CN116748016A - Flotation collector for copper oxide ore and preparation method and application thereof - Google Patents
Flotation collector for copper oxide ore and preparation method and application thereof Download PDFInfo
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- CN116748016A CN116748016A CN202310500262.3A CN202310500262A CN116748016A CN 116748016 A CN116748016 A CN 116748016A CN 202310500262 A CN202310500262 A CN 202310500262A CN 116748016 A CN116748016 A CN 116748016A
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- copper oxide
- flotation
- collector
- methylbenzamide
- oxime
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- 238000005188 flotation Methods 0.000 title claims abstract description 62
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 56
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 9
- NKJXMLIWSJATEE-UHFFFAOYSA-N n'-hydroxy-4-methylbenzenecarboximidamide Chemical group CC1=CC=C(C(N)=NO)C=C1 NKJXMLIWSJATEE-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 28
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 238000007790 scraping Methods 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical group CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 5
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- -1 hydroxylamine ions Chemical class 0.000 claims description 2
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical class C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005987 sulfurization reaction Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000012958 reprocessing Methods 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- 238000011084 recovery Methods 0.000 description 13
- UHBGYFCCKRAEHA-UHFFFAOYSA-N P-toluamide Chemical compound CC1=CC=C(C(N)=O)C=C1 UHBGYFCCKRAEHA-UHFFFAOYSA-N 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 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 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZSFDBVJMDCMTBM-UHFFFAOYSA-N ethane-1,2-diamine;phosphoric acid Chemical compound NCCN.OP(O)(O)=O ZSFDBVJMDCMTBM-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000012991 xanthate 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
- B03D1/01—Organic compounds containing nitrogen
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a flotation collector of copper oxide ore, a preparation method and application thereof, wherein the flotation collector is p-methylbenzamide oxime with a molecular formula of C 8 N 2 OH 9 The invention relates to a method for preparing a copper oxide by using hydroxylamine hydrochloride free, synthesizing the p-methylbenzamide oxime, acidifying with hydrochloric acid, standing, extracting, drying and filtering, wherein the p-methylbenzamide oxime is used as a collector in flotation of copper oxide ore to collect the copper oxide ore, and the collector of the amidoxime class, namely the p-methylbenzamide oxime, has the advantages of low dosage, no toxicity, no harm, both collection performance and selectivity, and can efficiently recover the copper oxide under the condition of neutral to strong alkali, adopts a direct flotation method, does not undergo sulfuration, and avoids the problems caused by insufficient sulfuration and excessive sulfuration in the sulfuration processThe dosage of other agents in the copper oxide flotation process can be reduced, the p-methylbenzamide oxime is environment-friendly, and the subsequent reprocessing difficulty and cost of tail water can be reduced.
Description
Technical Field
The invention relates to a flotation collector for copper oxide ores, a preparation method and application thereof, and belongs to the technical field of mineral processing flotation agents.
Background
Copper ore resources in China are deficient, copper reserves are about 3500 ten thousand tons, and only account for 3.93% of the global copper reserves. Copper mine resources in China are mainly distributed in regions such as Yunnan, tibet, xinjiang, sichuan, jiangxi and the like. China is the first world copper production country with large refining, but the exploitation intensity of copper concentrate is higher, but the requirement of copper concentrate smelting can not be met, so that the external dependence of Chinese copper concentrate exceeds 70%. The copper mine resource in China has the following characteristics: (1) the ore grade is low, and the symbiotic and associated ore is more. The average copper grade in China is 0.71%, and the proportion of refractory copper oxide ores is increased as the resources of high-grade copper sulfide ores are increasingly reduced. The copper oxide ore has low grade, high hydrophilicity, fine copper ore embedding granularity, and is associated with various other gangue components, so that the copper oxide ore is difficult to separate and recycle. (2) a large amount of refractory oxidized ores. Most of copper oxide ores in China have complex properties, and have not been effectively developed and utilized until now. (3) small scale deposit. Over 70% of the deposits are mixed deposits, with small and medium sized deposits being the main and very few large or oversized deposits. Along with the exhaustion of the resources of the copper sulfide which is easy to select and high-grade in China, the proportion of the copper sulfide ore which is easy to select is gradually reduced, the investigation difficulty of a new ore deposit is increased, and the development of the copper oxide ore resources which are difficult to treat is of great significance.
