CN103041929B - Double-ligand collecting agent and preparation and application thereof - Google Patents

Double-ligand collecting agent and preparation and application thereof Download PDF

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CN103041929B
CN103041929B CN201210570221.3A CN201210570221A CN103041929B CN 103041929 B CN103041929 B CN 103041929B CN 201210570221 A CN201210570221 A CN 201210570221A CN 103041929 B CN103041929 B CN 103041929B
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formula
thiourea
collecting agent
flotation
ether
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CN103041929A (en
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刘广义
肖静晶
王勇泉
钟宏
王帅
曹占芳
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Central South University
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Abstract

The invention discloses a double-ligand collecting agent-ether double thiourea or ethionine ester thiourea composite-radical compound and preparation and application thereof. The ether double thiourea or ethionine ester thiourea composite-radical compound shown as a formula (I) is used as a collecting agent for metal ore flotation, wherein R1 refers to an acyl radical with the general formula of R3-C(=O)- or an ester group with the general formula of R4O-C(=O)-, R3 and R4 respectively refer to C1-C8 alkyl radicals, R2 refers to hydrogen or methyl, X refers to O or NH, and n refers to 1-6. The compound with the structure shown as the formula (I) is used as the flotation collecting agent to efficiently recover value metal from nonferrous metal ores and precious metal ores. Flotation separation and extraction of the nonferrous metal ores and precious metal ores can be enhanced by the ether double thiourea or ethionine ester thiourea composite-radical compound. The melting point of the collecting agent can be lowered, dispersity of the collecting agent in aqueous solution is improved, adsorption of the collecting agent on the surfaces of ores is promoted, and flotation efficiency is improved while metal recovery rate is increased.

