CN102503874B - Thiourea compound, application thereof to metal ore flotation and preparation of thiourea compound - Google Patents
Thiourea compound, application thereof to metal ore flotation and preparation of thiourea compound Download PDFInfo
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- CN102503874B CN102503874B CN 201110341679 CN201110341679A CN102503874B CN 102503874 B CN102503874 B CN 102503874B CN 201110341679 CN201110341679 CN 201110341679 CN 201110341679 A CN201110341679 A CN 201110341679A CN 102503874 B CN102503874 B CN 102503874B
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Abstract
The invention discloses a thiourea compound, an application thereof to metal ore flotation and preparation of the thiourea compound. An N-carboalkoxy(aryloxy)-N'-carboalkoxypropyl thiourea compound shown in a formula (I) is taken as a collecting agent of non-ferrous metal ore and precious metal flotation. The formula (I) is shown in the specifications, wherein R1 represents alkyl, aryl or aralkylwith 1-8 carbon atoms, and R2 represents alkyl, aryl or aralkyl with 1-16 carbon atoms; or the formula (I) is R3OR4, wherein R3 represents alkyl with 1-3 carbon atoms, and R4 represents alkylene, aryl or aromatic alkylidene with 1-16 carbon atoms; and R1 and R2 are independent of each other. The compound shown as the formula (I) is taken as a flotation collecting agent, so that valent metal minerals are recovered efficiently from non-ferrous metal ore and precious metal ore. In the N-carboalkoxy(aryloxy)-N'-carboalkoxypropyl thiourea compound, ether is contained in a collecting agent molecule, so that the melting point of the collecting agent can be lowered, the dispersibility of the collecting in an aqueous solution is enhanced, and flotation separation extraction of the non-ferrous metal ore and noble metal ore is enhanced. The N-carboalkoxy(aryloxy)-N'-carboalkoxypropyl thiourea compound has the characteristics of easy and simple synthesizing method, high metal recovering rate, andthe like.
Description
[technical field]
The present invention relates to a kind of compound of new texture---N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound and preparation method thereof and the application in the metallic ore flotation.
[background technology]
Flotation reagent is the gordian technique of flotation process separation and Extraction valuable mineral component.More and more poorer along with Mineral resources, thin, assorted, research and develop new and effective flotation collector, process the development and use of ore for complicated difficult, improve the metal comprehensive recovery and have vital role.
Thiourea has become the mineral floating collecting agent of a quasi-representative because the metal ions such as copper, lead, zinc, gold are had good sequestering action.The thiourea compound of reporting for work at present as flotation collector has thiambutosine (to be commonly called as baiyao, see structural formula a, D.W.Fuerstenau, R.Herrera-Urbina, D.W.McGlashan.Studies on the applicability of chelating agents as universal collectors for copper minerals.Int.J.Miner.Process.2000,58:15-33), isothiourea (Wang Dian assistant, Lin Qiang, Jiang Yuren. ore dressing and the design of metallurgical agent molecule. Changsha: press of Zhongnan Polytechnic Univ, 1996), N-hydrocarbon carbonyl oxygen thiocarbamide (is seen structural formula b, Fu Yun-Lung, Wang Samuel S.Neutral hydrocarboxycarbonyl thiourea sulfide collectors.USRE32786,1988-11-22; Liu Guang-yi, Zhong Hong, Xia Liu-yin, Wang Shuai, Xu Zheng-he.Improving copper flotation recovery from a refractory copper porphyry ore by using ethoxycarbonyl thiourea as a collector.Minerals Engineering.2011,24:817-824), bis-thiourea (is seen structural formula c, d, e and f, Zhong Hong, Liu Guangyi, Wang Shuai. di-ester-base diisothiocyanic acid ester derivative application in sulfide flotation and preparation method thereof .CN101337206A, 2009-1-7; 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).
These thiocarbamide collecting agents show good collecting performance to Non-ferrous minerals and precious metal minerals, can realize that these valuable elements separate with the selective flotation of the gangue minerals such as pyrite, pyrrhotite in the pH scope widely.Yet existing thiocarbamide collecting agent generally is solid at normal temperatures, adds inconvenience, and dispersion is bad in ore pulp simultaneously, and is insufficient with the mineral surface effect, limits their application in flotation.