The sulfide flotation method is characterized in that the sulfide agent is added to presulfide the minerals, so that the surface structure of the vulcanized copper oxide ore is changed, the floatability of the sulfide flotation method is similar to that of the copper sulfide minerals, and the sulfide flotation method is the most widely applied place in industryThe method for treating copper oxide ore is suitable for carbonate-containing copper oxide ore, such as malachite, copper blue ore and the like. The sulfide flotation method mainly adopts xanthate or sulfhydryl as collecting agent and Na 2 S、NaHS、(NH 4 ) 2 S, caS, etc. as vulcanizing agents. Sulfidation flotation also has some drawbacks, such as an excessive sulfidation agent can have negative effects on flotation; in addition, (NH) in the presence of an oxidizing agent 4 ) 2 S or Na 2 S is unstable and H is easily generated 2 S gas; for some copper oxide ores with high calcium and magnesium impurity content, the vulcanizing effect of the vulcanizing agent is often not obvious, and the vulcanizing effect is enhanced by adding activating agents such as ethylenediamine phosphate, thiadiazole, triethanolamine and the like, so that the cost of environmental problems is increased; in addition, the negative effect of mineral mud exists in the vulcanization flotation, and the influence is eliminated by adding a dispersing agent and the like. Thus, direct flotation is considered.
The direct flotation method mainly uses fatty acid collector, amine collector and chelate collector for flotation. The flotation of the fatty acid and amine collectors on the copper oxide is mainly applicable to the copper oxide ore with simple gangue in minerals, easy flotation and high grade; therefore, low-grade copper oxide is considered to be collected with an oxime-type collector.
Oximes are compounds having a structure of-c=n-O-H, including hydroxamic acid, amidoxime, aldoxime, ketoxime, and the like, which are widely used in coordination chemistry and capable of forming complexes with many metals. The amidoxime has a lone pair in the molecule, is easy to form a stable chelate ring with metal cations, has similar flotation mechanism and chemical property with hydroxamic acid, and can enrich rare noble metals and simultaneously crystallize and precipitate the rare noble metals.
Therefore, there is a need in the art for a novel amidoxime collector that allows direct flotation of copper oxide ores and increases the recovery and grade of copper oxide ores.
Disclosure of Invention
The invention aims at providing a flotation collector of copper oxide ore, wherein the flotation collector is p-methylbenzamide oxime, and the molecular formula is C 8 N 2 OH 9 The invention is characterized in thatCompared with the existing sulfuration flotation and hydroxamic acid collector flotation, the p-methylbenzamide oxime collector has the advantages of low consumption, no toxicity and harm, collecting performance and selective performance, and can efficiently recover copper oxide under the condition of neutrality to strong alkali, and the recovery rate of the copper blue ore can reach 72-97.48 percent.
