CN116943871A - Efficient collector, preparation method thereof and application of efficient collector in fluorite flotation in high-calcium fluorite ore - Google Patents
Efficient collector, preparation method thereof and application of efficient collector in fluorite flotation in high-calcium fluorite ore Download PDFInfo
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- CN116943871A CN116943871A CN202310688345.XA CN202310688345A CN116943871A CN 116943871 A CN116943871 A CN 116943871A CN 202310688345 A CN202310688345 A CN 202310688345A CN 116943871 A CN116943871 A CN 116943871A
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- bha
- fluorite
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- flotation
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 239000010436 fluorite Substances 0.000 title claims abstract description 63
- 238000005188 flotation Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims abstract description 24
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 24
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims abstract description 20
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229960001716 benzalkonium Drugs 0.000 claims 1
- 125000005501 benzalkonium group Chemical group 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 11
- 239000011707 mineral Substances 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 239000011575 calcium Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011084 recovery Methods 0.000 description 17
- 229910004261 CaF 2 Inorganic materials 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 13
- 239000005642 Oleic acid Substances 0.000 description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 235000010755 mineral Nutrition 0.000 description 10
- 229910021532 Calcite Inorganic materials 0.000 description 9
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000010459 dolomite Substances 0.000 description 7
- 229910000514 dolomite Inorganic materials 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- -1 fatty acid salt Chemical class 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 3
- 239000001263 FEMA 3042 Substances 0.000 description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 3
- 229940033123 tannic acid Drugs 0.000 description 3
- 235000015523 tannic acid Nutrition 0.000 description 3
- 229920002258 tannic acid Polymers 0.000 description 3
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 2
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
- 229910052601 baryte Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000010665 pine oil Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000009282 microflotation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water 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
- B03D1/02—Froth-flotation processes
-
- 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
- B03D2201/02—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
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application discloses a high-efficiency collecting agent, a preparation method thereof and application of the collecting agent in fluorite flotation in high-calcium fluorite ore, and belongs to the technical field of mineral separation. Aiming at the problems of low selectivity, low sorting process index and the like of a high-calcium fluorite flotation collector in the prior art, the application provides an effective solution: the BHA-Ce metal complex and the BHA-Ce mixture synthesized by using the benzoic hydroxamic acid and the cerium trichloride as raw materials have excellent selectivity to fluorite, and the problems of poor selectivity, low flotation index and the like caused by taking calcium particles as adsorption sites in the traditional fluorite collector are effectively avoided. The synthetic preparation method of the BHA-Ce metal complex collector and the BHA-Ce mixture collector provided by the application is simple and feasible, has good performance and has no special requirements on the use environment.
Description
Technical Field
The application belongs to the technical field of mineral separation, and particularly relates to a collecting agent, in particular to a high-efficiency collecting agent, a preparation method thereof and application of the collecting agent in floatation of fluorite in high-calcium fluorite ore.
Background
At present, the floatation is the main process of the beneficiation of fluorite in China, and the fluorite ore can be classified into silicate type fluorite ore, barite type fluorite ore, carbonate type fluorite ore and the like according to the difference of fluorite gangue minerals. The gangue minerals in carbonate fluorite are calcite and dolomite, and the main component is calcium carbonate CaCO 3 . When the content of carbonate in the fluorite ore is about 10-20%, and the rest gangue is mainly quartz, fluorite ore concentrate can be obtained by adopting a collecting agent with better combination inhibitor and matching selectivity through repeated concentration under alkaline conditions, once the content of calcium carbonate is up to 20-50%, the content of quartz is reduced to about 10%, the conventional reagent system almost cannot reach satisfactory flotation index, and a large amount of acid is required to be used for regulating to acidic condition [ Yang Kailiu ] fluorite/dolomite flotation separation and mechanism research [ D]University of martial arts, 2018) or addition of a large amount of inhibitors [ e.g., chinese patent, a beneficiation method for high calcium carbonate fluorite, publication No. CN107377198B; chinese patent, a beneficiation method of fluorite ore with high calcium carbonate content, publication patent No. CN103706485B can only be selected, the selecting cost is greatly increased, and the effect is not reasonableThink about.