[summary of the invention]
The present invention proposes a kind of thiourea compound of new texture---N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound and application are as flotation collector, and the preparation method of this compounds.By the addition reaction of N-hydrocarbon carbonyl oxygen lsothiocyanates and hydrocarbon oxygen propanamine compounds, the efficient economy that has formed N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound is synthetic.N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound can reduce the fusing point of collecting agent and strengthen its dispersiveness in the aqueous solution, thereby the flotation separation of strengthening nonferrous metallic ores and precious metal ore is extracted owing to containing ether in the collecting agent molecule.Have simple synthetic method, metal recovery rate high.
At present, N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound has no report as flotation reagent in pneumatic flotation, does not also see the defined N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propyl group thiocarbamide and synthetic method and application in U.S. CA database.
The flotation collector that the purpose of this invention is to provide a kind of new texture---N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound, and as the application of the collecting agent of nonferrous metallic ores and precious metal ore flotation, to strengthen the comprehensive recovery of copper, lead, zinc, nickel, gold and silver etc. and to realize that these mineral separate with the efficient flotation separation of pyrite, pyrrhotite etc.
Another object of the present invention aims to provide the high efficiency preparation method of described N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound.
The objective of the invention is to realize by following manner:
A kind of name is called N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound and has the structure shown in the formula I:
R wherein
1Represent C
1-C
8Alkyl, C
6-C
8Aryl or C
7-C
8Aralkyl, R
2Represent C
1-C
16Alkyl, aryl or aralkyl, or R
3OR
4, R wherein
3Represent C
1-C
3Alkyl, R
4Represent C
1-C
16Alkylidene group, C
6-C
16Aryl or C
7-C
16Arylmethylene alkyl; R
1, R
2Separate.
R wherein
1Be preferably methyl, ethyl, sec.-propyl, butyl or isobutyl-; R
2Be preferably propyl group, sec.-propyl, butyl, isobutyl-or methoxyethyl.
Application of the present invention is the collecting agent of the N-hydrocarbon carbonyl oxygen-N ' shown in the formula I-hydrocarbon oxygen propylthio carbamide compound as nonferrous metals ore or precious metal ore flotation.
Operation primary process is: (a) enter flotation behind the grinde ore; (b) in ore grinding and/or floatation process, add flotation reagent and size mixing, contain at least a kind of N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound in the medicament of interpolation; (c) by froth-flotation method emersion useful metal mineral.
N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propylthio carbamide compound is 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, nickel mineral, gold and silver had strong collecting ability, a little less than the collecting ability to gangue minerals such as pyrite, pyrrhotite, selectivity is good.Adopt N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propylthio carbamide compound to unite use as flotation collector or with other collecting agent separately, under the condition of N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound consumption 1～100 gram/ton, pH values of pulp 5.0～14 scopes, compare with existing collecting agent, the flotation recovery rate of Non-ferrous minerals and precious metal minerals is improved, realize that valuable mineral separates with the efficient flotation separation of gangue mineral, reduce inhibitor consumption when separating, improve the metal comprehensive recovery.
Flotation collector N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propylthio carbamide compound can make by the following method.
N-hydrocarbon carbonyl oxygen lsothiocyanates and hydrocarbon oxygen propanamine compounds are carried out addition reaction, temperature of reaction-15 ℃～60 ℃, the reaction times is 1～6 hour, generates suc as formula the hydrocarbon carbonyl oxygen-N ' of N-shown in the I-hydrocarbon oxygen propylthio carbamide compound;
The general molecular formula of described N-hydrocarbon carbonyl oxygen lsothiocyanates is:
Formula II
R wherein
1Represent C
1-C
8Alkyl.Comprise N-methoxycarbonyl lsothiocyanates, N-ethoxycarbonyl isothiocyanate, N-the third oxygen carbony isorhodanate, N-butoxy carbonyl lsothiocyanates, N-penta oxygen carbony isorhodanate, the own oxygen carbony isorhodanate of N-, the different hot oxygen carbony isorhodanate of N-and N-carbobenzoxy-(Cbz) lsothiocyanates etc.
The chemical general formula of described hydrocarbon oxygen propanamine compounds is R
2OCH
2CH
2CH
2NH
2, R wherein
2Represent C
1-C
16Alkyl, C
6-C
16Aryl or C
7-C
16Aralkyl, or R
3OR
4, R wherein
3Represent C
1-C
3Alkyl, R
4Represent C
1-C
16Alkylidene group, C
6-C
16Aryl or C
7-C
16Arylmethylene alkyl.Comprise ethoxy propylamine, the third oxygen propylamine, isopropyl oxygen propylamine, fourth oxygen propylamine, isobutyl oxygen propylamine, hot oxygen propylamine, phenoxy propylamine, dodecane oxygen propylamine, first ethoxy propylamine etc.
