CN101757985B - Mineral flotation collectors - Google Patents
Mineral flotation collectors Download PDFInfo
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- CN101757985B CN101757985B CN 201010117288 CN201010117288A CN101757985B CN 101757985 B CN101757985 B CN 101757985B CN 201010117288 CN201010117288 CN 201010117288 CN 201010117288 A CN201010117288 A CN 201010117288A CN 101757985 B CN101757985 B CN 101757985B
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Abstract
The invention provides mineral flotation collectors, namely sulfur ammonia ester thiourea composite-group compounds. The structural formula of the collectors is as follows, wherein R1 represents C1 to C8 alkyl, acyl groups of which the general formula is R3-C(=O)- or ester groups of which the general formula is R40-C(=O)-; R3 and R4 in the structural formula represent C1 to C8 alkyl respectively;and R2 represents C2 to C9 alkylene. Due to a plurality of coordination atoms and coordination groups in collector molecules, the sulfur ammonia ester thiourea composite-group compounds serving as flotation collectors can enhance the flotation, separation and extraction of nonferrous metal ores and precious metal ores and improve flotation efficiency, metal recovery rate and other characteristics.
Description
Technical field
The present invention relates to a kind of mineral floating collecting agent---thiourethane thiocarbamide composite base compound.
Background technology
Floating agent is the key technology of floatation separation and Extraction valuable mineral component.More and more poorer along with mineral resources, thin, assorted, research and develop new and effective flotation collector, for the development and use of complicated difficult processing ore, improve the metal comprehensive recovery and have important function.
Xanthate is the general collecting agent of sulfide flotation, and its collecting ability is strong, but lacks selective.Compare with xanthate, dialkyl thiocarbamic acid ester (thiourethane) selective better, be conducive to copper in the sulfide ore, lead, zinc, gold or the beneficial element such as silver-colored comprehensively reclaims.For further improving the flotation performance of thiourethane collecting agent, pi-allyl thiourethane (the Lewellyn M.E..Process for the preparation ofN-allyl-O-alkyl thionocarbamates. U.S.: US4482500,1984-11-13; Goldenrain tree and woods, Yao Wen, military Rongcheng. a kind of preparation method of thioamino-formates compounds. China: CN1153774A, 1997-07-09), acyl group thiourethane (Bogdanov, O.S., Vainshenker, I.A., Podnek, A.K., et al., 1976.Trends in the search for effectivecollectors.Tsvet.Metal.49 (4), 72-80.), ester group thiourethane (Fu Yun-Lung, the Strydom P.J.Process for the production of isothiocyanate derivatives. U.S.: US4659853,1987-01-27; Kulkarni S.V.and Desai V.C..Processfor manufacture of N-alkoxy (or aryloxy) carbonyl isothiocyanatederivatives in the presence of N, the N-dialkylarylamine catalyst andaqueous solvent. U.S.: US6184412,2001-02-06; Kulkarni S.V.and DesaiV.C.. prepares the method for carbony isorhodanate and derivative thereof in the presence of dialkyl arylamine. China: CN12777190A, 2000-12-20; Zhong Hong, Liu Guangyi, Wang Hui is etc. the preparation method of a kind of N-oxyl carbony isorhodanate and derivative thereof. China: CN1220678C, 2005-9-28) etc. the thiourethane collecting agent of new structure in succession developed.In addition, the people such as Zhong Hong and Liu Guangyi has prepared di-ester-base two thiourethanes with di-ester-base diisothio-cyanate and fatty alcohol reaction and has been used for sulfide flotation collector (Zhong Hong, Liu Guangyi, Wang Shuai. di-ester-base diisothiocyanic acid ester derivant application in sulfide flotation and preparation method thereof .CN101337206A).
