Application of a class of selenium-containing organic compounds as flotation agents for copper sulfide

Abstract

The invention discloses an application of a class of selenium-containing organic compounds in copper sulfide flotation collectors, including organic compounds containing single or multiple selenium atoms with selenium atoms as functional groups, including but not limited to: selenophene, phenylselenol, diselenide as copper collectors, and an organic compound containing selenium atoms and nitrogen, oxygen, phosphorus, sulfur, and carbon, including but not limited to: selenoamine esters, carbonyl selenoamine esters, oxycarbonyl selenoamine esters, selenourea, selenium nitrogen, selenoxanthate, selenoxanthate, selenophosphoric acid, selenophosphate esters, triphenylphosphine selenide, and benzoselenadiazole molecules as copper collectors. The selenium-containing organic compound collector has good collection performance for copper sulfide minerals, and its flotation effect is consistent with that of traditional collectors with N, O, P, and S as structures. The flotation effect of some selenium-containing collectors even exceeds the current oxycarbonyl ester collectors for copper sulfide flotation effect.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing agents, in particular to the application of a class of selenium-containing organic compounds in copper sulfide flotation agents. Background Art

[0002] Flotation reagents are divided into collectors, inhibitors and frothers. The function of collectors is to regulate the hydrophobicity of mineral surfaces, and they play a very important role in mineral flotation. It is generally believed that the progress of flotation theory and technology mainly depends on the invention of new structures of collectors and their working principles. For example, the invention of O-isopropyl-N-ethylthiocarbamate (Z-200) in the 1960s significantly improved the flotation selectivity of copper minerals, and the global copper production increased significantly. However, looking back at the 100-year history of flotation reagent development, it is increasingly difficult to invent efficient flotation reagents with new structures. Since the invention of the thiocarbonic acid series collectors in the late 1920s, such as xanthate, black medicine and sulfur-nitrogen series, the invention of copper flotation ester collectors represented by O-isopropyl-N-ethylthiocarbamate (Z-200) in the 1960s, and the invention of sodium diisobutyl dithiophosphinate (3418A) with selective lead collection by Cytec in the 1990s, there have been few reports of flotation collectors with new structures that have significant effects since the 21st century. The invention of new structures of flotation reagents has entered a bottleneck period, mainly due to the limited ligand atoms in the existing molecular structure of flotation collectors.

[0003] Flotation collectors are generally organic compounds containing solid-loving groups and hydrophobic groups, among which the solid-loving groups are the key to determining the selectivity of flotation reagent molecules. The design of selective collectors is mainly the design of solid-loving groups. The atoms that constitute the functional groups of organic compounds for flotation are currently dominated by the four major ligand atoms of N, O, P, and S. Arsenic atoms were once used as functional group atoms, such as benzyl arsenic acid. Due to toxicity issues, this type of structure is no longer used. At present, all flotation reagents are designed and combined with the four major ligand atoms of N, O, P, and S, such as SS-type, OO-type, NN-type, SN-type, ON-type and SO-type collector functional groups. Phosphorus atoms are generally not used as functional group bonds and atoms, but as constituent atoms in the functional group structure, such as the black drug functional group -POSSH, whose bonding drug is sulfur atom, and its essence is still SS type. Another example is the phosphate functional group -O-PO(OH)2, in which the bonding atom is oxygen atom, and its essence is OO type. In fact, the atoms with coordination ability in the functional groups of flotation agents are mainly N, O, and S. Since the advent of flotation technology for a hundred years, the functional groups of flotation agents have undergone a large number of combinations and designs. It is already very difficult to find a new structure composed of the four atoms of N, O, P, and S. The traditional flotation agent structure has developed to a bottleneck stage and it is difficult to have a new breakthrough. The present invention is a brand-new copper sulfide flotation collector with a functional group structure with selenium atoms as the core. Its flotation effect is consistent with that of the traditional collector with N, O, P, and S as the structure. The flotation effect of some selenium-containing collectors even exceeds that of the best collector for copper flotation, oxycarbonyl ester collectors, such as phenylselenol, dibenzyl diselenide, etc. It is the biggest breakthrough in flotation collectors in the past hundred years. It develops the four major ligand atoms of N, O, P, and S in the traditional flotation agent to five major ligands of Se, N, O, P, and S, providing more new structural designs for the new structural design of flotation agents. Summary of the invention

[0004] The purpose of the present invention is to provide a type of application of selenium-containing organic compounds in copper sulfide flotation collectors, which are copper sulfide flotation collectors with a functional group structure based on selenium atoms as the core. The flotation effect of the present invention is consistent with that of traditional collectors with N, O, P, and S as the structure. The flotation effect of some selenium-containing collectors even exceeds that of the best copper flotation collector, oxycarbonyl ester collectors, such as phenylselenol and dibenzyl diselenide. This is the biggest breakthrough in flotation collectors in the past century, and the four major ligand atoms of traditional flotation agents, N, O, P, and S, are developed into five major ligands, Se, N, O, P, and S, providing more new structural designs for the new structural design of flotation agents.