The preparation method of N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propyl group thiocarbamide has following characteristics: preparation process is simple, efficient, practical, and conversion rate of products is greater than 92%, and crude product namely can be used as flotation collector.
[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 ratio all refer to quality except as otherwise herein provided among the embodiment.
(1) preparation of N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound
The preparation of embodiment 1 N-ethoxycarbonyl-N '-Ding oxygen propyl group thiocarbamide
131.2 parts of γ-butoxy propyl amines are added water, and to be configured to mass concentration be 30% γ-butoxy propyl amine aqueous solution, under temperature of reaction is-5～10 ℃ and agitation condition, slowly join in the three-necked flask that contains 131.2 parts of N-ethoxycarbonyl isothiocyanates, then stirring reaction 2 hours is warmed up to room temperature and reacted 1 hour again.Static layering gets 262.5 parts of yellow oil product N-ethoxycarbonyl-N '-Ding oxygen propyl group thiocarbamide, and product purity is 94.5%.
The preparation of embodiment 2 N-ethoxycarbonyl-N '-isopropyl oxygen propyl group thiocarbamide
117.2 parts of γ-isopropoxy propylamine is added water, and to be configured to mass concentration be 20% γ-isopropoxy propylamine aqueous solution, under temperature of reaction is-5～10 ℃ and agitation condition, slowly join in the three-necked flask that contains 131.2 parts of N-ethoxycarbonyl isothiocyanates, then stirring reaction 1 hour is warmed up to room temperature and reacted 1 hour again.Static layering gets 248.2 parts of yellow oil product N-ethoxycarbonyl-N '-isopropyl oxygen propyl group thiocarbamide, and product purity is 95.5%.
The preparation of the different hot oxygen carbonyl-N ' of embodiment 3 N--isopropyl oxygen propyl group thiocarbamide
117.2 parts of γ-isopropoxy propylamine is added water, and to be configured to mass concentration be 40% γ-isopropoxy propylamine aqueous solution, under temperature of reaction is-5～10 ℃ and agitation condition, slowly join in the three-necked flask that contains 215.2 parts of different hot oxygen carbony isorhodanates of N-, then stirring reaction 1.5 hours is warmed up to room temperature and reacted 1 hour again.Static layering gets 332.1 parts of the different hot oxygen carbonyl-N ' of yellow oil product N--isopropyl oxygen propyl group thiocarbamide, and product purity is 95.8%.
(2) N-hydrocarbon carbonyl oxygen-N '-application of hydrocarbon oxygen propylthio carbamide compound in the metallic ore flotation
Embodiment 4: certain Copper Ores sample ore, copper mineral is mainly chalcopyrite in the ore, is copper glance-alpha chalcocite, tetrahedrite-tennantite etc. secondly.Iron mineral is mainly pyrite.Raw ore cupric 0.37%, sulfur-bearing 1.42%.
Experiment process: one roughing; Grinding fineness :-0.074mm accounts for 64.6%; The medicament condition: lime consumption 1000 gram/ton, slurry pH is 8.5, all the other medicament conditions and the results are shown in Table 1.The test-results of table 1 shows, N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propyl group thiocarbamide collecting agent can be obtained than collecting agent butyl xanthate commonly used and the higher copper flotation recovery rate of N-ethoxycarbonyl-N '-propyl group thiocarbamide.
Flotation conditions and the result thereof of table 1 N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound
Embodiment 5 certain porphyry copper stone ore sample, copper mineral is mainly chalcopyrite in the ore, and sulfur mineral is mainly pyrite.Raw ore cupric 0.41%, sulfur-bearing 2.02%.
Experiment process: one roughing; Grinding fineness :-0.074mm accounts for 64.3%; The medicament condition: lime consumption 1200 gram/ton, slurry pH is 8.5, all the other medicament conditions and the results are shown in Table 2.The test-results of table 2 shows, N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propyl group thiocarbamide collecting agent is obtained than collecting agent butyl xanthate commonly used and the higher copper flotation recovery rate of N-ethoxycarbonyl-N '-propyl group thiocarbamide.
The flotation porphyry copper of table 2 N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propylthio carbamide compound
Embodiment 6 certain copper/lead/zinc ore, raw ore cupric about 0.58%.Experiment process: one roughing.Grinding fineness :-0.074mm80%.The medicament condition: yellow soda ash 1500 gram/ton, zinc sulfate 1000 grams/ton, S-WAT 1000 grams/ton, slurry pH is 8.0, all the other medicament conditions and the results are shown in Table 3.The test-results of table 3 shows, N-ethoxycarbonyl-N ' of the present invention-Ding oxygen propyl group thiocarbamide is obtained the copper flotation recovery rate higher than N-butoxy carbonyl-N '-propyl group thiocarbamide.
