirring time is 25min, and the hydrophobically modified ultrafine grain mineral is selectively adsorbed at an oil-water phase interface to form Pickering emulsion;
s4, after the Pickering emulsion is kept stand and stable, collecting cream-like liquid drops which float at the top of the slurry and contain ultrafine grain mineral, and separating the cream-like liquid drops from tailings deposited at the bottom of the slurry;
s5, centrifuging the creamy liquid drops, demulsifying and separating to obtain an oil phase and concentrate, filtering the residual slurry and tailings in the step 4 to obtain a water phase, and returning the water phase and the oil phase to the step S1 and the step S3 for recycling.
Referring to fig. 4, the above superfine phosphorite is separated according to a conventional flotation process, after conventional flotation, superfine phosphorite is obtained, and after detection, the grade of phosphorus in the superfine phosphorite is 30.03%, the recovery rate is 90.68%, and the concentrate obtained by the pickering emulsion separation process is detected, and in step S5, the concentrate is detected, the grade of phosphorus in the phosphate concentrate is 33.13%, which is improved by about 10% compared with conventional flotation, the recovery rate is 94.12%, and is improved by 3.44% compared with conventional flotation.
Example 4
A device system for realizing the mineral separation method for forming Pickering emulsion by using the ultrafine particles as a surfactant.
Referring to fig. 5, the system of devices comprises at least 3 sequentially connected mixing tanks connected by pipes provided with valves and/or pumps. According to the connection sequence, the first stirring barrel 11 and the second stirring barrel 12 are connected with the water tank 20, the second stirring barrel 12 is further provided with the dosing tank 30, the third stirring barrel 13 is connected with the oil tank 40, the third stirring barrel 13 is provided with the Pickering emulsion sorting device 50, the outlet of the Pickering emulsion sorting device 50 is connected with the centrifugal equipment 60, and the bottom of the third stirring barrel 13 is connected with the filtering device 70. The filtering device 70 is further connected to the water tank 20 through a first pump body 71 and a first recovery pipe 72, and the centrifugal device 60 is further connected to the oil tank 40 provided on the third stirring tank 13 through a second pump body 61 and a second recovery pipe 62.
Adding water into the first stirring barrel 11 for stirring and pulping for the first time to obtain suspension slurry; the suspension slurry enters a second stirring barrel 12 through a pipeline to be stirred and mixed for the second time, then enters a third stirring barrel 13, and is added with an oil phase to be stirred and mixed for the third time, so that the Pickering emulsion is produced in situ. After the Pickering emulsion is kept stand and stable, slurry at the top of the third stirring barrel 13 is collected by the Pickering emulsion sorting device 50 and enters the centrifugal equipment 60, the required concentrate is obtained through centrifugation, and the centrifugally separated oil phase is returned to the oil tank 40 for reuse. The tailings deposited at the bottom of the third stirring tank 13 enter the filtering device 70, and the filtered water phase returns to the water tank 20 for reuse.
In this embodiment, the pickering emulsion sorting device 50 is an electric scraper disposed at the top of the third stirring tank 13, and is capable of scraping off pickering emulsion containing the target minerals at the top of the third stirring tank 13.
The stirring barrels are internally provided with stirring devices 10, the stirring devices 10 comprise stirring shafts which are vertically arranged, the stirring shafts are eccentrically arranged, the distance between the central line of the stirring shafts of the stirring devices 10 in the third stirring barrel 13 and the vertical central line of an electric scraper of the Pickering emulsion sorting device 50 is 1/4-3/4 barrel radius, 1-3 impellers with adjustable inclination are uniformly distributed on the stirring shafts so as to avoid vortex formation and generate turbulence in a flow field, the number of blades of the impellers is 3-6, and the inclination angle is 20-60 degrees.
The rest of the system may be arranged according to the general understanding and actual use requirements of those skilled in the art, and the present embodiment is not particularly limited.
The above embodiments are only for illustrating the technical scheme of the present invention, and are not limiting to the present invention; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The mineral separation method for forming Pickering emulsion by using ultrafine particles as a surfactant is characterized by comprising the following steps:
step 1: adding water into the ultrafine mineral to perform primary stirring and size mixing to obtain suspension sizing agent;
step 2: adding a required dispersing agent matched with the separated ultrafine particle minerals and a collecting agent into the suspension slurry, and carrying out secondary stirring and slurry mixing;
step 3: continuously adding the oil phase to perform stirring and pulping for the third time to obtain Pickering emulsion;
step 4: after the Pickering emulsion is kept stand and stable, collecting cream-like liquid drops which float on the top of the slurry and contain ultrafine grain mineral, and separating the cream-like liquid drops from tailings deposited on the bottom of the slurry;
step 5: and centrifuging the creamy liquid drops, and demulsifying and separating to obtain an oil phase and required concentrate.
2. The mineral separation method according to claim 1, wherein the ultrafine mineral is an ultrafine fraction mineral having a mass ratio of not less than 80% of 38 μm.
3. The mineral separation method as claimed in claim 1, wherein the mass ratio of ultrafine mineral to water in the suspension slurry is 1 (18-22).
4. The mineral separation method according to claim 1, wherein in the step 2, the addition of the dispersing agent and the collecting agent satisfies that the superfine mineral in the slurry after the second stirring and the size mixing is uniformly dispersed and the contact angle of the target mineral is between 75 degrees and 110 degrees.
5. The mineral separation process of claim 4, wherein the dispersant is water glass and/or sodium hexametaphosphate.
6. The mineral separation method according to claim 1, 4 or 5, further comprising a pH adjuster in step 2, wherein the pH adjuster is any one or a combination of two or more of lime, sodium carbonate and sulfuric acid.
7. The mineral separation method according to claim 1, wherein in the step 3, the oil phase is a combination of any one or more of linear alkane, branched alkane and cycloalkane, and the oil phase is added in a mass ratio of 1/(9-12) to the mass of water added in the step 1.
8. The mineral separation method according to claim 1, wherein the stirring rotation speeds of the first stirring and size mixing, the second stirring and size mixing and the third stirring and size mixing are 1000-2000 rpm, and the stirring time is 3-25 min.
9. The mineral separation process of claim 1, wherein the slurry and tailings remaining in step 4 provide an aqueous phase, and the aqueous phase and the oil phase in step 5 are recycled back to step 1 and step 3.
10. A system for implementing a mineral separation process of ultra-fine particles of claim 1 as a surfactant to form a pickering emulsion.
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