The collecting ability of Thiourea collecting agent is better than corresponding thiourethane collecting agent usually, and can fine recovery noble metal.The thiocarbamide collecting agent that is used at present mineral floating has alkyl thiocarbamide (D.W.Fuerstenau, R.Herrera-Urbina, D.W.McGlashan.Studies on the applicability ofchelating agents as universal collectors for copper minerals.Int.J.Miner.Process.2000,58:15-33; The Wang Dian assistant; Lin Qiang; Jiang Yuren. ore dressing and the design of metallurgical agent molecule. Changsha: publishing house of Zhongnan Polytechnic Univ; 1996.); acylthioureas (Wang Dian assistant; Lin Qiang; Jiang Yuren. ore dressing and the design of metallurgical agent molecule. Changsha: publishing house of Zhongnan Polytechnic Univ; 1996.); diacyl bis-thiourea (Liu Guangyi; clock is grand. sulfide flotation collector and use method of diacyl bis-thiourea and preparation method .CN101337206A; 2009-01-07); ester group thiocarbamide (Fu Yun-Lung; Wang Samuel S.Neutral hydrocarboxycarbonyl thiourea sulfidecollectors.USRE32786; 1988-11-22) and di-ester-base two thiocarbamide (Zhong Hong; Liu Guangyi; Wang Shuai. di-ester-base diisothiocyanic acid ester derivant application in sulfide flotation and preparation method thereof .CN101337206A, 2009-1-7).The thiocarbamide collecting agent has very good selective to pyrite and magnetic iron ore, realize easily valuable metal element and the pyritic FLOTATION SEPARATION such as copper, lead, zinc when alkalescence is low; The thiocarbamide collecting agent also is used for strengthening the flotation recovery of precious metal minerals.
Summary of the invention
The mineral floating collecting agent that the purpose of this invention is to provide a kind of new construction---thiourethane thiocarbamide composite base compound, mainly as the collecting agent of nonferrous metallic ores and precious metal ore flotation, to strengthen the comprehensive recovery of copper, lead, zinc, nickel, gold, silver etc. and to realize that these mineral separate with the efficient flotation separation of pyrite, magnetic iron ore etc.
The objective of the invention is to realize by following manner:
Will be suc as formula the collecting agent of the thiourethane thiocarbamide composite base compound shown in (I) as the metalliferous mineral flotation.
Wherein R1 represent the alkyl of C1-C8 or general formula be R3-C (=O)-acyl group or general formula be R40-C (=O)-ester group, R3 and R4 represent respectively the alkyl of C1-C8 in the formula; R2 represents the alkylene of C2-C9.
Thiourethane thiocarbamide composite base compound shown in the formula (I) is used as collecting agent in nonferrous metals ore and precious metal ore flotation basic process is: (a) enter flotation behind the grinde ore; (b) in ore grinding and/or floatation process, add floating agent and size mixing, contain at least a kind of thiourethane thiocarbamide composite base compound in the medicament of interpolation; (c) by froth flotation method emersion useful metal mineral.
But flotation collector of the present invention--thiourethane thiocarbamide composite base compound economical and efficient ground is that the isothiocyanates of R1-N=C=S and hydramine addition that structural formula is HO-R2NH2 make by structural formula.Wherein R1 represent the alkyl of C1-C8 or general formula be R3-C (=O)-acyl group or general formula be R40-C (=O)-ester group, R3 and R4 represent respectively the alkyl of C1-C8 in the formula; R2 represents the alkylene of C2-C9.
Thiourethane thiocarbamide composite base compound of the present invention is as flotation collector, the precious metal minerals such as the zinc sulfide mineral of the copper sulfide minerals such as Non-ferrous minerals and precious metal minerals such as chalcopyrite, activated by copper ions, nickel sulfide mineral, gold and silver had strong collecting ability, a little less than the collecting ability to iron sulfide minerals such as pyrite, magnetic iron ore, selective good.Adopt thiourethane thiocarbamide composite base compound of the present invention to unite use as flotation collector or with other collecting agent separately, under the condition of thiourethane thiocarbamide composite base compound amount 1～100 gram/ton, pH values of pulp 5.0～11.5 scopes, compare with existing collecting agent, the flotation recovery rate of Non-ferrous minerals and precious metal minerals is improved, realize that simultaneously these mineral separate with the efficient flotation separation of iron sulfide mineral, lime consumption when reducing the sulphide ore separation improves the metal comprehensive recovery.
