CN115625042B - Lead depressant in copper-lead mixed concentrate separation flotation and its preparation method and application - Google Patents
Lead depressant in copper-lead mixed concentrate separation flotation and its preparation method and application Download PDFInfo
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- CN115625042B CN115625042B CN202211097460.1A CN202211097460A CN115625042B CN 115625042 B CN115625042 B CN 115625042B CN 202211097460 A CN202211097460 A CN 202211097460A CN 115625042 B CN115625042 B CN 115625042B
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- lead
- copper
- cyclodextrin
- inhibitor
- concentrate
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- 239000012141 concentrate Substances 0.000 title claims abstract description 92
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000005188 flotation Methods 0.000 title claims abstract description 53
- 238000000926 separation method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000000994 depressogenic effect Effects 0.000 title abstract 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 87
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 36
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 36
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 36
- 229960004853 betadex Drugs 0.000 claims abstract description 36
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 26
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 14
- -1 cyclic anhydride Chemical class 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032050 esterification Effects 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 239000003112 inhibitor Substances 0.000 claims description 116
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 50
- 229910052802 copper Inorganic materials 0.000 claims description 50
- 239000010949 copper Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 23
- 230000002000 scavenging effect Effects 0.000 claims description 23
- 239000004088 foaming agent Substances 0.000 claims description 21
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003586 protic polar solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 14
- 230000005764 inhibitory process Effects 0.000 abstract description 9
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001779 copper mineral Inorganic materials 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052951 chalcopyrite Inorganic materials 0.000 description 3
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 3
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical group O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052947 chalcocite Inorganic materials 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229940056932 lead sulfide Drugs 0.000 description 2
- 229910052981 lead sulfide Inorganic materials 0.000 description 2
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- CMGLSTYFWSQNEC-UHFFFAOYSA-N o-ethyl n-ethylcarbamothioate Chemical compound CCNC(=S)OCC CMGLSTYFWSQNEC-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010887 waste solvent 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
- B03D1/02—Froth-flotation processes
- B03D1/025—Froth-flotation processes adapted for the flotation of fines
-
- 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
- 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
本申请提供一种铜铅混合精矿分离浮选中的铅抑制剂及其制备方法与应用，包括：以β‑环糊精为原料和改性剂发生酯化，制得改性β‑环糊精；改性剂为二元羧酸形成的环状酸酐；按重量份，将50～100份改性β‑环糊精与10～20份无水硅酸钠混合均匀，即制得铅抑制剂。本申请制备的铅抑制剂以无水硅酸钠和改性β‑环糊精为主要成分，避免了传统重铬酸盐剧毒性以及污染环境的缺点；改性β‑环糊精和无水硅酸钠可提高对铅矿的选择性；本申请的铅抑制剂在弱碱性条件下使用，可避免酸性条件对设备腐蚀的问题。此外，本申请提供的铅抑制剂还具有低成本、易于存储、抑制效果佳、使用量小、不会对浮选后的精矿产生污染的特点。
The present application provides a lead depressant in the separation flotation of copper-lead mixed concentrate and its preparation method and application, including: using β-cyclodextrin as a raw material and a modifier for esterification to obtain modified β-cyclodextrin; the modifier is a cyclic anhydride formed by a dicarboxylic acid; 50 to 100 parts of modified β-cyclodextrin and 10 to 20 parts of anhydrous sodium silicate are mixed uniformly by weight to obtain a lead depressant. The lead depressant prepared in the present application uses anhydrous sodium silicate and modified β-cyclodextrin as the main components, avoiding the shortcomings of the traditional dichromate toxicity and environmental pollution; modified β-cyclodextrin and anhydrous sodium silicate can improve the selectivity for lead ore; the lead depressant of the present application is used under weakly alkaline conditions to avoid the problem of acidic conditions corroding the equipment. In addition, the lead depressant provided in the present application also has the characteristics of low cost, easy storage, good inhibition effect, small usage, and no pollution to the concentrate after flotation.
Description
Technical Field
The application relates to the technical field of mineral flotation, in particular to a lead inhibitor for copper-lead bulk concentrate separation flotation and a preparation method and application thereof.
Background
In nature, there are many copper minerals that have been found, but only over ten have been reported to be of industrial use. Copper and lead belong to copper ion structures and copper metal belongs to a sulfur-philic element group according to the geochemical property, so copper minerals and lead minerals mostly appear in the form of copper sulfide ores and lead sulfide ores in nature. Copper minerals can be classified into primary copper sulphide ores (e.g. chalcopyrite), secondary copper sulphide ores (e.g. chalcocite) and copper oxide ores (e.g. malachite) according to chemical composition and cause. Among the copper sulphides, chalcopyrite and chalcocite are the predominant and more common. Galena (PbS), which is the primary mineral, is the most essential constituent mineral of lead sulfide ores, and has very wide distribution.
The ores containing copper sulfide and lead are called complex sulfide ores, the mineral composition of the ores is extremely complex, the symbiotic relationship among the minerals is compact, the content fluctuation range of valuable components is large, the structure is various, and the variation range of the embedding granularity is large. They are refractory ores, the ore forming conditions of which have a controlled effect on the selectivity of the ores, and often very complex ore dressing processes are used for the treatment of such ores.
Aiming at complex copper-lead ores with non-uniform embedded minerals or compact symbiosis with each other, because the surface properties of copper and lead ores are similar, floatability is extremely similar, a method of separating copper concentrate from lead concentrate after copper-lead mixed concentrate is obtained by mixing and floating copper and lead ores is generally adopted, and the methods of separating copper concentrate from lead concentrate are a lead-inhibition copper-floatation method and a copper-inhibition lead-floatation method. The general principle is that lead is inhibited from floating copper when the lead content in the ore is much higher than copper, whereas copper is inhibited from floating lead when the copper content is close to or more than lead.