Description

A kind of pair of part collecting agent and preparation and application
[technical field]
The present invention relates to a kind of two part collecting agents of new construction---ether bis-thiourea or thiourethane thiocarbamide composite base compound, and the application in metallic ore flotation.
[background technology]
Flotation is the main method that reclaims metalliferous mineral from metallic ore, and flotation collector is one of key technology of floatation separation and Extraction valuable mineral component.Dispersed in hydrophilic-hydrophobic, water, close mineral is the critical nature of flotation collector, directly affects collecting agent at absorption and the floatation process of mineral surfaces.Along with poor, thin, the hydridization development of mineral resources, research and develop new and effective flotation collector, for improving metal comprehensive recovery, there is important function.
Thiocarbamide and thiourethane compounds are due to the metal ions such as copper, silver, gold are had to good chelation, become the important mineral floating collecting agent of a class, in bis-thiourea or thiourethane thiocarbamide composite base compound collecting agent molecule, contain two ligand groups and can strengthen itself and the effect of mineral interface metal ion, the FLOTATION SEPARATION recovery of strengthening nonferrous metallic ores and precious metal ore.The bis-thiourea or the thiourethane thiocarbamide composite base compound that appear in the newspapers at present as flotation collector have bis-thiourea (to see structural formula a, b, c and d, Zhong Hong, Liu Guangyi, Wang Shuai. di-ester-base diisothiocyanic acid ester derivant application in sulfide flotation and preparation method thereof .CN101337206A, 2009-01-07; Liu Guangyi, clock is grand. sulfide flotation collector and use method of diacyl bis-thiourea and preparation method .CN101337206A, 2009-01-07; Zhong Hong, Liu Guangyi, Yuan Lu, Wang Shuai, the summer shade of willow trees. a kind of flotation collector and preparation method thereof .CN101698161A, 2009-10-26) (see structural formula e, Liu Guangyi, Zhong Hong with thiourethane thiocarbamide composite base compound, Yuan Lu, Wang Shuai, the summer shade of willow trees. a kind of mineral floating collecting agent .CN101757985A, 2010-03-04).
Figure BDA00002650901600011
Figure BDA00002650901600021
These bis-thioureas or thiourethane thiocarbamide composite base compound collecting agent, Non-ferrous minerals and precious metal minerals are shown to good collecting performance, can within the scope of pH widely, realize these valuable elements separated with the selective floation of the gangue minerals such as pyrite, magnetic iron ore.Yet existing bis-thiourea or thiourethane thiocarbamide composite base compound collecting agent fusing point are higher, can not finely disperse in ore pulp, cause with mineral surfaces effect insufficiently, weakened them at flotation performance.
[summary of the invention]
The two part collecting agents that the object of this invention is to provide a kind of new construction---ether bis-thiourea or thiourethane thiocarbamide composite base compound, and mainly as the application of the collecting agent of nonferrous metallic ores and precious metal ore flotation, realize the flotation high efficiente callback to mineral such as copper, nickel, gold, silver.
Another object of the present invention aims to provide the simple preparation method efficiently of above-mentioned pair of part collecting agent.
The object of the invention is to realize by following manner:
Collecting agent by the ether bis-thiourea shown in formula I or thiourethane thiocarbamide composite base compound as metallic ore flotation;
Figure BDA00002650901600022
R wherein 1represent that general formula is R 3-C (=O)-acyl group or general formula be R 4o-C (=O)-ester group, R in formula 3and R 4independently be selected from separately the alkyl of C1-C8; R 2represent hydrogen or methyl; X represents O or NH; N represents 1-6.
The present invention proposes a kind of two part collecting agents of new construction---ether bis-thiourea or thiourethane thiocarbamide composite base compound, and the application in metallic ore flotation.Ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound collecting agent can reduce the fusing point of collecting agent, strengthen its dispersiveness in the aqueous solution, promote collecting agent in the absorption of mineral surfaces, thereby the FLOTATION SEPARATION of strengthening nonferrous metallic ores and precious metal ore reclaim.
At present, suc as formula the ether bis-thiourea shown in I or thiourethane thiocarbamide composite base compound and have no report as floating agent in froth flotation, in U.S. CA database, do not see the defined ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound and synthetic method and application yet.
R of the present invention 1be preferably acetyl group, propiono, bytyry, caprylyl, isopropyl acyl group, isobutyryl, different caprylyl, ethoxycarbonyl, propyl ester base, butyl ester base, monooctyl ester base, isopropyl ester group, isobutyl ester group, different monooctyl ester base; N is preferably 1-3.
The basic process that ether bis-thiourea shown in formula I or thiourethane thiocarbamide composite base compound are used as collecting agent in nonferrous metals ore and precious metal ore flotation is: (a) after grinde ore, enter flotation; (b) in ore grinding and/or floatation process, add floating agent to size mixing, in the medicament of interpolation, at least contain a kind of ether bis-thiourea or thiourethane thiocarbamide composite base compound; (c) by froth flotation method emersion useful metal mineral.
Ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound are as flotation collector, Non-ferrous minerals and precious metal minerals are had to strong collecting ability as precious metal minerals such as the zinc mineral of the copper minerals such as chalcopyrite, activated by copper ions, gold and silver, and to a little less than the collecting ability of the gangue minerals such as pyrite, magnetic iron ore, selectively good.Adopt ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound as flotation collector or with other collecting agent, to combine use separately, under the condition of pH values of pulp 5.0～14 scopes, can make the flotation recovery rate of Non-ferrous minerals and precious metal minerals improve, inhibitor consumption while reducing separation, realize valuable mineral separated with the efficient flotation separation of gangue mineral, improve metal comprehensive recovery, its consumption is between 1～100 gram of/ton of ore deposit.