Among the current research data for fluorite flotation, the most reported collectors for the flotation of fluorite and its gangue minerals (quartz, calcite, dolomite, barite, etc.) are oleic acid and fatty acid type anion collectors. It is generally believed that oleic acid and fatty acid collector molecules are capable of interacting with Ca on fluorite surfaces 2+ The particles are chemically adsorbed to generate calcium oleate or fatty acid salt, so that the fluorite surface is hydrophobic and floats upwards. Due to the absence of Ca on the quartz surface 2+ The particle has weaker action degree with oleic acid and fatty acid collector molecules, so that the collectors have better effect in the process of separating quartz type fluorite ores; whereas calcite and dolomite also have Ca on their surface 2+ Particles, which have very similar chemical properties to fluorite surfaces, can adsorb to oleic acid or fatty acid collector molecules, making separation from fluorite difficult by flotation. Many studies on the selectivity of fluorite collectors have shown that some higher fatty acids or deeply oxidized fatty acids are more selective than oleic acid but still insufficient to achieve good separation from carbonate gangue.
Besides the anionic collector, the cationic collector can play a certain role in collecting fluorite through electrostatic adsorption, and fatty amine cationic collectors have high fluorite collecting capacity, but cannot be separated from calcium-containing gangue. Only [ studies on the recovery performance of fluorite and calcite by lanthanide metal-benzohydroxamic acid organic complexes ] have been conducted in the past using Ce ions and BHA at a rate of 1: a 2 molar ratio mixture was reported as a fluorite to calcite pure mineral micro-flotation separation, but this study did not show an example of flotation in real ore. Furthermore, the molar ratio of Ce to BHA of the above prior art is 1:2, converted to cerium trichloride and benzoic hydroxamic acid, the BHA-Ce mixture prepared under the proportioning condition has a mass ratio of about 1:1, and the separation effect is seriously deteriorated in the flotation process of actual ores. From this, it can be seen that there is currently a lack of effective collectors that are particularly selective towards carbonate fluorite.
The present application has been made in view of the above-described reasons.
Disclosure of Invention
For the above reasons, the present application aims to solve or at least partially solve the above technical drawbacks of the prior art, and to provide a high-efficiency collector, a preparation method thereof and an application of the collector to fluorite flotation in high-calcium fluorite ore.
In order to achieve the first object of the present application, the present application adopts the following technical scheme:
a high efficiency collector which is a benzahydroxamic acid (BHA) -Ce metal complex or BHA-Ce mixture.
A second object of the present application is to provide a method for producing the collector.
On one hand, the BHA-Ce metal complex is prepared by the following method, and specifically comprises the following steps:
mixing the Benzoic Hydroxamic Acid (BHA) and the cerium trichloride (CeCl) 3 ) Sequentially dissolving in an organic solvent, placing the obtained mixed solution in a condition of 45-55 ℃ for stirring and uniformly mixing, and stirring and reacting the obtained uniform mixed solution for 4-6 hours at the condition of 10-55 ℃; and after the reaction is finished, filtering the obtained product, volatilizing or evaporating the solvent in the obtained filtrate completely to obtain white crystal powder, and purifying to obtain the BHA-Ce metal complex.
Further, according to the technical scheme, the mass ratio of the cerium trichloride to the benzoic hydroxamic acid is (1-3): 1, and under the condition of the dosage, ce ions are completely excessive in the reaction process. If the mass ratio of cerium trichloride to benzoic hydroxamic acid is lower than (1-3): 1, the yield of the synthesized BHA-Ce metal complex will be reduced, and the target product with higher yield can be obtained only in the above-mentioned ratio range.
Further, in the above technical solution, the organic solvent may be any one of anhydrous methanol, anhydrous ethanol, acetone, and the like.
Specifically, in the above technical scheme, the amount of the organic solvent is not particularly limited, so long as the reaction is not affected. For example, the benzoic hydroxamic acid can be used in an amount of 1mmol with respect to the organic solvent: (20-50) mL.
Further, according to the above technical scheme, the stirring time is not particularly limited, so long as the uniform mixing of the benzoic hydroxamic acid and the cerium trichloride in the organic solvent can be achieved.