Among the existing methods for suppressing lead and floating copper, two main types are inorganic lead inhibitors and organic lead inhibitors, wherein one type of reagent in the inorganic lead inhibitors is dichromate, and the dichromate has no influence on the flotation of copper minerals, so that the reagent is one of the most studied reagents. However, the dichromate needs to strictly control the pH value when in use, and the hexavalent chromium is extremely toxic and pollutes the environment, and the other reagent in the inorganic lead inhibitor is represented by sulfite or pyrophosphate, but the sulfite and the pyrophosphate need to be used under the condition of acidic ore pulp, so that the defects of equipment corrosion and stable production influence exist.
Among the organolead inhibitors, carboxymethyl cellulose is used in many cases, and the organolead inhibitor is easy to control, but has the disadvantage of poor selectivity.
Disclosure of Invention
The application provides a lead inhibitor for copper-lead bulk concentrate separation flotation, and a preparation method and application thereof, which are used for solving the problems that the lead inhibitor for the existing copper-lead bulk concentrate separation flotation has high toxicity, can corrode equipment when used in an acidic condition and has poor selectivity.
The application provides a preparation method of a lead inhibitor in copper-lead bulk concentrate separation and flotation, which comprises the steps of esterifying beta-cyclodextrin serving as a raw material and a modifier to prepare modified beta-cyclodextrin, wherein the modifier is annular anhydride formed by dicarboxylic acid, and uniformly mixing 50-100 parts of modified beta-cyclodextrin and 10-20 parts of anhydrous sodium silicate according to parts by weight to prepare the lead inhibitor.
According to the preparation method of the lead inhibitor, beta-cyclodextrin is used as a raw material, the beta-cyclodextrin reacts with cyclic anhydride to prepare the modified beta-cyclodextrin containing carboxyl and hydroxyl in molecules, the carboxyl on the modified beta-cyclodextrin and PbOH + on the surface of lead ore are utilized to generate electrostatic action, the hydroxyl on the modified beta-cyclodextrin and HPbO 2- on the surface of lead ore generate hydrogen bond action, and the cavity and hydroxyl of the modified beta-cyclodextrin are chelated with Pb 2+ on the surface of lead ore, so that the modified beta-cyclodextrin is adsorbed on the surface of lead ore, and the surface of the modified beta-cyclodextrin adsorbed on the surface of lead ore contains hydroxyl and carboxyl, so that a water film is formed on the surface of lead ore, lead ore is inhibited from floating upwards, and the modified beta-cyclodextrin has no influence on the floating of copper ore, so that copper and lead are separated during flotation.
The anhydrous sodium silicate can generate hydrophilic lead silicate with lead ions on the surface of the lead ore to form a water film, so that the hydrophilicity of the lead ore is increased, the floatability of the lead ore is inhibited, and the inhibition effect of the anhydrous sodium silicate and the modified beta-cyclodextrin on the lead ore can be enhanced in a synergistic manner. The method of the application takes the beta-cyclodextrin as the raw material, has the advantages of low raw material price and easy acquisition, and the method for preparing the lead inhibitor is easy to operate, has few synthesis steps and is easy to purify.
The lead inhibitor prepared by the application takes anhydrous sodium silicate and modified beta-cyclodextrin as main components, avoids the defects of severe toxicity and environmental pollution of the traditional dichromate, combines carboxyl and hydroxyl on the modified beta-cyclodextrin with ions and lead salt ions on the surface of lead ores, can also comprise or complex the lead salt ions and lead ions in holes of the modified beta-cyclodextrin so as to inhibit the floatability of the lead ores without affecting the floatability of copper ores, can form water-soluble lead silicate on the surface of the lead ores to form a water film with the sodium silicate and the lead ions, inhibits the floatability of the lead ores, and can improve the selectivity of the modified beta-cyclodextrin and the anhydrous sodium silicate on the lead ores.
Optionally, the structural formula of the modifier is:
Wherein R is n=1~8。
Optionally, the above-mentioned raw materials of beta-cyclodextrin and modifier take place the esterification, prepare modified beta-cyclodextrin, including the following steps:
S101, adding beta-cyclodextrin and a modifier into a reaction container, and uniformly mixing to obtain a substrate mixed system;
S102, heating a substrate mixed system to 85-92 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 5-10 min;
S103, after the reaction is finished, rapidly adding water into the reaction liquid, cooling to room temperature and filtering;
S104, recrystallizing the filter cake obtained by filtering in the S103 by using a polar proton solvent, filtering again, taking the filter cake, and drying at the constant temperature of 40-50 ℃ for 1-2 h under the pressure of-0.06 to-0.09 mpa to obtain the modified beta-cyclodextrin.
Alternatively, the molar ratio of beta-cyclodextrin to modifier is 1: 7~1:8.4;
The concentration of the concentrated sulfuric acid is 95-98%, and the consumption of the concentrated sulfuric acid is 0.5-1% of the mass of the substrate mixed system. In the application, concentrated sulfuric acid is used as a catalyst to play a role in breaking hydrogen bonds between beta-cyclodextrin hydroxyl groups and dehydrating.
Optionally, the polar protic solvent is one or more of water, methanol, ethanol, propanol, or isopropanol.