The thiourethane group and the thiourea group that contain simultaneously in the thiourethane thiocarbamide composite base compound molecule that the present invention proposes, the characteristics that possess simultaneously thiocarbamide collecting agent and thiourethane collecting agent, can significantly strengthen the chelation of collecting agent and mineral interface, increase simultaneously hydrophobic surface, thereby the FLOTATION SEPARATION of strengthening nonferrous metallic ores and precious metal ore is extracted, and has flotation efficiency height, characteristics that metal recovery rate is high.
The specific embodiment
The present invention is further specified by the following example, but is not subjected to the restriction of these embodiment.All umbers and percentage all refer to quality except as otherwise herein provided among the embodiment.
(1) preparation of thiourethane thiocarbamide composite base compound
Embodiment 1N, N '-diethyl-ester group-O, N "-preparation of (1,2-ethylidene) thiourethane thiocarbamide
30.54 parts of monoethanolamines are added acetone, and to be configured to mass concentration be monoethanolamine-acetone soln of 20%, under reaction temperature is 5～15 ℃ and stirring condition, slowly join in the three-neck flask that contains 131.2 parts of N-ethoxycarbonyl isothiocyanates, stirring reaction 2 hours, then reacted 4 hours 40-50 ℃ of lower the continuation, react complete.After decompression steams solvent acetone, get 157.5 parts of yellow product, wherein contain N, N '-diethyl-ester group-O, N "-145 parts of (1,2-ethylidene) thiourethane thiocarbamides, product purity 92.1%.
Embodiment 2N, N '-dibenzoyl-O, N "-preparation of (1,2-ethylidene) thiourethane thiocarbamide
30.54 parts of monoethanolamines are added oxolane, and to be configured to mass concentration be monoethanolamine-tetrahydrofuran solution of 20%; under reaction temperature is 5～20 ℃ and stirring condition; slowly join in the three-neck flask that contains 163.2 parts of N-benzoyl isothiocyanates; stirring reaction 2 hours; then 50-60 ℃ of lower the continuation reacted 5 hours, reacted complete.After decompression steams solvents tetrahydrofurane, get 191 parts of yellow product, wherein contain N, N '-dibenzoyl-O, N "-177 parts of (1,2-ethylidene) thiourethane thiocarbamides, product purity 92.8%.
(2) application of thiourethane thiocarbamide composite base compound in mineral floating
Embodiment 3: certain Copper Ores sample ore, copper mineral is mainly chalcopyrite in the ore, is vitreous copper-alpha chalcocite, tetrahedrite-tennantite etc. secondly.Iron mineral is mainly pyrite.Raw ore cupric 0.43%, sulfur-bearing 2.86%.
Experiment process: one roughing; Mog :-0.074mm accounts for 68%; The medicament condition: lime consumption 1600 gram/ton, slurry pH is 9.0, all the other medicament conditions and the results are shown in Table 1.The result of the test of table 1 shows, thiourethane thiocarbamide composite base collecting agent of the present invention can be obtained than collecting agent butyl xanthate commonly used, Z-200 (O-isopropyl-N-ethyl thiourethane) and the higher copper flotation recovery rate of N-carbethoxyl group-N '-propyl group thiocarbamide (single thiocarbamide collecting agent), and copper sulphur content from selective better.
