APPLICATION OF SELENIUM-CONTAINING ORGANIC COMPOUNDS IN COPPER SULFIDE FLOTATION COLLECTORS

Abstract

Disclosed is an application of a class of selenium-containing organic compounds in copper sulfide flotation collectors, including organic compound with selenium atoms as functional groups and containing single selenium atom or multiple selenium atoms, where the organic compound with selenium atoms as functional groups and containing single selenium atom or multiple selenium atoms includes but not limited to selenophene, phenylselenol and diselenide as copper collectors; and a class of organic compound containing selenium atoms combined with nitrogen, oxygen, phosphorus, sulfur and carbon, where the class of organic compound containing selenium atoms combined with nitrogen, oxygen, phosphorus, sulfur and carbon includes but not limited to selenomethyl ester, carbonyl selenomethyl ester, oxycarbonyl selenomethyl ester, selenourea, selenium nitrogen, selenoxanthonic acid, selenoxanthate, selenophosphoric acid, selenium phosphate ester, triphenylphosphine selenide, all kinds of benzoselenediazole molecules as copper collectors.

Claims

1. An application of a class of selenium-containing organic compounds in copper sulfide flotation collectors, wherein the selenium-containing organic compounds comprise organic compounds with selenium atoms as functional groups and containing single selenium atom or multiple selenium atoms and organic compound containing selenium atoms combined with nitrogen, oxygen, phosphorus, sulfur and carbon, including but not limited to selenophene, phenylselenol, diselenide, selenomethyl ester, carbonyl selenomethyl ester and oxycarbonyl selenomethyl ester, selenourea, selenium nitrogen, selenoxanthonic acid, selenoxanthate, selenophosphoric acid, selenium phosphate ester, triphenylphosphine selenide, all kinds of benzoselenediazole molecules as copper collectors.

2. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 1, wherein molecular structures of the organic compound with selenium atom as functional groups and containing single selenium atom or multiple selenium atoms as copper ore flotation collectors are as follows:

3. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 1, wherein molecular structures of the class of organic compound containing selenium atoms combined with nitrogen, oxygen, phosphorus, sulfur and carbon are as follows:

4. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 2, wherein using the dibenzyl diselenide as the collector comprises following steps: dissolving 0.5%-5% of the dibenzyl diselenide in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the dibenzyl diselenide.

5. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 2, wherein using the phenyl selenium chloride as the collector comprises following steps: dissolving 0.5%-5% of the phenyl selenium chloride in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the phenyl selenium chloride.

6. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 2, wherein using the phenylselenol as the collector comprises following steps: dissolving 0.5%-5% of the phenylselenol in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the phenylselenol.

7. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 2, wherein using the dimethyl diselenide as the collector comprises following steps: dissolving 0.5%-5% of the dimethyl diselenide in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the dimethyl diselenide.

8. The application of a class of selenium-containing organic compounds in copper sulfide flotation collectors according to claim 2, wherein using the selenophene as the collector comprises following steps: dissolving 0.5%-5% of the selenophene in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the selenophene.

9. An application of the class of organic compound containing selenium atoms combined with nitrogen, oxygen, phosphorus, sulfur and carbon in copper ore flotation collectors according to claim 3, wherein using the triphenylphosphine selenide as the collector comprises following steps: dissolving 0.5%-5% of the triphenylphosphine selenide in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the triphenylphosphine selenide.

10. The application of the class of organic compound containing selenium atoms combined with nitrogen, oxygen, phosphorus, sulfur and carbon in copper ore flotation collectors according to claim 3, wherein using the 2,1,3-benzoselenediazole as the collector comprises following steps: dissolving 0.5%-5% of the benzoselenediazole in 95%-99.5% of dichloromethane according to percentage by mass, and stirring for 5 minutes to completely dissolve the benzoselenediazole.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0014] The technical scheme of the present application will be further described in detail by the following specific embodiment.