In a second aspect, the application provides a lead inhibitor for copper-lead bulk concentrate separation flotation, which is prepared by the method in the first aspect, wherein the modified beta-cyclodextrin has the structural formula:
Wherein R 1、R2、R3、R4、R5、R6、R7 is hydroxy or
R isn=1~8。
The modified beta-cyclodextrin has the characteristics that the beta-cyclodextrin has the characteristic that holes can complex or contain lead ions and the characteristic that modified groups are easy to complex lead ions and lead salt ions on the surface of lead ores, and can be quickly complexed or combined with lead ions on the surface of the lead ores by utilizing the hydrophilia of hydroxyl groups and carboxyl groups and the characteristics of the holes of the beta-cyclodextrin, so that the modified beta-cyclodextrin can be attached to the surface of the lead ores, form a hydrophilic film and inhibit the floating of the lead ores during flotation, and the anhydrous sodium silicate and the surface of the lead ores form hydrophilic lead silicate and further inhibit the flotation of the lead ores. Therefore, the lead inhibitor of the application takes the modified beta-cyclodextrin as the main component and is matched with anhydrous sodium silicate, has the characteristics of easy water dissolution, easy preparation, low cost and no toxicity, and also has the characteristic of short precipitation time.
Optionally, the lead inhibitor further comprises 15-25 parts of aluminum sulfate. Aluminum sulfate is added into the lead inhibitor, aluminum ions in the aluminum sulfate can be hydrolyzed in a solution, particularly in a weak alkaline condition to form aluminum hydroxide, and colloidal precipitation generated after the aluminum sulfate is hydrolyzed can effectively adsorb and flocculate lead ore particles to accelerate the precipitation of lead ore.
The application provides an application of a lead inhibitor in copper-lead bulk concentrate separation and flotation, which comprises the following steps of preparing the lead inhibitor into a solution with the mass concentration of 1-10% and then adding the solution.
The lead inhibitor is applied to the separation flotation of copper-lead bulk concentrates, has good effect of inhibiting lead ores, and can replace the traditional extremely toxic dichromate which pollutes the environment.
In a fourth aspect, the application provides a method for using a lead inhibitor in copper-lead bulk concentrate separation flotation, wherein the lead inhibitor is added in roughing, concentration and scavenging in the copper-lead bulk concentrate flotation separation process, and the flotation separation process comprises one roughing, three concentration and one scavenging.
The lead inhibitor in the copper-lead bulk concentrate separation flotation has the advantages of no pollution to the environment, small dosage, high selectivity to lead ores and good inhibition performance in the use process.
Optionally, the flotation separation process comprises the steps of
A) Adding calcium oxide into a ball mill according to the dry weight of each ton of copper-lead mixed concentrate, adding the copper-lead mixed concentrate and water into the ball mill according to the proportion of 1:1 for grinding until the grinding fineness of the discharged materials of the ball mill is not more than 0.074mm and accounts for 75-80%, and the pH value of ore pulp is 7.0-12.0;
b) Adding a lead inhibitor, a collector Z200 (ethyl thiourethane, chemical name: O-isopropyl-N-ethyl thiourethane) and a MIBC foaming agent (methyl isobutyl carbinol, chemical name: 1, 3-dimethylbutanol) into ore pulp, and performing primary roughing to obtain copper rough concentrate and copper rough tailings, wherein the usage amount of the lead inhibitor is 100-500 g/t, the usage amount of the collector Z200 is 10-50 g/t and the usage amount of the MIBC foaming agent is 40-60 g/t;
c) The copper rough concentrate is subjected to three-time concentration to obtain copper concentrate, wherein the first concentration is added with 100-300 g/t of lead inhibitor, 200-40 g/t of collector Z and 40-60 g/t of MIBC foaming agent, the second concentration is added with 200-400 g/t of lead inhibitor and 200-50 g/t of collector Z, and the third concentration is added with 300-500 g/t of lead inhibitor;
d) The method comprises the steps of (1) carrying out primary scavenging on copper roughing tailings to obtain lead concentrate, wherein 300-450 g/t of a lead inhibitor, 200-45 g/t of a collector Z and 50-60 g/t of a MIBC foaming agent are added in the scavenging process;
e) Middlings produced in each step of fine selection and scavenging are returned to the previous step in sequence.
The lead inhibitor for copper-lead bulk concentrate separation and flotation, and the preparation method and application thereof provided by the application have the following beneficial effects that the modified beta-cyclodextrin introduced with carboxyl is used as a main component, and the lead inhibitor is obtained by matching with anhydrous sodium silicate:
1) The preparation method of the lead inhibitor can prepare the target compound-modified beta-cyclodextrin through one-step reaction, has the characteristics of short synthesis step, easiness in operation, low requirements on equipment, simple and easy operation of a product purification method, and low cost and easiness in acquisition of raw material beta-cyclodextrin, thus having low preparation cost.
2) The lead inhibitor provided by the application has the characteristics of no toxicity, low cost and environmental friendliness, and the main components of the modified beta-cyclodextrin and anhydrous sodium silicate can form a water film on the surface of lead ore to inhibit the floatability of the lead ore without affecting the floatability of copper ore, so that the lead inhibitor has the characteristic of good separation effect. The main component of the modified beta-cyclodextrin is easy to prepare and purify, and the finished lead inhibitor is nonflammable, explosion-proof, dangerous and easy to store.
3) The lead inhibitor provided by the application is used under the weak alkaline condition, so that corrosion of acidic use conditions to equipment is avoided, the inhibition effect on lead ore is good, the selectivity is good, pollution to concentrate after flotation is avoided, and the lead inhibitor can completely replace dichromate to be an excellent lead ore inhibitor in copper-lead mixed concentrate separation flotation.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions of 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 some embodiments of the present application, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a closed-loop test process provided in experimental example 2 of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are also within the scope of the application.