The second purpose of the invention is to provide a preparation method of the flotation collector of copper oxide ore, which comprises the following specific steps:
(1) Free hydroxylamine hydrochloride: placing hydroxylamine hydrochloride and NaOH into an ethanol solution, and stirring to obtain a free hydroxylamine solution with free hydroxylamine ions;
(2) Synthesis of p-methylbenzamide oxime: putting the p-methylbenzonitrile and hydroxylamine solution into a flask, and reacting for 12 hours to obtain a target product, namely p-methylbenzamide oxime;
(3) Acidifying with hydrochloric acid: dropwise adding hydrochloric acid into the solution after the reaction in the step (2) for acidification, and adjusting the final pH value to 6-7;
(4) Standing: volatilizing excessive ethanol at a constant temperature of 45 ℃;
(5) Extraction: pouring the completely volatilized solution into a separating funnel, extracting with dichloromethane, and separating the oil phase of the lower layer;
(6) And (3) drying: drying with anhydrous sodium sulfate for 1 hour;
(7) And (3) filtering: and after the drying is finished, filtering anhydrous sodium sulfate, volatilizing dichloromethane at a constant temperature of 40 ℃ to obtain a crude product of the p-methylbenzamide oxime, repeating the process for three times to obtain the high-purity p-methylbenzamide oxime, and drying in a vacuum drying oven.
In the step (1), the molar ratio is 1:1.35 hydroxylamine hydrochloride and NaOH are put into ethanol solution at normal temperature and stirred for 0.5h;
in the step (2), the molar ratio is 1:1.35 and hydroxylamine solution are put into a three-neck flask, the temperature is regulated to 45 ℃, and the target product of the p-methylbenzamide oxime is obtained after the reaction for 12 hours.
In the step (5), the completely volatilized solution is poured into a separating funnel, 30mL of dichloromethane is added for continuous extraction twice, and the oil phase of the lower layer is separated.
The preparation method has the advantages of simple process, low equipment requirement and small technical difficulty.
The invention further aims to provide an application of the flotation collector for copper oxide ores in flotation of copper oxide ores, wherein firstly, 2g of copper oxide ore samples are placed in a 40mL flotation tank, 38mL deionized water is added, the rotating speed of an impeller is controlled to 1750r/min in the whole flotation process, pH of a solution is regulated by adding a pH regulator (NaOH/HCl) after stirring for 1min, the collector is added after reacting for 2min, a foaming agent is added after stirring for 3min, stirring is continued for 1min, foam scraping is started and continued for 3min, and a flotation foam product (concentrate) and tailings are filtered and dried after foam scraping is finished.
The foaming agent is MIBC.
The synthetic chemical reaction formula of the p-methylbenzamide oxime is as follows:
the amine oxime group has relatively short distance between nitrogen and oxygen atoms and has lone pair electrons, and is easy to form stable chelate with metal ions (copper, gold, silver and uranium), thus being an important metal ion chelating agent.
The p-methylbenzamide oxime of the invention is an amidoxime medicament with a molecular formula of C 8 N 2 OH 9 Copper oxide is recovered from the p-methylbenzamide oxime, mainly by C-NH in the amidoxime group 2 and-c=n-O bond forms coordination bond with copper ion on copper oxide ore surface, i.e. amidoxime and copper ion on copper oxide ore surface are chelated with O, N to form stable five-membered ring chelate. Under alkaline condition, the amidoxime nonpolar group or molecule is adsorbed on the original single molecule adsorption layer in a hydrogen bond form under the ion-molecule co-adsorption effect, so that the activity of the amidoxime is greatly improved. The adsorption capacity of the amidoxime collector on the copper oxide ore can be enhanced by increasing the carbon chain and the functional group, so that the recovery rate of the copper oxide ore is improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) The amidoxime collector-p-methylbenzamide has the advantages of low dosage, no toxicity and harm, and both the collection performance and the selective performance, and can efficiently recover copper oxide under the condition of neutrality to strong alkali, and the recovery rate of the copper blue ore reaches 72-97.48 percent.
(2) The p-methylbenzamide oxime collector adopts a direct flotation method, does not undergo sulfuration, and avoids the problems caused by insufficient sulfuration and excessive sulfuration in the sulfuration process.
(3) The p-methylbenzamide oxime collector can be used for efficiently recovering copper oxide under the condition of neutrality and strong alkali, and can reduce the dosage of other agents in the copper oxide flotation process.
(4) The p-methylbenzamide oxime collector is environment-friendly, and can reduce the subsequent reprocessing difficulty and cost of tail water.