Table 3 new collector flotation copper/lead/zinc ore test-results
Embodiment 7 certain copper tin ore, raw ore contains Cu 0.41%, Sn 0.39%, S 8.6%, Fe 25.1%, and wherein the copper oxidation ratio is 6.3%, secondary rate is 14.1%.Experiment process: one roughing once purging selection.Grinding fineness :-0.074mm65%; The medicament condition: ball milling lime 3000 gram/ton, slurry pH is that 8.5,730A is pore forming material, all the other medicament conditions and the results are shown in Table 4.The test-results of table 4 shows, N-hydrocarbon carbonyl oxygen-N ' of the present invention-hydrocarbon oxygen propyl group thiocarbamide collecting agent also can be obtained than collecting agent butyl xanthate commonly used and the higher copper flotation recovery rate of N-ethoxycarbonyl-N '-propyl group thiocarbamide.
Table 4 new collector Floatation of Copper tin ore test-results
Claims (5)
1. a thiourea compound is characterized in that, described thiourea compound is N-hydrocarbon carbonyl oxygen-N '-hydrocarbon oxygen propyl group thiocarbamide, has structure shown in the formula I; Collecting agent for the nonferrous metallic ores flotation;
R wherein
1Represent C
1-C
8Alkyl, C
6-C
8Aryl or C
7-C
8Aralkyl; R
2Represent C
1-C
16Alkyl, C
6-C
16Aryl or C
7-C
16Aralkyl, or R
3OR
4, R wherein
3Represent C
1-C
3Alkyl, R
4Represent C
1-C
16Alkylidene group, C
6-C
16Arylidene or C
7-C
16Arylmethylene alkyl; R
1, R
2Separate.
2. thiourea compound according to claim 1 is characterized in that, wherein R
1Be methyl, ethyl, sec.-propyl, butyl or isobutyl-; R
2Be propyl group, sec.-propyl, butyl, isobutyl-or methoxyethyl.
3. the preparation method of N-hydrocarbon carbonyl oxygen-N ' claimed in claim 1-hydrocarbon oxygen propylthio carbamide compound, it is characterized in that, N-hydrocarbon carbonyl oxygen lsothiocyanates and hydrocarbon oxygen propanamine compounds are carried out addition reaction, temperature of reaction-15 ℃～60 ℃, reaction times is 1～6 hour, generates N-hydrocarbon carbonyl oxygen-N ' with structure shown in the formula I-hydrocarbon oxygen propylthio carbamide compound;
Described N-hydrocarbon carbonyl oxygen lsothiocyanates have a structure shown in the formula II:
R wherein
1Represent C
1-C
8Alkyl, C
6-C
8Aryl or C
7-C
8Aralkyl;
The chemical general formula of described hydrocarbon oxygen propanamine compounds is R
2OCH
2CH
2CH
2NH
2, R wherein
2Represent C
1-C
16Alkyl, C
6-C
16Aryl or C
7-C
16Aralkyl, or R
3OR
4, R wherein
3Represent C
1-C
3Alkyl, R
4Represent C
1-C
16Alkylidene group, C
6-C
16Arylidene and C
7-C
16Arylmethylene alkyl.
4. the application of claim 1 or 2 described thiourea compounds is with the collecting agent of the N-hydrocarbon carbonyl oxygen-N ' of structure shown in the formula I-hydrocarbon oxygen propylthio carbamide compound as the nonferrous metallic ores flotation.
5. the application of thiourea compound according to claim 4, its nonferrous metallic ores be copper-containing ore, zinc-containing ores, contain lead ore, nickel-containing ore, contain molybdenum ore, golden precious metal ore or silver-colored precious metal ore.
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| CN104084313B (en) * | 2014-06-24 | 2018-06-26 | 云南科力新材料股份有限公司 | A kind of flotation collector and frother and preparation method thereof |
| CN107377232A (en) * | 2017-07-12 | 2017-11-24 | 湖南有色金属研究院 | A kind of composite restrainer being used in lead concentrate floatation process |
| CN110681495B (en) * | 2019-09-28 | 2021-08-06 | 北京矿冶科技集团有限公司 | Thiourea compound flotation separation inhibitor and flotation separation method thereof |
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