In a first aspect, the application provides a method for preparing a lead inhibitor in copper-lead bulk concentrate separation flotation, comprising the following steps:
the beta-cyclodextrin is taken as a raw material and esterified with a modifier to prepare modified beta-cyclodextrin, wherein the modifier is cyclic anhydride formed by dicarboxylic acid;
and uniformly mixing 50-100 parts by weight of modified beta-cyclodextrin and 10-20 parts by weight of anhydrous sodium silicate to obtain the lead inhibitor.
Optionally, the structural formula of the modifier is:
Wherein R is n=1~8。
Preferably, n=1 to 3, i.e. the modifier is malonic anhydride, succinic anhydride or glutaric anhydride, because these three anhydrides are easy to obtain and cheap, and the carbon chain is short, and the combination with the surface of lead ore is stable.
In the application, the modifier is acid anhydride formed by dicarboxylic acid, in the reaction with beta-cyclodextrin, ring opening can be hydrolyzed, one molecule of carboxylic acid and hydroxyl on the beta-cyclodextrin generate ester, and then the carboxyl of the other molecule is in a free state, so that carboxyl is introduced into the beta-cyclodextrin, and compared with acid anhydride or dicarboxylic acid formed by monocarboxylic acid, the acid anhydride formed by dicarboxylic acid is used as the modifier, not only can carboxyl be introduced into the beta-cyclodextrin, but also no carboxylic acid is free after the reaction to cause resource waste, and the reaction selectivity is high, so that the acid anhydride formed by dicarboxylic acid is used as the modifier, and the method has the advantage of high atom utilization rate.
Alternatively, the structure of the modifier is specifically such as:
Etc.
Optionally, in another possible implementation, the method for preparing the lead inhibitor includes the steps of:
S101, adding beta-cyclodextrin and a modifier into a reaction container, and uniformly mixing to obtain a substrate mixed system;
S102, heating a substrate mixed system to 85-92 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 5-10 min;
S103, after the reaction is finished, rapidly adding water with the volume of 2-5 times of the volume of the reaction solution into the reaction solution, cooling to room temperature, and filtering;
S104, recrystallizing the filter cake obtained by filtering in the S103 by using a polar proton solvent, filtering again, taking the filter cake, and drying at the constant temperature of 40-50 ℃ for 1-2 h under the pressure of-0.06 to-0.09 mpa to obtain the modified beta-cyclodextrin.
And S105, uniformly mixing 50-100 parts by weight of modified beta-cyclodextrin, 15-25 parts by weight of aluminum sulfate and 10-20 parts by weight of anhydrous sodium silicate to obtain the lead inhibitor.
The method has the characteristics of short synthesis steps, easy operation, cheap and easily obtained reaction raw materials, no other organic solvent used in the reaction process, easy separation and purification, and recycling of the concentrated sulfuric acid used in the reaction process, thus having low cost, easy operation in the post-treatment process of the reaction, and almost no waste solvent.
In the application, aluminum sulfate is also added in the lead inhibitor, aluminum ions in the aluminum sulfate can be hydrolyzed in the solution to form hydrophilic aluminum hydroxide, and the aluminum hydroxide and lead ions on the surface of lead ore form a water film by electrostatic force or hydrogen bonding, thereby playing a role in inhibition, and colloid-shaped precipitate generated after the aluminum sulfate is hydrolyzed can effectively adsorb and flocculate lead ore particles, so that the precipitation of lead ore is accelerated.
Optionally, the mol ratio of the beta-cyclodextrin to the modifier is 1: 7~1:8.4, the concentration of the concentrated sulfuric acid is 95-98%, and the dosage of the concentrated sulfuric acid is 0.5-1% of the mass of the substrate mixed system. In the application, concentrated sulfuric acid is used as a catalyst to play a role in breaking hydrogen bonds between beta-cyclodextrin hydroxyl groups and dehydrating.
Optionally, the polar protic solvent is one or more of water, methanol, ethanol, propanol, or isopropanol.
In a second aspect, the application provides a lead inhibitor for copper-lead bulk concentrate separation and flotation, comprising anhydrous sodium silicate and modified beta-cyclodextrin prepared by the method of the first aspect, wherein the modified beta-cyclodextrin has the structural formula:
wherein R1, R2, R3, R4, R5, R6, R 7 are hydroxy or R isn=1~8;
50-100 Parts of modified beta-cyclodextrin and 10-20 parts of anhydrous sodium silicate.
In the application, the body of the beta-cyclodextrin has the characteristic of 'inner hydrophobic and outer hydrophilic', carboxyl and hydroxyl in the beta-cyclodextrin are modified, the groups can be combined with the surface of lead ore through electrostatic action or hydrogen bond, the hydroxyl outside the beta-cyclodextrin is combined with water molecules through hydrogen bond to form a water film, the beta-cyclodextrin body has a cavity structure and can be complexed with ions on the surface of lead ore, the modified beta-cyclodextrin molecules are combined to the surface of lead ore, so that the hydrophilicity of the lead ore is increased, and anhydrous sodium silicate can generate hydrophilic lead silicate with lead ions on the surface of lead ore to form the water film. Therefore, the lead inhibitor provided by the application can form a water film by combining the inhibitor and the surface of the lead ore, so that the hydrophilicity of the lead ore is increased, the floatability of the lead ore is inhibited, and the inhibition effect on the lead ore can be enhanced by the cooperation of the anhydrous sodium silicate and the modified beta-cyclodextrin.