[0005] The technical solution of the present invention is: the application of a class of selenium-containing organic compounds in copper sulfide flotation collectors, the selenium-containing organic compounds are organic compounds containing a single selenium atom or multiple selenium atoms with selenium atoms as functional groups, including but not limited to: selenophene, phenylselenol, and diselenide as copper collectors.

[0006] A class of organic compounds containing selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon. The organic compounds contain structures composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon, including but not limited to: selenoamine, carbonyl selenoamine, oxycarbonyl selenoamine, selenourea, selenonitrogen, selenoxanthate, selenoxanthate, selenophosphoric acid, selenophosphate ester, triphenylphosphine selenide, and various benzoselenadiazole molecules as copper collectors.

[0007] The organic compound containing a single selenium atom or multiple selenium atoms with selenium atom as a functional group is used as a copper ore flotation collector, and its molecular structure is as follows:

[0008]

[0009]

[0010] The organic compound composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon is used as a copper ore flotation collector, and its molecular structure is as follows:

[0011]

[0012]

[0013]

[0014]

[0015] Working principle:

[0016] According to the hard-soft acid-base principle, the copper ions in copper sulfide minerals are relatively soft acids, and the traditional copper flotation collectors such as black medicine, thiocarbamate, oxycarbonyl ester, etc. are relatively soft bases. These agents have good selectivity for copper sulfide flotation. As an atom softer than sulfur, selenium atoms are ranked later than black medicine functional groups and sulfur-nitrogen functional groups in the ligand spectrum series, which means that selenium-containing functional groups are stronger ligands than black medicine, thiocarbamate, oxycarbonyl ester, etc. Therefore, collectors containing selenium atoms are theoretically easier to interact with copper sulfide minerals than traditional copper mine collectors, and have better selectivity.

[0017] In addition, according to the flotation coordination chemistry theory, when the π electron pairs of metal ions on the mineral surface form feedback π bonds with the empty π orbitals on the collector molecules, the selective interaction between the collector and the mineral surface is the strongest. Quantum calculation results show that collectors containing selenium atoms all contain empty π orbitals in their molecular structures, which can form strong feedback π bonds with copper atoms on the surface of copper sulfide minerals, thus achieving selective flotation of copper sulfide minerals.

[0018] The outstanding advantage of the present invention is that the flotation effect of the copper sulfide flotation collector with selenium atoms as the core functional group structure is consistent with that of the traditional collector with N, O, P, and S as the structure. The flotation effect of some selenium-containing collectors even exceeds that of the best oxycarbonyl ester collectors for copper flotation, such as phenylselenol and dibenzyl diselenide. This invention develops the four major ligand atoms of N, O, P, and S in the traditional flotation reagent to five major ligands of Se, N, O, P, and S, providing more new structural designs for the new structural design of flotation reagents. DETAILED DESCRIPTION

[0019] The technical solution of the present invention is further described in detail below through specific embodiments.

[0020] Example 1

[0021] This embodiment is an application example of the organic compound containing a single selenium atom with a selenium atom as a functional group according to the present invention, and comprises the following steps:

[0022] Mineral raw materials:

[0023] In a large porphyry copper mine in Tibet, the contents of the target elements Cu, Au, Ag and S in the ore are 0.66%, 0.13g / t, 2.99g / t and 4.12% respectively. Other elements are mainly SiO2, Al2O3, Fe and K2O, with contents of 63.87%, 16.41%, 3.99% and 2.15% respectively. There are also small amounts of MgO, Na2O and CaO. MLA, scanning electron microscope, X-ray diffractometer and X-ray energy spectrometer were used to analyze and count the mineral particles in the ore to determine its mineral composition. The gangue minerals mainly include quartz, muscovite, kaolinite, pyrophyllite and pyrite; the copper minerals are mainly blue chalcocite / chalcocite and bornite, with contents of 0.44% and 0.38% respectively, followed by chalcopyrite, arsenic tetrahedrite and arsenic sulfide, with contents of 0.09%, 0.04% and 0.04% respectively, and covellite and antimony tetrahedrite are occasionally seen; sulfur minerals include metallic minerals and sulfate minerals. In addition to copper minerals, sulfur metallic minerals also include pyrite, with a content of 7.07%, and a small amount of pyrrhotite, galena, sphalerite and molybdenite; the sulfate minerals are mainly alunite, with a content of 1.17%, and a small amount of gypsum and barite.

