CN103041929A - 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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CN103041929A
CN103041929A CN2012105702213A CN201210570221A CN103041929A CN 103041929 A CN103041929 A CN 103041929A CN 2012105702213 A CN2012105702213 A CN 2012105702213A CN 201210570221 A CN201210570221 A CN 201210570221A CN 103041929 A CN103041929 A CN 103041929A
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thiourea
collecting agent
thiourethane
ether
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CN103041929B (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 the metallic ore flotation.
[background technology]
Flotation is the main method that reclaims metalliferous mineral from metallic ore, and flotation collector then is one of key technology of floatation separation and Extraction valuable mineral component.Dispersed in hydrophilic-hydrophobic, the 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, have important function for improving the metal comprehensive recovery.
Thiocarbamide and thiourethane compounds are owing to have good chelation to metal ions such as copper, silver, gold, become the important mineral floating collecting agent of a class, contain two ligand groups in bis-thiourea or the thiourethane thiocarbamide composite base compound collecting agent molecule and can strengthen itself and the effect of mineral interface metal ion, strengthen the FLOTATION SEPARATION recovery of nonferrous metallic ores and precious metal ore.Bis-thiourea or the thiourethane thiocarbamide composite base compound that is used as flotation collector that appear in the newspapers at present has 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 BDA00002650901600021
These bis-thioureas or thiourethane thiocarbamide composite base compound collecting agent, Non-ferrous minerals and precious metal minerals are shown good collecting performance, can realize that these valuable elements separate with the selective floation of the gangue minerals such as pyrite, magnetic iron ore in the pH scope widely.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 the mineral surfaces effect insufficiently, have weakened them at flotation performance.
[summary of the invention]
The two part collecting agents that the purpose of this invention is to provide a kind of new construction---ether bis-thiourea or thiourethane thiocarbamide composite base compound, reach the application mainly as 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 efficiently preparation method of above-mentioned pair of part collecting agent.
The objective of the invention is to realize by following manner:
With the ether bis-thiourea shown in the formula I or the thiourethane thiocarbamide composite base compound collecting agent as the metallic ore flotation;
R wherein 1Representing general formula is R 3-C (=O)-acyl group or general formula be R 4O-C (=O)-ester group, R in the 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 the 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 the I or thiourethane thiocarbamide composite base compound and in froth flotation, have no report as floating agent, 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.
Ether bis-thiourea shown in the formula I or thiourethane thiocarbamide composite base compound are 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 ether bis-thiourea or thiourethane thiocarbamide composite base compound in the medicament of interpolation; (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, the precious metal minerals such as the zinc mineral of the copper minerals such as Non-ferrous minerals and precious metal minerals such as chalcopyrite, activated by copper ions, gold and silver had strong collecting ability, and a little less than the collecting ability to gangue minerals such as pyrite, magnetic iron ore, selective good.Adopt ether bis-thiourea of the present invention or thiourethane thiocarbamide composite base compound to unite use as flotation collector or with other collecting agent separately, the flotation recovery rate of Non-ferrous minerals and precious metal minerals is improved, reduce inhibitor consumption when separating, realize that valuable mineral separates with the efficient flotation separation of gangue mineral, improve the metal comprehensive recovery, its consumption is between 1～100 gram/ton 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 the II with carry out addition reaction suc as formula ether diamine shown in the III or ether alcohol amine, reaction temperature-15 ℃～80 ℃, the reaction time is 1～6 hour, generates suc as formula the bis-thiourea of ether shown in the I or thiourethane thiocarbamide composite base compound.
R 1-N=C=S formula II
R wherein 1Representing general formula is R 3-C (=O)-acyl group or general formula be R 4O-C (=O)-ester group, R in the 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: the preparation method is simple, efficient, practical, and conversion rate of products is greater than 95%, and crude product namely can be used as flotation collector.
[description of drawings]
Fig. 1 N, the different hot oxygen carbonyl-N of N '-two ", N " '-infrared spectrum of Ya isopropyl ether bis-thiourea.
Fig. 2 N, N '-diethoxy carbonyl-N ", the infrared spectrum of the inferior ether base of O-thiourethane thiocarbamide composite base compound.
[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 ether bis-thiourea or thiourethane thiocarbamide composite base compound
Embodiment 1N, the different hot oxygen carbonyl-N of N '-two ", N " '-preparation of Ya isopropyl ether bis-thiourea
In the aqueous solution that contains 431 parts of different hot oxygen carbony isorhodanates of N-, splash into slowly that to contain 230 parts of polyetheramine D-230 concentration be 30% the aqueous solution, 0 ℃～10 ℃ left and right sides stirring reactions 2 hours, then room temperature reaction is 30 minutes, obtain 647 parts of N, the different hot oxygen carbonyl-N of N '-two ", N " '-Ya isopropyl ether bis-thiourea, yield is 98%.
Embodiment 2N, N '-diethoxy carbonyl-N ", the preparation of the inferior ether base of O-thiourethane thiocarbamide composite base compound
In the hexane solution that contains 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 inferior ether base of O-thiourethane thiocarbamide, yield is 97%.
Embodiment 3N, N '-dibutyryl-N ", N " '-preparation of Ya ether base bis-thiourea
In the hexane solution that contains 259 parts of N-bytyry isothiocyanates; slowly splash into and contain 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 the 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 sees 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 the 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, copper mineral is mainly chalcopyrite in the ore, is vitreous copper-alpha chalcocite, tetrahedrite-tennantite etc. secondly; Iron mineral is mainly pyrite; The molybdenum ore thing is molybdenite.Raw ore cupric 0.35% contains molybdenum 0.016%.
Experiment process: one roughing; Mog :-0.074mm accounts for 65%; The medicament condition: lime consumption 800 gram/ton, 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 that 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
Figure BDA00002650901600051
Embodiment 6 certain high-sulfur copper sulfurized ore, raw ore cupric 0.40%.
Experiment process: one roughing.Mog :-0.074mm65%.The medicament condition: grey consumption is 400g/t, and 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 that 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, the major metal mineral are chalcopyrite, tetrahedrite and pyrite in the ore.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: lime 1200 grams/ton, N, N '-dibutyryl-N ", N " '-Ya propyl ether base bis-thiourea 30 grams/ton, butyl xanthate 10 grams/ton, MIBC25 gram/ton.Rough concentrate productive rate 9.16% wherein contains copper grade 7.73%, contains golden 4.23g/t, argentiferous 34.26g, and copper, the rate of recovery of Jin Heyin is respectively 87.42%, 86.10% and 85.51%.