Optionally, the lead inhibitor further comprises 15-25 parts of aluminum sulfate.
In the application, aluminum sulfate is also added in the lead inhibitor, aluminum ions in the aluminum sulfate can be hydrolyzed in the solution to form hydrophilic aluminum hydroxide, and the aluminum hydroxide and lead ions on the surface of lead ore form a water film by electrostatic force or hydrogen bonding, thereby playing a role in inhibition, and colloid-shaped precipitate generated after the aluminum sulfate is hydrolyzed can effectively adsorb and flocculate lead ore particles, so that the precipitation of lead ore is accelerated.
Optionally, the flotation separation process comprises the steps of:
a) Adding calcium oxide into a ball mill according to the dry weight of each ton of copper-lead mixed concentrate, adding the copper-lead mixed concentrate and water into the ball mill according to the proportion of 1:1 for grinding until the grinding fineness of the discharged materials of the ball mill is not more than 0.074mm and accounts for 75-80%, and the pH value of ore pulp is 7.0-12.0;
b) Adding a lead inhibitor, a collector Z200 and a MIBC foaming agent into ore pulp, and obtaining copper rough concentrate and copper rough tailings after primary roughing, wherein the use amount of the lead inhibitor is 100-500 g/t, the use amount of the collector Z200 is 10-50 g/t and the use amount of the MIBC foaming agent is 40-60 g/t;
c) The copper rough concentrate is subjected to three-time concentration to obtain copper concentrate, wherein the first concentration is added with 100-300 g/t of lead inhibitor, 200-40 g/t of collector Z and 40-60 g/t of MIBC foaming agent, the second concentration is added with 200-400 g/t of lead inhibitor and 200-50 g/t of collector Z, and the third concentration is added with 300-500 g/t of lead inhibitor;
d) The method comprises the steps of (1) carrying out primary scavenging on copper roughing tailings to obtain lead concentrate, wherein 300-450 g/t of a lead inhibitor, 200-45 g/t of a collector Z and 50-60 g/t of a MIBC foaming agent are added in the scavenging process;
e) Middlings produced in each step of fine selection and scavenging are returned to the previous step in sequence.
In the application, before the roughing step, the copper-lead mixed concentrate is required to be subjected to the reagent removing treatment. Optionally, the drug removal treatment in the drug removal mode adopts stirring, washing and drug removal or active carbon drug removal.
The steps of stirring, washing and removing the chemicals include adding water into copper-lead mixed concentrate to be floated according to the solid-to-liquid ratio of 1:1-1:2 to prepare ore pulp, stirring at the rotating speed of 300-400 rpm for 0.5-1.5 h, filtering, and washing filter cakes with clear water with the mass of 1.2-2 times of that of the copper-lead mixed concentrate for 3 times after filtering, thus finishing the chemical removal.
The active carbon stripping is that 1000-1400 g/t active carbon is added into copper-lead mixed concentrate to be floated, and then the mixture is stirred for 10-30min at the rotating speed of 600-800 rpm, thus the stripping is completed.
In a specific example, the drug removal treatment can also adopt at least one of regrinding, sodium sulfide drug removal, sodium sulfide and active carbon combined drug removal and heating drug removal.
The present invention will be described in further detail with reference to examples.
Example 1:
a preparation method of a lead inhibitor in copper-lead bulk concentrate separation flotation comprises the following steps:
1) Adding beta-cyclodextrin and succinic anhydride into a reaction container, and uniformly mixing to obtain a substrate mixed system, wherein the molar ratio of the beta-cyclodextrin to the succinic anhydride is 1:7.8;
2) Heating the substrate mixed system to 85 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 10min, wherein the concentration of the concentrated sulfuric acid is 98%, and the dosage of the concentrated sulfuric acid is 0.5% of the mass of the substrate mixed system.
3) After the reaction is finished, water with the volume 3 times of that of the reaction solution is rapidly added into the reaction solution, cooled to room temperature and filtered;
4) And 3) recrystallizing the filter cake obtained in the step 3) with water, filtering again, taking the filter cake, and drying at the constant temperature of 40 ℃ under the pressure of-0.06 mpa for 2 hours to obtain the modified beta-cyclodextrin.
5) And (3) taking 75 parts of modified beta-cyclodextrin and 15 parts of anhydrous sodium silicate according to parts by weight, and uniformly mixing to obtain the lead inhibitor.
Example 2:
a preparation method of a lead inhibitor in copper-lead bulk concentrate separation flotation comprises the following steps:
1) Adding beta-cyclodextrin and malonic anhydride into a reaction container, and uniformly mixing to obtain a substrate mixed system, wherein the molar ratio of the beta-cyclodextrin to the malonic anhydride is 1:8.4;
2) Heating the substrate mixed system to 92 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 5min, wherein the concentration of the concentrated sulfuric acid is 96%, and the dosage of the concentrated sulfuric acid is 0.8% of the mass of the substrate mixed system.
3) After the reaction is finished, water with the volume 2 times of that of the reaction solution is rapidly added into the reaction solution, cooled to room temperature and filtered;
4) And 3) recrystallizing the filter cake obtained in the step 3) with methanol, filtering again, taking the filter cake, and drying at the constant temperature of 50 ℃ under the pressure of-0.09 mpa for 1h to obtain the modified beta-cyclodextrin.
5) According to the weight parts, 100 parts of modified beta-cyclodextrin and 10 parts of anhydrous sodium silicate are taken and uniformly mixed to obtain the lead inhibitor.