Embodiment 1

[0015] This embodiment is an application example of the organic compound with selenium atoms as functional groups and containing single selenium atom, including: [0016] mineral raw materials: [0017] in a large porphyry copper mine in Tibet, contents of target elements Cu (copper), Au (gold), Ag (silver) and S (sulfur) are 0.66%, 0.13 g/t, 2.99 g/t and 4.12% respectively, while the other elements are mainly SiO.sub.2 (silicon dioxide), Al.sub.2O.sub.3(aluminum oxide), Fe (ferrum) and K.sub.2O (potassium oxide), with contents of 63.87%, 16.41%, 3.99% and 2.15% respectively. The mineral particles in the ore are analyzed and counted by mineral liberation analyser (MLA), scanning electron microscope (SEM), X-ray diffractometer and X-ray energy spectrometer, and it is determined that gangue minerals are mainly quartz, muscovite, kaolinite, pyrophyllite and pyrite, etc. Main copper minerals are blue chalcocite/chalcocite and bornite, with the contents of 0.44% and 0.38% respectively, followed by chalcopyrite, tennantite and enargite, with the contents of 0.09%, 0.04% and 0.04% respectively, and covellite and antimony tetrahedrite are rare. The sulfur minerals include metal minerals and sulfate minerals. Besides copper minerals, the metal minerals of sulfur also include pyrite with a content of 7.07%, and a small amount of pyrrhotite, galena, sphalerite and molybdenite. Sulfate minerals are mainly alunite with a content of 1.17%, and a small amount of gypsum and barite. [0018] phenyl selenium chloride (structural formula C.sub.6H.sub.5SeCl), phenylselenol (structural formula C.sub.6H.sub.5SeH) and selenophene (structural formula C.sub.4H.sub.4Se) are used as collectors, where a flotation process includes following conditions: [0019] (1) a grinding fineness is?200 mesh, a content is 65%, a pH regulator is lime, and a pulp conditioning time is 3 minutes; [0020] (2) methyl isobutyl carbinol as foaming agent is added in a dosage of 20 g/t, and pulp conditioning is carried out for 2 minutes; [0021] (3) the collectors are added, and pulp conditioning is carried out for 2 minutes; [0022] (4) roughing duration is 3 minutes.

[0023] With the best conventional collector O-isobutyl-N-ethoxycarbonyl thiocarbamate (structural formula C.sub.2H.sub.5OOCNC(SH)OC.sub.4H.sub.9), a grade of roughing copper is 6.03% and a recovery rate is 87.74%.

[0024] When the phenyl selenium chloride (structural formula C.sub.6H.sub.5SeCl) is used as the collector, with optimum dosage of 30 g/t, a roughing copper grade is 6.95% and a recovery rate is 89.04% at pH of 8.27. When the phenylselenol (structural formula C.sub.6H.sub.5SeH) is used as the collector, with optimum dosage of 30 g/t, a roughing copper grade is 6.76% and a copper recovery rate is 89.15% at pH of 8.27. The flotation effect of these two organic compounds with selenium atom as functional group and containing single selenium atom as the collectors is better than that of the conventional collector, and the grade and recovery rate are higher than those of the conventional collector, showing better selectivity.

[0025] When the selenophene (structural C.sub.4H.sub.4Se) is used as the collector, with optimum dosage of 300 g/t, a roughing grade of copper is 5.20% and a recovery rate of copper is 77.24% at pH of 8.27. The flotation effect of this organic compound with selenium atom as functional group and containing single selenium atom as the collector is basically the same as that of conventional collector, and this organic compound obtains a better copper flotation index.

Embodiment 2

[0026] This embodiment is an application example of the organic compound with selenium atoms as functional groups and containing multiple selenium atoms, including: [0027] the same raw materials as those in embodiment 1.

[0028] Dibenzyl diselenide (structural formula C.sub.6H.sub.5Se2C.sub.6H.sub.5) and dimethyl diselenide (structural formula CH.sub.3Se.sub.2CH.sub.3) are used as collectors, where the flotation process includes following conditions: [0029] (1) the grinding fineness is ?200 mesh, the content is 65%, the pH regulator is lime, and the pulp conditioning time is 3 minutes; [0030] (2) the methyl isobutyl carbinol as foaming agent is added in a dosage of 20 g/t, and pulp conditioning is carried out for 2 minutes; [0031] (3) the collectors are added, and pulp conditioning is carried out for 2 minutes; [0032] (4) roughing duration is 3 minutes.