Drawings
FIG. 1 is a schematic diagram of a device for synthesizing the collector p-methylbenzamide oxime according to the invention;
FIG. 2 is a flow chart of the collector p-methylbenzamide oxime of the invention in a copper oxide flotation application;
FIG. 3 is a graph of the flotation performance of the collector of the present invention, p-methylbenzamide usage versus copper oxide;
FIG. 4 is a graph showing the flotation performance of the collector of the invention on copper oxide at various pH values for p-methylbenzamide oxime;
FIG. 5 is a flow chart of the process for synthesizing p-methylbenzamide as collector of the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, which are only for the purpose of illustrating the invention, and the scope of the invention is not limited to the above.
Example 1: the flotation collector of the copper oxide ore of the embodiment is p-methylbenzamide oxime with a molecular formula of C 8 N 2 OH 9 . The preparation method comprises the following specific steps:
(1) Free hydroxylamine hydrochloride: the molar ratio was set to 1:1.35 hydroxylamine hydrochloride and NaOH are put into ethanol solution at normal temperature and stirred for 0.5h;
(2) Synthesis of p-methylbenzamide oxime: the molar ratio was set to 1:1.35, placing the p-methylbenzonitrile and hydroxylamine solution into a three-neck flask, regulating the temperature to 45 ℃, and reacting for 12 hours to obtain a target product, namely p-methylbenzamide oxime;
(3) Acidifying with hydrochloric acid: pouring the crude product after the reaction in the step (2) into a beaker for natural cooling, dropwise adding hydrochloric acid for acidification, and adjusting the final pH value to 6;
(4) Standing: volatilizing excessive ethanol at a constant temperature of 45 ℃;
(5) Pouring the completely volatilized solution into a separating funnel, adding 30mL of dichloromethane, continuously extracting twice, and separating the oil phase of the lower layer;
(6) And (3) drying: drying with anhydrous sodium sulfate for 1 hour;
(7) And (3) filtering: and after the drying is finished, filtering anhydrous sodium sulfate, volatilizing dichloromethane at a constant temperature of 40 ℃ to obtain a crude product of the p-methylbenzamide oxime, repeating the process for three times to obtain the high-purity p-methylbenzamide oxime, and drying in a vacuum drying oven.
The synthesis apparatus is shown in fig. 1.
The p-methylbenzamide oxime with higher purity prepared in the embodiment is applied to copper oxide ore and copper ore floatation, a flow chart is shown in figure 2, 2g of copper ore and ore sample is placed in a 40mL floatation tank, 38mL of deionized water is added, the rotating speed of an impeller is controlled to 1750r/min in the whole floatation process, a pH regulator NaOH is added after stirring for 1min to regulate the pH value of the solution, a collector is added after reacting for 2min, a foaming agent MIBC is added after stirring for 3min, stirring is continued for 1min, foam scraping is started for 3min, after foam scraping is finished, a floatation foam product (concentrate) and tailings are filtered and dried, and recovery rates are weighed and calculated according to the following formula.
Wherein:represents the recovery rate of the copper blue ore;
k represents the concentrate weight (g) obtained by flotation;
t represents the weight (g) of tailings obtained by flotation.
In this example, the conditions of 5, 10, 25, 50, 57 and 100 mol/L of the p-methylbenzamide collector were examined to obtain a graph of collector usage-recovery rate, as shown in FIG. 3, and as shown in FIG. 3, cu recovery rate increased with increasing amount of PBH reagent, when the collector usage reached 50X 10 -5 The mol/L was smoothed, and the Cu recovery was 97.48%.
This example also carried out the immobilization of the p-methylbenzamide collector in an amount of 20X 10 -5 The experiment was performed under conditions of mol/L and pH change, and pH values of 5, 6.5, 8, 9.5 and 11 respectively, to obtain a graph of pH-recovery ratio, and as shown in FIG. 4, it can be seen from FIG. 4 that the recovery ratio of the chalcopyrite is highest and reaches 90.10% at pH value of 11.