Example 3:
a preparation method of a lead inhibitor in copper-lead bulk concentrate separation flotation comprises the following steps:
1) Adding beta-cyclodextrin and glutaric anhydride into a reaction vessel, and uniformly mixing to obtain a substrate mixed system, wherein the molar ratio of the beta-cyclodextrin to the glutaric anhydride is 1:7;
2) Heating the substrate mixed system to 87 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 10min, wherein the concentration of the concentrated sulfuric acid is 95%, and the dosage of the concentrated sulfuric acid is 1% of the mass of the substrate mixed system.
3) After the reaction is finished, water with the volume 4 times of that of the reaction solution is rapidly added into the reaction solution, cooled to room temperature and filtered;
4) And 3) recrystallizing the filter cake obtained in the step 3) with ethanol, filtering again, taking the filter cake, and drying at the constant temperature of 40-50 ℃ for 1-2 h under the pressure of-0.06 mpa to obtain the modified beta-cyclodextrin.
5) And (3) taking 75 parts of modified beta-cyclodextrin and 15 parts of anhydrous sodium silicate according to parts by weight, and uniformly mixing to obtain the lead inhibitor.
Example 4:
the method for preparing the lead inhibitor in the separation and flotation of copper-lead bulk concentrate is different from example 1 in that:
22 parts of aluminum sulfate are also added during the mixing in step 5).
Example 5:
the application method of the lead inhibitor in the separation and flotation of the copper-lead bulk concentrate comprises the following steps:
1) Adding calcium oxide into a ball mill according to the dry weight of each ton of copper-lead mixed concentrate, adding the copper-lead mixed concentrate and water into the ball mill according to the proportion of 1:1 for grinding until the grinding fineness of the discharged materials of the ball mill is not more than 0.074mm and accounts for 75-80%, and the pH value of ore pulp is 9.0;
2) Adding the lead inhibitor, the collector Z200 and the MIBC foaming agent obtained in the embodiment 1 into ore pulp, and carrying out primary roughing to obtain copper rough concentrate and copper rough tailings, wherein the use amount of the lead inhibitor is 500g/t, the use amount of the collector Z200 is 50g/t and the use amount of the MIBC foaming agent is 40g/t;
3) The copper rough concentrate is subjected to three-time concentration to obtain copper concentrate, wherein 300g/t of lead inhibitor, 200 g/t of collector Z and 40-60 g/t of MIBC foaming agent are added in the first concentration, 400g/t of lead inhibitor and 200 50g/t of collector Z are added in the second concentration, and 300g/t of lead inhibitor is added in the third concentration;
4) The copper roughing tailings are subjected to primary scavenging to obtain lead concentrate, wherein 450g/t of lead inhibitor, 200 g/t of collector Z and 60g/t of MIBC foaming agent are added in the scavenging process;
5) Middlings produced in each step of fine selection and scavenging are returned to the previous step in sequence.
Example 6:
The method of using the lead inhibitor in the separation and flotation of copper-lead bulk concentrates differs from example 5 only in that the lead inhibitor used in the primary roughing, tertiary beneficiation and secondary scavenging steps was prepared in example 4.
Example 7:
the application method of the lead inhibitor in the separation and flotation of the copper-lead bulk concentrate comprises the following steps:
1) Adding beta-cyclodextrin and a modifier into a reaction container, and uniformly mixing to obtain a substrate mixed system, wherein the molar ratio of the beta-cyclodextrin to the succinic anhydride is 1:7.8;
2) Heating the substrate mixed system to 85 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 10min, wherein the concentration of the concentrated sulfuric acid is 98%, and the dosage of the concentrated sulfuric acid is 0.5% of the mass of the substrate mixed system.
3) After the reaction is finished, water with the volume 5 times of that of the reaction solution is rapidly added into the reaction solution, cooled to room temperature and filtered;
4) And 3) recrystallizing the filter cake obtained in the step 3) with water, filtering again, taking the filter cake, and drying at the constant temperature of 40 ℃ under the pressure of-0.06 mpa for 2 hours to obtain the modified beta-cyclodextrin.
5) And (3) taking 75 parts of modified beta-cyclodextrin and 15 parts of anhydrous sodium silicate according to parts by weight, and uniformly mixing to obtain the lead inhibitor.
6) Adding water into copper-lead mixed concentrate to be floated according to the solid-liquid ratio of 1:2 to prepare ore pulp, stirring for 0.5h at the rotating speed of 400rpm, filtering, and washing filter cakes for 3 times by using clear water with the mass of 2 times of the copper-lead mixed concentrate after filtering, thus finishing the removal of the drugs.
7) Adding calcium oxide into a ball mill according to the dry weight of each ton of copper-lead mixed concentrate, adding the copper-lead mixed concentrate and water into the ball mill according to the proportion of 1:1 for grinding until the grinding fineness of the discharged materials of the ball mill is not more than 0.074mm and accounts for 75-80%, and the pH value of ore pulp is 9.0;
8) Adding the lead inhibitor, the collector Z200 and the MIBC foaming agent obtained in the embodiment 1 into ore pulp, and carrying out primary roughing to obtain copper rough concentrate and copper rough tailings, wherein the use amount of the lead inhibitor is 500g/t, the use amount of the collector Z200 is 50g/t and the use amount of the MIBC foaming agent is 40g/t;
9) The copper rough concentrate is subjected to three-time concentration to obtain copper concentrate, wherein 300g/t of lead inhibitor, 200 g/t of collector Z and 40-60 g/t of MIBC foaming agent are added in the first concentration, 400g/t of lead inhibitor and 200 50g/t of collector Z are added in the second concentration, and 300g/t of lead inhibitor is added in the third concentration;
10 The copper roughing tailings are subjected to primary scavenging to obtain lead concentrate, wherein 450g/t of lead inhibitor, 200 g/t of collector Z and 60g/t of MIBC foaming agent are added in the scavenging process;
11 Middlings produced in each step of fine selection and scavenging are returned to the previous step in sequence.
Comparative example 1:
the method of using the lead inhibitor in the separation and flotation of copper-lead bulk concentrates differs from example 5 only in that in one roughing, three beneficiation and one scavenging steps, the lead inhibitor used is aluminum sulfate.