Flotation collector ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound can make by the following method:
Will suc as formula isothiocyanates shown in II with suc as formula ether diamine shown in III or ether alcohol amine, carry out addition reaction, reaction temperature-15 ℃～80 ℃, the reaction time is 1～6 hour, generates suc as formula the bis-thiourea of ether shown in I or thiourethane thiocarbamide composite base compound.
R 1-N=C=S formula II
R wherein 1represent that general formula is R 3-C (=O)-acyl group or general formula be R 4o-C (=O)-ester group, R in formula 3and R 4independently be selected from separately the alkyl of C1-C8;
Figure BDA00002650901600031
R wherein 2represent hydrogen or methyl; X represents O or NH; N represents 1-6.
R wherein 1be preferably acetyl group, propiono, bytyry, caprylyl, isopropyl acyl group, isobutyryl, different caprylyl, ethoxycarbonyl, propyl ester base, butyl ester base, monooctyl ester base, isopropyl ester group, isobutyl ester group, different monooctyl ester base; N is preferably 1-3.
The preparation method of ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound has following characteristics: preparation method is simple, efficient, practical, and conversion rate of products is greater than 95%, and crude product can be used as flotation collector.
[accompanying drawing explanation]
Fig. 1 N, the different pungent oxygen carbonyl-N of N '-bis-", N " ' infrared spectrum of-Ya isopropyl ether bis-thiourea.
Fig. 2 N, N '-diethoxy carbonyl-N ", the infrared spectrum of the sub-ether base of O-thiourethane thiocarbamide composite base compound.
[specific embodiment]
The present invention is further illustrated by the following example, but is not subject to the restriction of these embodiment.In embodiment, unless otherwise specified all umbers and percentage all refer to quality.
(1) preparation of ether bis-thiourea or thiourethane thiocarbamide composite base compound
Embodiment 1N, the different pungent oxygen carbonyl-N of N '-bis-", N " ' preparation of-Ya isopropyl ether bis-thiourea
In containing the aqueous solution of 431 parts of different pungent oxygen carbony isorhodanates of N-, slowly splash into containing 230 parts of aqueous solution that polyetheramine D-230 concentration is 30%, 0 ℃～10 ℃ left and right stirring reactions 2 hours, then room temperature reaction is 30 minutes, obtain 647 parts of N, the different pungent oxygen carbonyl-N of N '-bis-", N " '-Ya isopropyl ether bis-thiourea, yield is 98%.
Embodiment 2N, N '-diethoxy carbonyl-N ", the preparation of the sub-ether base of O-thiourethane thiocarbamide composite base compound
Containing in the hexane solution of 262 parts of N-ethoxycarbonyl isothiocyanates, slowly splash into 105 parts of diglycolamines, 0 ℃～15 ℃ stirring reactions 2 hours, then be warmed up to 55 ℃ of reactions 2 hours, obtain 356 parts of N, N '-diethoxy carbonyl-N "; the sub-ether base of O-thiourethane thiocarbamide, yield is 97%.
Embodiment 3N, N '-dibutyryl-N ", N " ' preparation of-Ya ether base bis-thiourea
In containing the hexane solution of 259 parts of N-bytyry isothiocyanates; slowly splash into containing 104 part 2; the hexane solution of 2 '-oxygen two (ethamine); 0 ℃～25 ℃ stirring reactions 2 hours; then be warmed up to 45 ℃ of reactions 2 hours, obtain 348 parts of N, N '-dibutyryl-N "; N " '-Ya ether base bis-thiourea, yield is 96%.
(2) ether bis-thiourea or the application of thiourethane thiocarbamide composite base compound in metallic ore flotation
The fusing point contrast of embodiment 4 two ester group alkylene ether bis-thioureas or thiourethane thiocarbamide and two ester group alkylidene bis-thioureas
The fusing point of two ester group alkylene ether bis-thioureas or thiourethane thiocarbamide and two ester group alkylidene bis-thioureas is in Table 1.It shows, compares with two ester group alkylidene bis-thioureas, and two ester group alkylene ether bis-thioureas or thiourethane thiocarbamide have lower fusing point.This explanation, two ester group alkylene ether bis-thioureas or thiourethane thiocarbamide molecular energy improve its dispersibility in ore pulp, increase itself and the effect chance of mineral surfaces, improve value flotation recovery.
The fusing point of table 1 ether bis-thiourea or thiourethane thiocarbamide composite base compound
Figure BDA00002650901600041
Embodiment 5 certain porphyry copper-molybdenum mine stone ore sample, in ore, copper mineral is mainly chalcopyrite, is secondly vitreous copper-alpha chalcocite, tetrahedrite-tennantite etc.; Iron mineral is mainly pyrite; Molybdenum ore thing is molybdenite.Raw ore cupric 0.35%, containing molybdenum 0.016%.
Experiment process: one roughing; Mog :-0.074mm accounts for 65%; Medicament condition: 800 grams/ton of lime consumptions, slurry pH is 8.0, all the other medicament conditions and the results are shown in Table 2.The result of the test of table 2 shows, two ester group alkylene ether thiourethane thiocarbamide collecting agents of the present invention are obtained than collecting agent butyl xanthate and higher copper and the molybdenum flotation recovery rate of two ester group alkylidene thiourethane thiocarbamides.
Table 2 collecting agent contrast flotation conditions and copper molybdenum flotation results
Figure BDA00002650901600042
Embodiment 6 certain high-sulfur copper sulfurized ore, raw ore cupric 0.40%.
Experiment process: one roughing.Mog :-0.074mm65%.Medicament condition: grey consumption is 400g/t, slurry pH is 7.5, all the other medicament conditions and the results are shown in Table 3.The result of the test of table 3 shows, two ester group alkylene ether bis-thioureas of the present invention are obtained than the higher copper flotation recovery rate of two ester group alkylidene bis-thioureas.
Table 3 collecting agent contrast flotation conditions and copper flotation results
Figure BDA00002650901600052
Embodiment 7 certain Copper sulfide ore containing gold stone, in ore, major metal mineral are chalcopyrite, tetrahedrite and pyrite.Head grade: copper 0.81%, Au0.45g/t, silver-colored 3.67g/t, sulphur 2.43%.Mog :-0.074mm75%.Experiment process is one roughing.Floating agent condition: 1200 grams/ton, lime, N, N '-dibutyryl-N ", N " ' 30 grams/ton of-Ya propyl ether base bis-thioureas, 10 grams/ton of butyl xanthates, MIBC25 gram/ton.Rough concentrate productive rate 9.16%, wherein containing copper grade 7.73%, containing golden 4.23g/t, argentiferous 34.26g, copper, the rate of recovery of Jin Heyin is respectively 87.42%, 86.10% and 85.51%.