Further, according to the above technical scheme, the stirring reaction is preferably performed under a normal temperature condition, wherein the normal temperature is a natural room temperature condition in four seasons, no additional cooling or heating treatment is performed, and the normal temperature is generally controlled to be 10-30 ℃, preferably 15-25 ℃.
Further, according to the technical scheme, the solvent in the filtrate can be volatilized naturally in a normal temperature environment, and the volatilization time is more preferably 26-35 days.
Specifically, according to the technical scheme, solvent in the obtained filtrate can be evaporated and crystallized by using a rotary evaporator, and the evaporation temperature is not higher than 55 ℃.
Specifically, according to the technical scheme, the BHA-Ce metal complex is a solid complex, and the solid complex can be dissolved in water according to various proportions to serve as a flotation collector according to a flotation reagent system or process requirements.
On the other hand, the BHA-Ce mixture is prepared by adopting the following method, and specifically comprises the following steps:
mixing the Benzoic Hydroxamic Acid (BHA) and the cerium trichloride (CeCl) 3 ) Sequentially adding the mixture into deionized water, and uniformly mixing to obtain the BHA-Ce mixture.
Further, according to the technical scheme, the mass ratio of cerium trichloride to the benzoic hydroxamic acid is 1: 30-1: 20. if the concentration of Ce ions is too high, sediment is formed with the BHA directly, which is equivalent to consuming the BHA and has no effect of collecting.
Further, according to the above technical scheme, the stirring time is not particularly limited, so long as the uniform mixing and dissolution of the benzohydroxamic acid and the cerium trichloride in water can be realized. For example, the stirring time may be 30 minutes.
Specifically, according to the technical scheme, the BHA-Ce mixture can be used as a flotation collector by properly changing the concentration according to the flotation reagent system or the process requirement.
A third object of the present application is to provide the use of the BHA-Ce complex and/or BHA-Ce mixture described above for the flotation of fluorite in high calcium fluorite ores.
The solid complex or the liquid mixture of the collector provided by the application is consistent with the use method of the conventional flotation collector, the solid complex collector is soluble in water, the solid complex collector is mixed with the water according to the dosage requirement, the solid complex collector is fully dissolved by mechanical stirring and then added into the flotation operation, and the liquid mixture is directly added into the flotation operation according to the flotation dosage requirement. The BHA-Ce metal complex collector and the BHA-Ce mixture collector prepared by the method are not limited by seasonal room temperature conditions, but the solid complex is not more than 55 ℃ when dissolved and prepared, so that the performance of the collector is not reduced.
Compared with the prior art, the application has the following beneficial effects:
(1) The application provides a preparation process and a use method of a complex fluorite efficient collector BHA-Ce synthesized by organic matters and metal ions, wherein the collector mainly comprises Benzoic Hydroxamic Acid (BHA) and metal cerium ions (Ce) 3+ ) Is produced by the reaction of the soluble metal salt. In addition, the application also provides a preparation process and a use method of the BHA-Ce mixture. Since fluorite is calcium fluoride (CaF) 2 ) The dissociated surface of fluorite crystal breakage will have more F atoms exposed. Cerium ions have high affinity with fluoride ions, and can generate strong chemical adsorption. However, cerium ions do not react with gangue minerals such as calcite, dolomite, quartz, which are common to fluorite ores, mainly because the surfaces of these gangue minerals have no effective sites capable of adsorbing cerium ions. When the BHA-Ce complex and/or BHA-Ce mixture contacts the fluorite surface in the flotation solution environment, ce selectively adsorbs fluoride ions from the fluorite surface but does not adsorb other gangue minerals. The BHA ions at the other end play a role in hydrophobic effect so as to lead the fluorite surface to float upwards in a hydrophobic manner, thereby playing a role in high-selectivity collection.