Comparative example 2:
The method of using the lead inhibitor in the separation and flotation of copper-lead bulk concentrates differs from example 5 only in that the lead inhibitor used is modified beta-cyclodextrin in one roughing, three beneficiation and one scavenging steps.
Comparative example 3:
The method of using the lead inhibitor in the separation and flotation of copper-lead bulk concentrates differs from example 5 only in that the lead inhibitor used is anhydrous sodium silicate in one roughing, three beneficiation and one scavenging steps.
Test example 1:
Actual mineral flotation test (copper lead ore)
The test method comprises the steps of taking a certain copper-lead mixed concentrate as a raw material, wherein the copper grade is 4.79%, and the lead grade is 36.35%. Copper mainly exists in the form of chalcopyrite, lead mainly exists in the form of galena, and gangue minerals mainly exist in the form of silicate minerals. The experiment is carried out in an XFG type hanging tank flotation machine, the rotation speed of the flotation machine is 1650rpm, 2.0g of copper-lead mixed concentrate is taken, the mixed concentrate is placed in a 40mL flotation tank after being vibrated by ultrasonic waves for 5min, 30mL of distilled water is added, the pH value of ore pulp is regulated to be 9-10 after stirring for 1min, then the lead inhibitor prepared in the embodiment 1 and the embodiment 4 of the application is respectively added according to the amount of 500g/t (mixed concentrate), the collecting agent Z200 is respectively added according to the amount of 35g/t (mixed concentrate) after stirring for 5min, finally 40g/t (mixed concentrate) is respectively added into the MIBC foaming agent after stirring for 1min, foam scraping is started, foam products and minerals in the tank are filtered, dried and weighed, and under the condition of the same other conditions, the same amount of potassium dichromate is added as a control group. Each test example was set up with 3 replicates and averaged. The grade and recovery rate of lead in the copper concentrate obtained by roughing were measured, and the results are shown in Table 1.
TABLE 1
| Example 1 | Example 4 | Control group | |
| Grade of lead% | 10.75 | 8.40 | 11.02 |
| Lead recovery% | 4.96 | 3.87 | 5.03 |
As can be seen from the results of example 1 and the control group, the lead inhibition effect of the inhibitor of the present application is slightly better than that of the potassium dichromate control group, while the results of example 4 show that the lead inhibition effect is significantly improved after aluminum sulfate is added on the basis of the inhibitor of the present application. The data show that the lead inhibitor can effectively inhibit lead ores in copper-lead bulk concentrates, reduce the content of the lead ores in the copper concentrates, and also show that the lead inhibitor has good selectivity.
Test example 2:
Closed circuit test
The raw materials are the raw materials in test example 1, and the closed-loop test process flow is shown in figure 1. The lead inhibitors of the test groups are respectively selected from the lead inhibitors prepared in the examples 1-4 in the invention, and the comparison groups are potassium dichromate with the same dosage. The grade of copper and lead in concentrate obtained by flotation and the recovery rate of copper and lead are measured, and the selectivity index I is adopted for evaluating the copper-lead separation effect:
Wherein epsilon 1Cu、ε1Pb is the recovery rate of copper and lead in the copper concentrate, and epsilon 2Cu、ε2Pb is the recovery rate of copper and lead in the lead concentrate. The results are shown in Table 2.
TABLE 2
As can be seen from the selectivity coefficients shown in Table 2, the selectivity of the lead inhibitor prepared by the method of the application is higher than that of the traditional potassium dichromate inhibitor, the selectivity coefficient of the example 4 is higher than that of the examples 1-3, the comparative examples 1-3 and the comparative group, the results of the comparative examples 1 and 3 show that the separation effect of aluminum sulfate and anhydrous sodium sulfate alone is extremely poor, the result of the comparative example 1 shows that the separation effect of modified beta-cyclodextrin alone is poor, but the result of the lead inhibitor is poor compared with that of the examples 1, 4 and the potassium dichromate comparative group, the combined use of the anhydrous sodium silicate and the modified beta-cyclodextrin contained in the formula can improve the separation effect of copper-lead concentrate, and the selectivity is better than that of potassium dichromate, and the result of the example 4 shows that the separation effect can be improved by adding aluminum sulfate on the basis of the lead inhibitor of the application.
In the present invention, the concentration, the proportion, etc. which are not specifically described are weight concentration, weight ratio, etc. which are common writing habits of those skilled in the art, and therefore are not described in detail in the present invention.
It should be noted that, in the present invention, detailed steps of part of operations are not described in detail, but are known in the prior art by those skilled in the art, and thus are not described herein.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present application, and not for limiting the same, and although the present application has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not deviate the essence of the corresponding technical solution from the scope of the technical solution of the embodiments of the present application.