Claims (4)

1. two part collecting agents, is characterized in that, the collecting agent by the ether bis-thiourea suc as formula structure shown in I or thiourethane thiocarbamide composite base compound as metallic ore flotation;
Figure FDA0000421722870000011
formula I
R wherein 1represent that general formula is R 3-C (=O)-acyl group or general formula be R 4o-C (=O)-ester group, R in formula 3and R 4independently be selected from separately the alkyl of C1-C8; R 2represent hydrogen or methyl; X represents O or NH; N represents 1-6.
2. according to claim 1 pair of part collecting agent, is characterized in that R 1for acetyl group, propiono, bytyry, caprylyl, isopropyl acyl group, isobutyryl, different caprylyl, ethoxycarbonyl, propyl ester base, butyl ester base, monooctyl ester base, isopropyl ester group, isobutyl ester group or different monooctyl ester base; N is 1-3.
3. the application of the two part collecting agents described in claim 1 or 2, as the flotation collector as metallic ore.
4. the preparation method of the two part collecting agents described in claim 1 or 2, it is characterized in that, by suc as formula isothiocyanates shown in II with suc as formula the ether diamine shown in III or ether alcohol amine, carry out addition reaction, reaction temperature-15 ℃～80 ℃, reaction time is 1～6 hour, generates suc as formula the bis-thiourea of ether shown in I or thiourethane thiocarbamide composite base compound;
R 1-N=C=S formula II
R wherein 1represent that general formula is R 3-C (=O)-acyl group or general formula be R 4o-C (=O)-ester group, R in formula 3and R 4independently be selected from separately the alkyl of C1-C8;
Figure FDA0000421722870000012
formula III
R wherein 2represent hydrogen or methyl; X represents O or NH; N represents 1-6.
CN201210570221.3A 2012-12-25 2012-12-25 Double-ligand collecting agent and preparation and application thereof Expired - Fee Related CN103041929B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358368A (en) * 1979-03-02 1982-11-09 Berol Kemi Ab Process for the froth flotation of calcium phosphate-containing minerals and flotation agents therefor
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
CN101698161A (en) * 2009-10-26 2010-04-28 中南大学 Flotation collector and preparation method thereof
CN101757985A (en) * 2010-03-04 2010-06-30 中南大学 Mineral flotation collectors

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5831222B2 (en) * 1980-03-10 1983-07-05 同和鉱業株式会社 Preferential flotation of lead minerals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358368A (en) * 1979-03-02 1982-11-09 Berol Kemi Ab Process for the froth flotation of calcium phosphate-containing minerals and flotation agents therefor
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
CN101698161A (en) * 2009-10-26 2010-04-28 中南大学 Flotation collector and preparation method thereof
CN101757985A (en) * 2010-03-04 2010-06-30 中南大学 Mineral flotation collectors

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