Flotation conditions and the result thereof of table 1 thiourethane thiocarbamide composite base compound
Embodiment 4 certain cu-ni sulphide ore stone, head grade: Cu0.83%, Ni1.31%.Experiment process: one roughing, twice selected, the open circuit flotation.Mog :-0.074mm81%.Medicament condition: sodium carbonate 500 grams/ton, calgon 100 grams/ton, copper sulphate 100 grams/ton, butyl xanthate 90 grams/ton, N, N '-dibutyl ester base-O, N "-(1,2-ethylidene) thiourethane thiocarbamide 25 grams/ton, butyl ether alcohol 20 grams/ton.Small-scale test result of the test: concentrate yield 11.86%, concentrate Ni grade 8.82%, Cu grade 5.23%, the concentrate Ni rate of recovery 79.85%, the Cu rate of recovery 74.73%.
Embodiment 5 certain Micro-disseminated Gold Deposits, head grade: Au4.2 gram/ton, Ag6.5 gram/ton.Experiment process: one roughing.Mog :-0.074mm87%.Medicament condition: sodium carbonate 500 grams/ton, waterglass 350 grams/ton, butyl ammonium aerofloat 35 grams/ton, N, N '-dibenzoyl-O, N "-(1,2-ethylidene) thiourethane sulphur 25 grams/ton, 2# oil 20 grams/ton.Bench test: rough concentrate productive rate 14.66%, rough concentrate Au grade 24.8 grams/ton, Ag grade 37.6 grams/ton, the concentrate Au rate of recovery 86.56%, the Ag rate of recovery 84.80%.
Embodiment 6 certain cupric oxide ore, raw ore Cu grade 1.26%, oxygenation efficiency 68.4%.Experiment process: one roughing.Mog :-0.074mm90%; Medicament condition: sodium carbonate 1500 grams/ton, calgon 300 grams/ton, waterglass 1000 grams/ton, vulcanized sodium 2500 grams/ton, Y89100 gram/ton, N, N '-dibutyl ester base-O, N "-(1; the 2-ethylidene) thiourethane thiocarbamide 50 grams/ton, MIBC30 gram/ton, flotation pH10.5-11.Bench test: rough concentrate productive rate 9.35%, rough concentrate Cu grade 9.8%, the rate of recovery 72.72%.
Embodiment 7 certain plumbous zinc sulphur ore deposit, head grade: Pb2.3%, Zn3.7%, S19.2%.Mog :-0.074mm65%.The test principle process is diffeential floatation, and order of floatation is followed successively by Pb, Zn, S.Zn flotation flowsheet: one roughing; Zn floating agent condition: copper sulphate 150 grams/ton, butyl xanthate 35 grams/ton, N, N '-diethyl-ester group-O, N "-(1,2-ethylidene) thiourethane thiocarbamide 40 grams/ton, MIBC25 gram/ton.Zn roughly selects index: concentrate yield 25.68%, rough concentrate Zn grade 13.4%, the rough concentrate Zn rate of recovery 93.00%.
Claims (3)
1. mineral floating collecting agent, chemical name is: thiourethane thiocarbamide composite base compound, structural formula is suc as formula shown in (I):
R wherein
1The alkyl or the general formula that represent C1-C8 are R
3-C (=O)-acyl group or general formula be R
4O-C (=O)-ester group, R in the formula
3And R
4Represent respectively the alkyl of C1-C8; R
2Represent the alkylene of C2-C9.
2. flotation collector according to claim 1 is characterized in that, R
1Be preferably pi-allyl, benzyl, formoxyl, acetyl group, propiono, bytyry, carbomethoxy, ethoxycarbonyl, propyl ester base or butyl ester base; R
2Be preferably ethylidene or propylidene.
3. flotation collector according to claim 1 is characterized in that: use this compound in the flotation of nonferrous metallic ores and/or precious metal ore.