Claims (8)
1. The preparation method of the lead inhibitor in the separation and flotation of the copper-lead bulk concentrate is characterized by comprising the following steps of:
Esterifying beta-cyclodextrin serving as a raw material with a modifier to obtain modified beta-cyclodextrin, wherein the modifier is cyclic anhydride formed by dicarboxylic acid;
uniformly mixing 50-100 parts by weight of modified beta-cyclodextrin and 10-20 parts by weight of anhydrous sodium silicate to obtain a lead inhibitor;
The method for preparing the modified beta-cyclodextrin by using the beta-cyclodextrin as a raw material and a modifier for esterification comprises the following steps:
S101, adding beta-cyclodextrin and a modifier into a reaction container, and uniformly mixing to obtain a substrate mixed system;
S102, heating a substrate mixed system to 85-92 ℃ in a water bath, adding concentrated sulfuric acid into the substrate mixed system, and stirring for reaction for 5-10 min;
s103, after the reaction is finished, rapidly adding water with the volume of 2-5 times of the volume of the reaction solution into the obtained reaction solution, cooling to room temperature, and filtering;
S104, recrystallizing the filter cake obtained by filtering in the S103 by using a polar proton solvent, filtering again, and drying the filter cake at the constant temperature of-0.06 to-0.09 Mpa and 40-50 ℃ for 1-2 hours to obtain modified beta-cyclodextrin;
The molar ratio of the beta-cyclodextrin to the modifier is 1:7-1:8.4, the concentration of the concentrated sulfuric acid is 95-98%, and the dosage of the concentrated sulfuric acid is 0.5-1% of the mass of the substrate mixed system.
2. The method for preparing the lead inhibitor in the copper-lead bulk concentrate separation flotation according to claim 1, wherein the modifier has the structural formula:
Wherein R is ,n=1~8。
3. The method for preparing the lead inhibitor in the copper-lead bulk concentrate separation flotation according to claim 1, wherein the polar protic solvent is one or more of water, methanol, ethanol, propanol or isopropanol.
4. The lead inhibitor in copper-lead bulk concentrate separation and flotation is characterized by comprising the lead inhibitor prepared by the method of any one of claims 1-3, wherein the modified beta-cyclodextrin has the structural formula:
Wherein R 1、R2、R3、R4、R5、R6、R7 is hydroxy or ;
R is,n=1~8。
5. The lead inhibitor for copper-lead bulk concentrate separation flotation according to claim 4, further comprising 15-25 parts of aluminum sulfate.
6. The application of the lead inhibitor in the copper-lead bulk concentrate separation flotation of claim 4 or 5 is characterized in that the lead inhibitor is added in a mode that the lead inhibitor is prepared into a solution with the mass concentration of 1-10% and then added.
7. A method of using the lead inhibitor in the separation flotation of copper-lead bulk concentrates as claimed in claim 4 or 5, characterized in that the lead inhibitor is added during roughing, beneficiation and scavenging in the flotation separation process of copper-lead bulk concentrates;
The flotation separation process comprises one roughing, three fine selection and one scavenging.
8. The method of using the lead inhibitor in the separation and flotation of copper-lead bulk concentrates as claimed in claim 7, wherein the steps of the flotation separation process are as follows:
a) Adding calcium oxide into a ball mill according to the dry weight of each ton of copper-lead mixed concentrate, adding the copper-lead mixed concentrate and water into the ball mill according to the proportion of 1:1 for grinding until the grinding fineness of the discharged materials of the ball mill is not more than 0.074mm and accounts for 75-80%, and the pH value of ore pulp is 7.0-12.0;
b) Adding a lead inhibitor, a collector Z200 and a MIBC foaming agent into ore pulp, and performing primary roughing to obtain copper rough concentrate and copper rough tailings, wherein the usage amount of the lead inhibitor is 100-500 g/t, the usage amount of the collector Z200 is 10-50 g/t, and the usage amount of the MIBC foaming agent is 40-60 g/t;
c) The copper rough concentrate is subjected to three-time concentration to obtain copper concentrate, wherein the first concentration is added with 100-300 g/t of lead inhibitor, 200-40 g/t of collector Z and 40-60 g/t of MIBC foaming agent, the second concentration is added with 200-400 g/t of lead inhibitor and 200-50 g/t of collector Z, and the third concentration is added with 300-500 g/t of lead inhibitor;
d) The copper coarse tailings are subjected to primary scavenging to obtain lead concentrate, wherein 300-450 g/t of lead inhibitor, 200-45 g/t of collector Z and 50-60 g/t of MIBC foaming agent are added in the scavenging process;
e) And the middlings generated in each step of fine selection and scavenging are sequentially returned to the previous step.
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| CN101507951A (en) * | 2009-03-24 | 2009-08-19 | 西藏中凯矿业有限公司 | Mineral separation process capable of separating copper, lead, zinc polymetal sulphide ore |
| CN102076419A (en) * | 2008-07-02 | 2011-05-25 | 佐治亚-太平洋化工品有限公司 | Collectors |
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| US4339331A (en) * | 1980-12-05 | 1982-07-13 | American Cyanamid Company | Crosslinked starches as depressants in mineral ore flotation |
| CN104437818B (en) * | 2014-11-24 | 2016-09-21 | 西北矿冶研究院 | A kind of beneficiation method of copper-lead-zinc polymetallic ore |
| CN106238010B (en) * | 2016-08-04 | 2019-02-22 | 郑州大学 | A chelated metal ion flotation agent, its preparation method and its use method |
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| CN102076419A (en) * | 2008-07-02 | 2011-05-25 | 佐治亚-太平洋化工品有限公司 | Collectors |
| CN101507951A (en) * | 2009-03-24 | 2009-08-19 | 西藏中凯矿业有限公司 | Mineral separation process capable of separating copper, lead, zinc polymetal sulphide ore |
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