(2) The application provides an effective solution to the problems of low selectivity, low sorting process index and the like of a high-calcium fluorite flotation collector in the prior art. The BHA-Ce metal complex and the BHA-Ce mixture synthesized by using the benzoic hydroxamic acid and the cerium trichloride as raw materials have excellent selectivity to fluorite, and the problems of poor selectivity, low flotation index and the like caused by taking calcium particles as adsorption sites in the traditional fluorite collector are effectively avoided. The synthetic preparation method of the BHA-Ce metal complex collector and the BHA-Ce mixture collector provided by the application is simple and feasible, has good performance and has no special requirements on the use environment.
(3) The application aims to provide a high-selectivity collector which can effectively float fluorite in fluorite ores with high calcium content, does not need to add acid or a large amount of inhibitors in the separation process, and is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the application, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a graph showing the IR spectrum of BHA-Ce complex prepared in example 1 of the present application and BHA;
FIG. 2 is a flow chart of the raw ore classification process in application example 1;
fig. 3 is a flow chart of the raw ore separation process in application example 2.
Detailed Description
The application is described in further detail below by way of examples. The present embodiment is implemented on the premise of the present technology, and a detailed embodiment and a specific operation procedure are now given to illustrate the inventive aspects of the present application, but the scope of protection of the present application is not limited to the following embodiments.
Various modifications to the precise description of the application will be readily apparent to those skilled in the art from the information contained herein. It is to be understood that the scope of the application is not limited to the defined processes, properties or components, as these embodiments, as well as other descriptions, are merely illustrative of specific aspects of the application.
For a better understanding of the present application, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless specifically indicated otherwise, the numerical parameters set forth in the specification are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The equipment and materials used in the present application are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The BHA-Ce metal complex of the embodiment is prepared by the following method, and specifically comprises the following steps:
first, 50mmol (6.857 g) of Benzoic Hydroxamic Acid (BHA) and 18.6235g of cerium trichloride (CeCl) were weighed out, respectively 3 ) Sequentially dissolved in 1000mL of methanol. The obtained mixed solution is stirred for 30min at the temperature of 55 ℃ in water bath, stirred at the normal temperature (24 ℃) for reaction for 5.0h, and then filtered. The obtained filtrate was crystallized by evaporation by a rotary evaporator for 24 hours at a temperature of not more than 55 ℃. White crystalline powder was obtained.
And (3) placing the white crystal powder into 500mL of ultrapure water, heating and stirring for 1 hour at the temperature of 55 ℃ in a water bath until the precipitate is not dissolved any more, filtering the hot solution to remove solid particles, standing and cooling the filtrate to room temperature to obtain precipitated white crystals, and naturally air-drying the white crystals obtained after filtering to obtain the pure Benzoic Hydroxamic Acid (BHA) -Ce metal complex. 14.4877g of product were finally obtained in a yield of approximately 56.86%.
The infrared spectrum comparison chart of the BHA-Ce complex synthesized in the example and the BHA is shown in FIG. 1. As can be seen from FIG. 1, comparing the infrared spectra of BHA, BHA-Ce showed a new characteristic peak of Ce-Cl bond around 600nm wavelength, indicating the presence of BHA-Ce complex.
Example 2
The BHA-Ce mixture of the embodiment is prepared by the following method, and specifically comprises the following steps:
cerium trichloride (CeCl) 3 ) And Benzoic Hydroxamic Acid (BHA) in a mass ratio of 1:30 are sequentially and directly mixed and stirred in deionized water for 30min to obtain the BHA-Ce mixture.
Comparative example 1
A BHA-Ce (molar ratio of BHA to Ce of 2:1) mixture of the comparative example was prepared by the following method, which specifically comprises the following steps:
cerium trichloride (CeCl) 3 ) And a molar ratio of Benzoic Hydroxamic Acid (BHA) of 1:2 are sequentially and directly mixed and stirred in deionized water for 30min to obtain a BHA-Ce (molar ratio of BHA to Ce is 2:1) mixture.
Application example 1
The BHA-Ce metal complex prepared in example 1, the BHA-Ce mixture prepared in comparative example 1 and oleic acid were respectively used as collectors for the flotation of fluorite in high-calcium fluorite ore, and the specific application method is as follows:
the sample of high-calcium fluorite ore is a calcite type high-calcium fluorite raw ore sample, wherein calcite (calcium carbonate CaCO) 3 ) The proportion is up to 32.8%, the fluorite grade is only about 8%, and the analysis of main components of the raw ore sample is shown in table 1. The process flow of the raw ore sorting is shown in figure 2.