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| CN101757985B true CN101757985B (en) | 2013-04-10 |
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Families Citing this family (15)
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| CN102516144B (en) * | 2011-11-02 | 2014-11-05 | 中南大学 | Thiourea compound and preparation thereof and application thereof to metal ore floatation |
| CN103041929B (en) * | 2012-12-25 | 2014-04-02 | 中南大学 | Double-ligand collecting agent and preparation and application thereof |
| CN103801460B (en) * | 2014-01-26 | 2017-01-25 | 乌鲁木齐金石徽龙矿业有限公司 | Low-grade copper flotation technology |
| CN103801461B (en) * | 2014-01-26 | 2017-01-25 | 乌鲁木齐金石徽龙矿业有限公司 | Low-grade copper-nickel ore flotation technology |
| CN103785545B (en) * | 2014-02-20 | 2016-08-24 | 西北有色地质研究院 | A kind of combination medicament improves the method for carbon containing cupric oxide ore Cu Concentrate Grade |
| CN104056725B (en) * | 2014-05-15 | 2016-06-29 | 中南大学 | A kind of ether thiourethane collecting agent and methods for making and using same thereof |
| CN104475266A (en) * | 2014-12-25 | 2015-04-01 | 昆明冶金研究院 | Copper sulfide flotation collector as well as preparation method and application thereof |
| CN105149106A (en) * | 2015-09-30 | 2015-12-16 | 广西大学 | Preparation method of auxiliary collecting agent for improving recovery rate of associated gold in antimonite |
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| CN105665148B (en) * | 2016-01-15 | 2018-05-04 | 中南大学 | A kind of isocyanate derivative and its preparation method and application |
| CN106955790B (en) * | 2017-04-10 | 2019-12-24 | 中南大学 | N-alkyl hydroximic acid-O-alkyl thiourethane collecting agent, preparation and application thereof |
| CN108906332A (en) * | 2018-07-27 | 2018-11-30 | 广西大学 | A kind of zinc sulfide ore method for floating |
| CN112844855B (en) * | 2021-01-03 | 2021-11-30 | 中南大学 | Flotation reagent for selectively separating galena and sphalerite and application method thereof |
| CN112657681B (en) * | 2021-03-16 | 2021-07-09 | 矿冶科技集团有限公司 | Cationic collector and preparation method and application thereof |
| CN113751205A (en) * | 2021-09-10 | 2021-12-07 | 紫金矿业集团股份有限公司 | N-tert-butyl ester collecting agent and preparation method thereof |
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| AU570131B2 (en) * | 1984-08-17 | 1988-03-03 | American Cyanamid Company | Hydrocarboxycarbonyl thionocarbamate collectors |
| RU2042433C1 (en) * | 1993-05-07 | 1995-08-27 | Уральский научно-исследовательский и проектный институт медной промышленности "УНИПРОМЕДЬ" | Method for flotation of sulfide copper/zinc ores |
| CN101337206A (en) * | 2008-08-13 | 2009-01-07 | 中南大学 | Sulphide ore floation collector and use method of diacyl bis-thiourea and preparation method thereof |
| CN101337205A (en) * | 2008-08-13 | 2009-01-07 | 中南大学 | Use of diester isosulfocyanate in sulphide ore floation and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61204053A (en) * | 1985-03-05 | 1986-09-10 | Dowa Mining Co Ltd | Copper-lead separating floatation method |
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- 2010-03-04 CN CN 201010117288 patent/CN101757985B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU570131B2 (en) * | 1984-08-17 | 1988-03-03 | American Cyanamid Company | Hydrocarboxycarbonyl thionocarbamate collectors |
| RU2042433C1 (en) * | 1993-05-07 | 1995-08-27 | Уральский научно-исследовательский и проектный институт медной промышленности "УНИПРОМЕДЬ" | Method for flotation of sulfide copper/zinc ores |
| CN101337206A (en) * | 2008-08-13 | 2009-01-07 | 中南大学 | Sulphide ore floation collector and use method of diacyl bis-thiourea and preparation method thereof |
| CN101337205A (en) * | 2008-08-13 | 2009-01-07 | 中南大学 | Use of diester isosulfocyanate in sulphide ore floation and preparation method thereof |
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