Claims (4)

1. a two part collecting agent is characterized in that, the collecting agent that will be used as the metallic ore flotation suc as formula ether bis-thiourea or the thiourethane thiocarbamide composite base compound of structure shown in the I;
R wherein 1Representing general formula is R 3-C (=O)-acyl group or general formula be R 4O-C (=O)-ester group, R in the 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. ether bis-thiourea according to claim 1 or thiourethane thiocarbamide composite base compound is characterized in that R 1Be 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 claim 1 or 2 described ether bis-thioureas or thiourethane thiocarbamide composite base compound is as the flotation collector as metallic ore.
4. the preparation method of claim 1 or 2 described ether bis-thioureas or thiourethane thiocarbamide composite base compound, it is characterized in that, to and carry out addition reaction suc as formula the ether diamine shown in the III or ether alcohol amine suc as formula isothiocyanates shown in the II, reaction temperature-15 ℃～80 ℃, reaction time is 1～6 hour, generates suc as formula the bis-thiourea of ether shown in the I or thiourethane thiocarbamide composite base compound.
R 1-N=C=S formula II
R wherein 1Representing general formula is R 3-C (=O)-acyl group or general formula be R 4O-C (=O)-ester group, R in the formula 3And R 4Independently be selected from separately the alkyl of C1-C8;
Figure FDA00002650901500012
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56126459A (en) * 1980-03-10 1981-10-03 Dowa Mining Co Ltd Selective floatating method of lead mineral
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

Patent Citations (5)

* 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
JPS56126459A (en) * 1980-03-10 1981-10-03 Dowa Mining Co Ltd Selective floatating method of lead mineral
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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