Grinding raw ore until the particle size of-0.074 mm is 88%, adding the raw ore into a flotation tank, adding a proper amount of water, and stirring in a flotation machine. Firstly adding a pH regulator sodium bicarbonate, stirring for 3 minutes, regulating the pH of ore pulp to about 7.5, then sequentially adding gangue inhibitor acidified sodium silicate and sodium humate, stirring for 5 minutes, and then adding a collector, stirring for 3 minutes. In this application example, oleic acid, the BHA-Ce mixture prepared in comparative example 1, and the BHA-Ce metal complex prepared in example 1 were used as fluorite roughing collectors, respectively. When oleic acid was used as the collector, the flotation was started by aeration after stirring for 3 minutes with the addition of the collector, and the flotation time was 10 minutes. When the BHA-Ce mixture prepared in comparative example 1 or the BHA-Ce metal complex prepared in example 1 is used as a fluorite roughing collector, the collector is added and stirred for 3 minutes, then the foaming agent, the pine oil and the air are continuously added, and finally the flotation is started, wherein the flotation time is 10 minutes. And after the flotation is finished, obtaining a foam product, namely a fluorite rough concentrate product, and obtaining a pulp sand setting, namely a tailing product.
The acidified water glass in this application example was prepared by mixing 1500g sulfuric acid with 2200g water glass (sodium silicate) and stirring uniformly. In addition, the dosage of the acidified water glass adopted by the flotation by using three different collectors in the application example is 3700 g/ton (namely, the dosage of the acidified water glass required for treating 1 ton of high-calcium fluorite raw ore is 3700 g); the amount of sodium humate used in the flotation performed using three different collectors in this application example was 450 g/ton (i.e., 450 g for the 1 ton high calcium fluorite ore). In addition, the amount of oleic acid used in the present application example was 50 g/ton (i.e., the amount of oleic acid required for treating 1 ton of high-calcium fluorite raw ore was 50 g); the BHA-Ce mixture prepared in comparative example 1 was used in an amount of 320 g/ton (i.e., the BHA-Ce mixture prepared in comparative example 1 required to treat 1 ton of high calcium fluorite raw ore was used in an amount of 320 g); the amount of BHA-Ce metal complex prepared in example 1 was 320 g/ton (i.e., 320 g for BHA-Ce metal complex prepared in example 1 required to treat 1 ton of high calcium fluorite raw ore); the amount of foaming agent pinitol oil used when using the BHA-Ce mixture prepared in comparative example 1 or the BHA-Ce metal complex prepared in example 1, respectively, as a fluorite roughing collector was 50 g/ton (i.e., 50g needed to treat 1 ton of high-calcium fluorite raw ore). Other flotation conditions (e.g., pH adjuster, amount of inhibitor, etc.) were exactly the same, and flotation tests were performed separately, and the results are compared in table 2.
The data in Table 1 are obtained by XRF fluorescence semi-quantitative or chemical analysis, and the analysis results are from a detection mechanism with detection analysis qualification.
The grade results of the raw ore and fluorite rough concentrate in table 2 are obtained from the chemical analysis results of a detection mechanism with detection analysis qualification, and the recovery rates of tailings and all products are calculated according to a recovery rate calculation formula:
coarse concentrate CaF 2 Recovery = (coarse concentrate CaF 2 Grade x coarse concentrate yield)/(raw ore CaF 2 Grade x raw ore yield) x 100%;
tailing CaF 2 Recovery = (1-coarse concentrate CaF 2 Recovery) x 100%.