Example 2: the flotation collector of the copper oxide ore of the embodiment is p-methylbenzamide oxime with a molecular formula of C 8 N 2 OH 9 . The preparation method comprises the following specific steps:
(1) Free hydroxylamine hydrochloride: the molar ratio was set to 1:1.35 hydroxylamine hydrochloride and NaOH are put into ethanol solution at normal temperature and stirred for 0.5h;
(2) Synthesis of p-methylbenzamide oxime: the molar ratio was set to 1:1.35, placing the p-methylbenzonitrile and hydroxylamine solution into a three-neck flask, regulating the temperature to 45 ℃, and reacting for 12 hours to obtain a target product, namely p-methylbenzamide oxime;
(3) Acidifying with hydrochloric acid: pouring the crude product after the reaction in the step (2) into a beaker for natural cooling, dropwise adding hydrochloric acid for acidification, and adjusting the final pH value to 7;
(4) Standing: volatilizing excessive ethanol at a constant temperature of 45 ℃;
(5) Pouring the completely volatilized solution into a separating funnel, adding 30mL of dichloromethane, continuously extracting twice, and separating the oil phase of the lower layer;
(6) And (3) drying: drying with anhydrous sodium sulfate for 1 hour;
(7) And (3) filtering: and after the drying is finished, filtering anhydrous sodium sulfate, volatilizing dichloromethane at a constant temperature of 40 ℃ to obtain a crude product of the p-methylbenzamide oxime, repeating the process for three times to obtain the high-purity p-methylbenzamide oxime, and drying in a vacuum drying oven.
The p-methylbenzamide oxime with higher purity prepared in the embodiment is applied to flotation of copper oxide ore and copper blue ore, 2g of copper blue ore sample is placed in a 40mL flotation tank, 38mL deionized water is added, the rotating speed of an impeller is controlled to 1750r/min in the whole flotation process, the pH value of the solution is adjusted to 8 by adding a pH regulator HCL after stirring for 1min, and 20 multiplied by 10 is added after 2min of reaction - 5 And (3) adding a foaming agent MIBC after stirring and reacting for 3min, starting to scrape bubbles after stirring for 1min, continuing for 3min, and filtering and airing a flotation foam product (concentrate) and tailings after scraping. The recovery rate reaches 83 percent.
Example 3: the flotation collector of the copper oxide ore of the embodiment is p-methylbenzamide oxime with a molecular formula of C 8 N 2 OH 9 . The preparation method comprises the following specific steps:
(1) Free hydroxylamine hydrochloride: the molar ratio was set to 1:1.35 hydroxylamine hydrochloride and NaOH are put into ethanol solution at normal temperature and stirred for 0.5h;
(2) Synthesis of p-methylbenzamide oxime: the molar ratio was set to 1:1.35, placing the p-methylbenzonitrile and hydroxylamine solution into a three-neck flask, regulating the temperature to 45 ℃, and reacting for 12 hours to obtain a target product, namely p-methylbenzamide oxime;
(3) Acidifying with hydrochloric acid: pouring the crude product after the reaction in the step (2) into a beaker for natural cooling, dropwise adding hydrochloric acid for acidification, and adjusting the final pH value to 6.5;
(4) Standing: volatilizing excessive ethanol at a constant temperature of 45 ℃;
(5) Pouring the completely volatilized solution into a separating funnel, adding 30mL of dichloromethane, continuously extracting twice, and separating the oil phase of the lower layer;
(6) And (3) drying: drying with anhydrous sodium sulfate for 1 hour;
(7) And (3) filtering: and after the drying is finished, filtering anhydrous sodium sulfate, volatilizing dichloromethane at a constant temperature of 40 ℃ to obtain a crude product of the p-methylbenzamide oxime, repeating the process for three times to obtain the high-purity p-methylbenzamide oxime, and drying in a vacuum drying oven.