[0024] Phenyl selenium chloride (structural formula C6H5SeCl), phenylselenol (structural formula C6H5SeH), and selenophene (structural formula C4H4Se) are used as collectors, and the flotation process includes:

[0025] (1) The grinding fineness is -200 mesh and the content is 65%, the pH adjuster is lime, and the slurry mixing time is 3 minutes;

[0026] (2) The dosage of methyl isobutyl carbinol as a foaming agent is 20 g / t, and the slurry is mixed for 2 minutes after adding the foaming agent;

[0027] (3) Add collector and mix the slurry for 2 minutes;

[0028] (4) The rough selection time is 3 minutes.

[0029] By using the best traditional collector O-isobutyl-N-ethoxycarbonylthiocarbamate (structural formula C2H5OOCNC(SH)O-C4H9), a rough copper grade of 6.03% and a recovery rate of 87.74% can be obtained.

[0030] When phenylselenium chloride (structural formula C6H5SeCl) is used as a collector, the optimal dosage is 30g / t. At a pH of 8.27, a rough copper grade of 6.95% and a recovery rate of 89.04% are obtained; when phenylselenol (structural formula C6H5SeH) is used as a collector, the optimal dosage is 30g / t. At a pH of 8.27, a rough copper grade of 6.76% and a copper recovery rate of 89.15% are obtained. The flotation effect of these two organic compounds containing a single selenium atom with selenium atoms as functional groups as collectors is better than that of traditional collectors, and the grade and recovery rate are higher than those of traditional collectors, showing better selectivity.

[0031] When selenophene (structural formula C4H4Se) is used as a collector, the optimal dosage is 300g / t. At a pH of 8.27, a copper roughing grade of 5.20% and a copper recovery rate of 77.24% are obtained. The flotation effect of this organic compound containing a single selenium atom with a selenium atom as a functional group as a collector is basically equivalent to that of a traditional collector, and a relatively good flotation copper index can be obtained.

[0032] Example 2

[0033] This embodiment is an application example of the organic compound containing multiple selenium atoms with selenium atoms as functional groups described in the present invention, and comprises the following steps:

[0034] The mineral raw materials are the same as those in Example 1.

[0035] Using dibenzyl diselenide (structural formula C6H5Se2C6H5) and dimethyl diselenide (structural formula CH3Se2CH3) as collectors, the flotation process includes:

[0036] (1) The grinding fineness is -200 mesh and the content is 65%, the pH adjuster is lime, and the slurry mixing time is 3 minutes;

[0037] (2) The dosage of methyl isobutyl carbinol as a foaming agent is 20 g / t, and the slurry is mixed for 2 minutes after adding the foaming agent;

[0038] (3) Add collector and mix the slurry for 2 minutes;

[0039] (4) The rough selection time is 3 minutes.

[0040] By using the best traditional collector O-isobutyl-N-ethoxycarbonylthiocarbamate (structural formula C2H5OOCNC(SH)O-C4H9), a rough copper grade of 6.03% and a recovery rate of 87.74% can be obtained.

[0041] When dibenzyl diselenide (structural formula C6H5Se2C6H5) is used as a collector, the optimal dosage is 30g / t. At a pH of 8.27, a rough copper grade of 6.03% and a recovery rate of 89.14% are obtained. This organic compound containing multiple selenium atoms with selenium atoms as functional groups has a better flotation effect than traditional collectors, and both the grade and recovery rate are higher than traditional collectors, showing better selectivity.

[0042] When dimethyl diselenide (structural formula CH3Se2CH3) is used as a collector, the optimal dosage is 30g / t, and the copper grade is 6.56% at a pH of 8.27, and the copper recovery rate is 85.81%. The flotation effect of this organic compound containing multiple selenium atoms with selenium atoms as functional groups as a collector is basically equivalent to that of traditional collectors, and a relatively good flotation copper index can be obtained.

[0043] Example 3

[0044] This embodiment is an application example of the organic compounds of various structures composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon as a copper ore flotation collector according to the present invention, comprising the following steps:

[0045] The mineral raw materials are the same as those in Example 1.

[0046] Triphenylphosphine selenide (structural formula (C6H5)3PSe) is used as a collector.

[0047] (1) The grinding fineness is -200 mesh and the content is 65%, the pH adjuster is lime, and the slurry mixing time is 3 minutes;

[0048] (2) The dosage of methyl isobutyl carbinol as a foaming agent is 20 g / t, and the slurry is mixed for 2 minutes after adding the foaming agent;

[0049] (3) Add collector and mix the slurry for 2 minutes;

[0050] (4) The rough selection time is 3 minutes.

[0051] By using the best traditional collector O-isobutyl-N-ethoxycarbonylthiocarbamate (structural formula C2H5OOCNC(SH)O-C4H9), a rough copper grade of 6.03% and a recovery rate of 87.74% can be obtained.