TABLE 1 analysis of principal Components of raw mineral samples
| Composition of the components | SiO 2 | Al 2 O 3 | CaCO 3 | MgO | K 2 O | Na 2 O | CaF 2 |
| Content of% | 17.61 | 20.54 | 32.8 | 11.27 | 0.79 | 3.48 | 8.00 |
| Composition of the components | BaO | S | Fe | As | |||
| Content of% | 1.10 | 0.004 | 0.42 | 0.01 |
Table 2 flotation test results
Table 2 shows that, compared with oleic acid, the use of BHA-Ce (including the BHA-Ce mixture prepared in comparative example 1 and the BHA-Ce metal complex prepared in example 1) as a collector significantly improves the coarse concentrate CaF 2 The grade can be ensured, and the recovery rate can be ensured, and the selectivity to fluorite is obviously higher than that of oleic acid. The collecting agent of the BHA-Ce mixture prepared in the comparative example 1 has very poor collecting capability on fluorite, and the recovery rate is about 27 percent lower than the sorting effect of oleic acid even under the condition of the same dosage of the BHA-Ce metal complex prepared in the example 1.
Application example 2
The BHA-Ce mixture prepared in example 2, the BHA-Ce mixture prepared in comparative example 1, and sodium oleate were applied as collectors to the flotation of fluorite in high-calcium fluorite ore, respectively, by the following methods:
the sample of high-calcium fluorite ore is a dolomite type high-calcium fluorite raw ore sample, wherein dolomite and calcite (calcium carbonate CaCO) 3 ) The proportion is up to 50%, the fluorite grade is about 32%, and the analysis of main components of the raw ore sample is shown in Table 3. The process flow of the raw ore sorting is shown in figure 3.
Grinding raw ore until the grain size of-0.074 mm is 92%, adding the raw ore into a flotation tank, adding a proper amount of water, and stirring in a flotation machine. Firstly adding a pH regulator sodium hydroxide, stirring for 3 minutes, regulating the pH of ore pulp to about 7.5, then sequentially adding gangue inhibitor acidified water glass, sodium humate and tannic acid, stirring for 5 minutes, and then adding a collector, stirring for 3 minutes. Sodium oleate, the BHA-Ce mixture prepared in comparative example 1 and the BHA-Ce mixture prepared in example 2 are respectively used as fluorite roughing collectors in the application example. When sodium oleate is used as a collector, the collector is added and stirred for 3 minutes, and then aeration starts to perform flotation, wherein the flotation time is 10 minutes. When the BHA-Ce mixture prepared in comparative example 1 or the BHA-Ce mixture prepared in example 2 is used as a fluorite roughing collector, the collector is added and stirred for 3 minutes, then the foaming agent, the pine oil, is added continuously, and finally, aeration is carried out, and flotation is started, wherein the flotation time is 10 minutes. And after the flotation is finished, obtaining a foam product, namely a fluorite rough concentrate product, and obtaining a pulp sand setting, namely a tailing product.
The acidified water glass is prepared by mixing 250g of sulfuric acid with 250 water glass (sodium silicate) and uniformly stirring.
In this application example, when three different collectors are used for flotation, the acidified water glass used is 500 g/ton, the sodium humate used is 100 g/ton (i.e., the sodium humate used for treating 1 ton of high-calcium fluorite raw ore is 100 g), and the tannic acid used is 200 g/ton (i.e., the tannic acid used for treating 1 ton of high-calcium fluorite raw ore is 200 g). The sodium oleate dosage in this application example is 65 g/ton (i.e. the sodium oleate dosage required for treating 1 ton of high calcium fluorite raw ore is 65 g); the BHA-Ce mixture prepared in comparative example 1 was used in an amount of 400 g/ton (i.e., 400 g for comparative example 1 required to treat 1 ton of high calcium fluorite raw ore); the BHA-Ce mixture prepared in example 2 was used in an amount of 400 g/ton (i.e., 400 g for the BHA-Ce mixture prepared in example 2 required to treat 1 ton of high calcium fluorite raw ore); the amount of foaming agent pinitol oil used when using the BHA-Ce mixture prepared in comparative example 1 or the BHA-Ce mixture prepared in example 2 as a fluorite roughing collector, respectively, was 50 g/ton (i.e., 50g needed to treat 1 ton of high-calcium fluorite raw ore). Other flotation conditions (e.g., pH adjuster, amount of inhibitor, etc.) were exactly the same, and flotation tests were performed separately, and the comparison of the results is shown in table 4.
The data in Table 3 are based on XRF fluorescence semi-quantitative or chemical analysis, with the analysis results from a detection facility qualified for detection analysis.