The p-methylbenzamide oxime with higher purity prepared in the embodiment is applied to flotation of copper oxide ore and copper blue ore, 2g of copper blue ore sample is placed in a 40mL flotation tank, 38mL deionized water is added, the rotating speed of an impeller is controlled to 1750r/min in the whole flotation process, the pH value of the solution is adjusted to 11 by adding a pH regulator HCL after stirring for 1min, and 100X 10 is added after 2min of reaction - 5 And (3) adding a foaming agent MIBC after stirring and reacting for 3min, starting to scrape bubbles after stirring for 1min, continuing for 3min, and filtering and airing a flotation foam product (concentrate) and tailings after scraping. The recovery rate reaches 97.48 percent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A flotation collector of copper oxide ore is characterized in that the collector is p-methylbenzamide oxime, and the molecular formula is C 8 N 2 OH 9 。
2. A method for preparing a flotation collector of copper oxide ores according to claim 1, comprising the following specific steps:
(1) Free hydroxylamine hydrochloride: placing hydroxylamine hydrochloride and NaOH into an ethanol solution, and stirring to obtain a free hydroxylamine solution with free hydroxylamine ions;
(2) Synthesis of p-methylbenzamide oxime: putting the p-methylbenzonitrile and hydroxylamine solution into a three-neck flask to obtain a target product p-methylbenzamide oxime;
(3) Acidifying with hydrochloric acid: pouring the reacted crude product of the p-methylbenzamide oxime into a beaker for natural cooling, dropwise adding hydrochloric acid for acidification, and adjusting the final pH value to be 6-7;
(4) Standing: volatilizing redundant ethanol from the acidified solution in the step (3) at a constant temperature of 45 ℃;
(5) Extraction: pouring the completely volatilized solution into a separating funnel, extracting with dichloromethane, and separating the oil phase of the lower layer;
(6) And (3) drying: drying with anhydrous sodium sulfate for 1 hour;
(7) And (3) filtering: and after the drying is finished, filtering anhydrous sodium sulfate, volatilizing dichloromethane at a constant temperature of 40 ℃ to obtain a crude product of the p-methylbenzamide oxime, repeating the process for three times to obtain the high-purity p-methylbenzamide oxime, and drying in a vacuum drying oven.
3. The method for preparing a flotation collector for copper oxide ores according to claim 2, wherein: the molar ratio of hydroxylamine hydrochloride to NaOH in the step (1) is 1:1.35, put into ethanol solution at normal temperature and stirred for 0.5h.
4. The method for preparing a flotation collector for copper oxide ores according to claim 2, wherein: in the step (2), the molar ratio is 1:1.35 and hydroxylamine solution are put into a three-neck flask, the temperature is regulated to 45 ℃, and the target product of the p-methylbenzamide oxime is obtained after the reaction for 12 hours.
5. The method for preparing a flotation collector for copper oxide ores according to claim 2, wherein: in the step (5), 30mL of dichloromethane is added for continuous extraction twice, and then the oil phase of the lower layer is separated.
6. The use of a flotation collector of copper oxide ore in flotation of copper oxide ore, as claimed in claim 1, characterized in that firstly 2g of a copper oxide ore sample is placed in a 40mL flotation tank, 38mL of deionized water is added, the rotation speed of an impeller is controlled to 1750r/min in the whole flotation process, the pH of the solution is regulated by adding a pH regulator HCL after stirring for 1min, the collector is added after reacting for 2min, the foaming agent is added after stirring for 3min, the stirring is continued for 1min, the scraping is started and continued for 3min, and the flotation foam product and tailings are filtered and dried after the scraping is finished.
7. Use of a flotation collector for copper oxide ores in the flotation of copper oxide ores according to claim 6, wherein: the foaming agent is MIBC.
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