[0052] When triphenylphosphine selenide (structural formula (C6H5)3PSe) is used as a collector, the optimal dosage is 200g / t, at a pH of 8.27. A rough copper grade of 6.94% and a copper recovery rate of 84.47% are obtained. The flotation effect of this organic compound containing a structure composed of selenium atoms and phosphorus atoms is basically equivalent to that of traditional collectors, and relatively good flotation copper indicators can be obtained.

[0053] Example 4

[0054] This embodiment is another application example of the organic compounds of various structures composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon as a copper ore flotation collector according to the present invention, comprising the following steps:

[0055] The mineral raw materials are the same as those in Example 1.

[0056] 2,1,3-Benzoselenadiazole (structural formula C4H4C2N2Se) is used as the collector.

[0057] (1) The grinding fineness is -200 mesh and the content is 65%, the pH adjuster is lime, and the slurry mixing time is 3 minutes;

[0058] (2) The dosage of methyl isobutyl carbinol as a foaming agent is 20 g / t, and the slurry is mixed for 2 minutes after adding the foaming agent;

[0059] (3) Add collector and mix the slurry for 2 minutes;

[0060] (4) The rough selection time is 3 minutes.

[0061] By using the best traditional collector O-isobutyl-N-ethoxycarbonylthiocarbamate (structural formula C2H5OOCNC(SH)O-C4H9), a rough copper grade of 6.03% and a recovery rate of 87.74% can be obtained.

[0062] When 2,1,3-benzoselenadiazole (structural formula C4H4C2N2Se) is used as a collector, the optimal dosage is 30g / t. At a pH of 8.27, a copper roughing grade of 6.61% and a copper recovery rate of 80.59% are obtained. The flotation effect of this organic compound with a structure composed of selenium atoms and nitrogen atoms is basically equivalent to that of traditional collectors, and relatively good flotation copper indicators can be obtained.

Claims

1. Application of a class of selenium-containing organic compounds in copper sulfide flotation traps, characterized in that: Selenium-containing organic compounds include organic compounds containing a single selenium atom or multiple selenium atoms with selenium atoms as functional groups, as well as organic compounds composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur, and carbon, including but not limited to: selenophene, phenylselenol, diselenide, selenoamine, carbonylselenoamine, oxycarbonylselenoamine, selenourea, selenonitrogen, selenoxanthate, selenoxanthate, selenophosphoric acid, selenophosphate esters, triphenylphosphine selenide, and various benzoselenadiazole molecules as copper collectors.

2. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 1, characterized in that: Its molecular structure is as follows:

3. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 1, characterized in that: A class of organic compounds containing selenium atoms and nitrogen, oxygen, phosphorus, sulfur, and carbon. Its molecular structure is as follows:

4. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 2, characterized in that: Using dibenzyl diselenide as a collector, the method comprises the following steps: Dissolve dibenzyl diselenide in dichloromethane and stir for 5 minutes to completely dissolve the dibenzyl diselenide. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% dibenzyl diselenide.

5. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 2, characterized in that: Using phenylselenium chloride as a collector, the method comprises the following steps: Dissolve phenylselenium chloride in dichloromethane and stir for 5 minutes to completely dissolve the phenylselenium chloride. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% phenylselenium chloride.

6. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 2, characterized in that: Using phenylselenol as a collector, the method comprises the following steps: Dissolve phenylselenol in dichloromethane and stir for 5 minutes to completely dissolve the phenylselenol. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% phenylselenol.

7. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 2, characterized in that: Using dimethyl diselenide as a collector, the method comprises the following steps: Dissolve dimethyl diselenide in dichloromethane and stir for 5 minutes to completely dissolve the dimethyl diselenide. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% dimethyl diselenide.

8. The use of a class of selenium-containing organic compounds in copper sulfide flotation traps according to claim 2, characterized in that: Selenophene is used as a collector, and the method comprises the following steps: Dissolve selenophene in dichloromethane and stir for 5 minutes to completely dissolve the selenophene. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% selenophene.

9. The use of an organic compound composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon in a copper ore flotation collector according to claim 3, characterized in that: Using triphenylphosphine selenide as a collector, the method comprises the following steps: Dissolve triphenyl phosphine selenide in dichloromethane and stir for 5 minutes to completely dissolve the triphenyl phosphine selenide. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% triphenyl phosphine selenide.

10. The use of an organic compound composed of selenium atoms and nitrogen, oxygen, phosphorus, sulfur and carbon in a copper ore flotation collector according to claim 3, characterized in that: Using 2,1,3-benzoselenadiazole as a collector, the method comprises the following steps: Dissolve 2,1,3-benzoselenadiazole in dichloromethane and stir for 5 minutes to completely dissolve 2,1,3-benzoselenadiazole. The composition by mass percentage is: 95%-99.5% dichloromethane and 0.5%-5% 2,1,3-benzoselenadiazole.

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