The fluorite rough concentrate and tailing grade results in table 4 are obtained from the chemical analysis results of a detection mechanism with detection analysis qualification, and the raw ore grade and the recovery rate of all products are calculated according to the following recovery rate calculation formula:
raw ore CaF 2 Grade= (concentrate CaF 2 Grade x coarse concentrate yield + tailings CaF 2 Grade x tailings yield)/raw ore yield x 100%;
coarse concentrate CaF 2 Recovery = (concentrate CaF 2 Grade x coarse concentrate yield)/(raw ore CaF 2 Grade x raw ore yield) x 100%;
tailing CaF 2 Recovery = (1-coarse concentrate CaF 2 Recovery) x 100%.
TABLE 3 analysis of principal Components of raw mineral samples
| Composition of the components | SiO 2 | Al 2 O 3 | CaCO 3 | MgO | K 2 O | Na 2 O | CaF 2 |
| Content of% | 2.66 | 7.10 | 50 | 3.27 | 1.07 | 2.77 | 32.34 |
| Composition of the components | BaO | Li 2 O | Fe 2 O 3 | P 2 O 5 | |||
| Content of% | 0.013 | 0.02 | 0.07 | 0.02 |
Table 4 flotation test results
Table 4 shows that, compared with sodium oleate, the BHA-Ce mixture prepared in example 2 is used as collector to raise CaF of coarse concentrate 2 The grade can be ensured, and the recovery rate can be ensured, and the selectivity to fluorite is obviously higher than that of sodium oleate. The collecting agent of the BHA-Ce mixture prepared in comparative example 1 has very poor collecting capability on fluorite, and the recovery rate is about 45 percent lower than that of the BHA-Ce mixture prepared in example 2, and even far lower than the sorting effect of sodium oleate.
The standard for selectivity is usually reference to grade rather than recovery rate, the recovery rate is generally used as the judging basis of the collecting capacity of the collector, the grade of sodium oleate rough concentrate is only 43.68%, and the grade of the rough concentrate of the BHA-Ce mixture prepared in example 2 reaches 52.91%, and the grade is improved by nearly 10%.
Claims (8)
1. The utility model provides a high-efficient collector which characterized in that: the collector is a Benzalkonium Hydroxamic Acid (BHA) -Ce metal complex or a BHA-Ce mixture.
2. The method for preparing the BHA-Ce metal complex according to claim 1, wherein: the method specifically comprises the following steps:
mixing the Benzoic Hydroxamic Acid (BHA) and the cerium trichloride (CeCl) 3 ) Sequentially dissolving in organic solventStirring and uniformly mixing the obtained mixed solution at 45-55 ℃, and stirring and reacting the obtained uniform mixed solution at 10-55 ℃ for 4-6 h; and after the reaction is finished, filtering the obtained product, volatilizing or evaporating the solvent in the obtained filtrate completely to obtain white crystal powder, and purifying to obtain the BHA-Ce metal complex.
3. The method according to claim 2, characterized in that: the mass ratio of the cerium trichloride to the benzoic hydroxamic acid is about (1-3): 1.
4. The method according to claim 2, characterized in that: the dosage of the benzohydroxamic acid and the organic solvent is 1mmol: (20-50) mL.
5. The method according to claim 2, characterized in that: the solvent in the obtained filtrate is evaporated at a temperature not exceeding 55 ℃.
6. A process for preparing a BHA-Ce mixture according to claim 1, wherein: the method specifically comprises the following steps:
mixing the Benzoic Hydroxamic Acid (BHA) and the cerium trichloride (CeCl) 3 ) Sequentially adding the mixture into deionized water, and uniformly mixing to obtain the BHA-Ce mixture.
7. The method according to claim 6, wherein: the mass ratio of cerium trichloride to the benzoic hydroxamic acid is 1: 30-1: 20.
8. use of the high efficiency collector of claim 1 or the BHA-Ce metal complex prepared by the method of claims 2 to 5 or the BHA-Ce mixture prepared by the method of claims 6 to 7 for the flotation of fluorite in high calcium fluorite ores.
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