[0033] With the best conventional collector O-isobutyl-N-ethoxycarbonyl thiocarbamate (structural formula C.sub.2H.sub.5OOCNC(SH)OC.sub.4H.sub.9), the grade of roughing copper is 6.03% and the recovery rate is 87.74%.

[0034] When the dibenzyl diselenide (structural formula C.sub.6H.sub.5Se.sub.2C.sub.6H.sub.5) is used as the collector, with optimum dosage of 30 g/t, the roughing copper grade is 6.03% and the recovery rate is 89.14% at pH 8.27. The flotation effect of this organic compound with selenium atoms as functional groups and containing multiple selenium atoms as collector is better than that of conventional collectors, and the grade and recovery rate are higher than those of conventional collectors, showing better selectivity.

[0035] When the dimethyl diselenide (structural formula CH.sub.3Se.sub.2CH.sub.3) is used as the collector, with optimum dosage of 30 g/t, the copper grade is 6.56% and the copper recovery rate is 85.81% at pH 8.27. The flotation effect of this organic compound with selenium atoms as functional groups and containing multiple selenium atoms as collector is basically the same as that of the conventional collector, and this organic compound obtains a better copper flotation index.

Embodiment 3

[0036] This embodiment is an application example of the organic compound containing various structures composed of selenium atom and nitrogen, oxygen, phosphorus, sulfur and carbon as collectors for copper ore flotation, including: [0037] the same raw materials as those in embodiment 1.

[0038] Triphenylphosphine selenide (structural formula (C.sub.6H.sub.5).sub.3PSe) is adopted as a collector, where the flotation process includes following conditions: [0039] (1) the grinding fineness is ?200 mesh, the content is 65%, the pH regulator is lime, and the pulp conditioning time is 3 minutes; [0040] (2) the methyl isobutyl carbinol as foaming agent is added in a dosage of 20 g/t, and pulp conditioning is carried out for 2 minutes; [0041] (3) the collector is added and pulp conditioning is carried out for 2 minutes; [0042] (4) roughing duration is 3 minutes.

[0043] With the best conventional collector O-isobutyl-N-ethoxycarbonyl thiocarbamate (structural formula C.sub.2H.sub.5OOCNC(SH)OC.sub.4H.sub.9), the grade of roughing copper is 6.03% and the recovery rate is 87.74%.

[0044] When the triphenylphosphine selenide (structural formula (C.sub.6H.sub.5).sub.3PSe) is used as the collector, with optimum dosage of 200 g/t, the grade of roughed copper is 6.94% and the recovery rate of copper is 84.47% at pH of 8.27. The flotation effect of this organic compound containing selenium atoms combined with phosphorus atoms is basically the same as that of conventional collectors, and this organic compound obtains a better copper flotation index.

Embodiment 4

[0045] This embodiment is another application example of the organic compound with various structures composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon as copper ore flotation collectors, including: [0046] the same raw materials as those in embodiment 1. [0047] 2,1,3-benzoselenediazole (structural formula C.sub.4H.sub.4C.sub.2N.sub.2Se) is adopted as a collector where the flotation process includes following conditions: [0048] (1) the grinding fineness is?200 mesh, the content is 65%, the pH regulator is lime, and the pulp conditioning time is 3 minutes; [0049] (2) the methyl isobutyl carbinol as foaming agent is added in a dosage of 20 g/t, and pulp conditioning is carried out for 2 minutes; [0050] (3) the collector is added, and pulp conditioning is carried out for 2 minutes; [0051] (4) roughing duration is 3 minutes.

[0052] With the best conventional collector O-isobutyl-N-ethoxycarbonyl thiocarbamate (structural formula C.sub.2H.sub.5OOCNC(SH)OC.sub.4H.sub.9), the grade of roughing copper is 6.03% and the recovery rate is 87.74%.

[0053] When the 2,1,3-benzoselenediazole (structural formula C.sub.4H.sub.4C.sub.2N.sub.2Se) is used as the collector, with optimum dosage of 30 g/t, the roughing grade of copper is 6.61% and the recovery rate of copper is 80.59% at pH of 8.27. The flotation effect of this organic compound containing selenium atom combined with nitrogen atoms is basically the same as that of conventional collectors, and this organic compound obtains a better copper flotation index.