CN113617536B - Collecting agent and preparation method and application thereof - Google Patents
Collecting agent and preparation method and application thereof Download PDFInfo
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- CN113617536B CN113617536B CN202111067231.0A CN202111067231A CN113617536B CN 113617536 B CN113617536 B CN 113617536B CN 202111067231 A CN202111067231 A CN 202111067231A CN 113617536 B CN113617536 B CN 113617536B
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- collector
- copper
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- molybdenum
- methyl isobutyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a collector, a preparation method and application thereof, wherein the collector comprises a combination of N, N-diethyl dithio-carbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol ethoxylates and diesel oil. The collector has excellent solubility, dispersibility and fluidity by compounding N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol ethoxylates and diesel; the copper-molybdenum ore has good selectivity and strong collecting capacity, copper-molybdenum concentrate with high grade and high recovery rate can be obtained, and the better flotation effect can be achieved by using less amount in the ore dressing process. Meanwhile, the collecting agent has wide raw material sources, simple preparation process and good application prospect.
Description
Technical Field
The invention belongs to the technical field of mineral processing, and particularly relates to a collecting agent, a preparation method and application thereof.
Background
The world has ascertained that the copper zebra ore accounts for about 76% of the total copper, and the associated molybdenum in the copper zebra ore is an important source of molybdenum metal. In terms of sustainable development and resource conservation, the efficient treatment of copper-molybdenum ores and the collection of copper-molybdenum metals also attracts more and more attention.
In the prior art, a mixed flotation method is mostly adopted to treat copper-molybdenum ores, and medicines such as esters (ethyl thiourethane, ester-105 and the like), xanthates (ethyl xanthate, butyl xanthate and the like), black medicines (butyl ammonium black medicine, sodium isobutyl black medicine and the like) and hydrocarbon oils (kerosene, diesel oil and the like) are mainly adopted as collecting agents. For example, CN108435437a discloses a copper-molybdenum flotation collector with low alkalinity and high selectivity and a preparation method thereof, the active ingredients of the copper-molybdenum flotation collector comprise heavy oil, thiocarbamate, hydrocarbon oil mixture and diesel oil, and the weight parts ratio of the components are as follows: 22-28 parts of heavy oil, 8-12 parts of thiocarbamate, 22-28 parts of hydrocarbon oil mixture and 35-45 parts of diesel oil. The copper-molybdenum flotation collector can realize the efficient collection of copper minerals and molybdenum minerals in a low-alkalinity environment with the pH value of 7-9, is easy to sort and has strong selectivity, can not cause corrosion to equipment, and has extremely high popularization value and application prospect. But the copper molybdenum flotation collectors have to be further improved for copper mineral recovery.
CN101844107a discloses a combined collector for the flotation of porphyry copper-molybdenum ores and a flotation method thereof. The combined collector at least contains phthalate and hydrocarbon oxycarbonyl thiourea, and can perform a molybdenum-copper floatable process mainly comprising molybdenum, so that molybdenite and copper sulfide minerals with good part of floatability are subjected to floatation, and a molybdenum-copper mixed concentrate with high molybdenum recovery rate is obtained; and then the copper sulfide minerals with poor floatability are recovered in an intensified manner. The invention effectively solves the problem of strong inhibition effect of lime high alkali environment on molybdenite in the existing mixed flotation process of the zebra copper molybdenum ore, and has the characteristics of simple and reasonable flow, high molybdenum recovery rate and the like. However, copper recovery cannot be achieved at the same time, and copper recovery is reduced.
The general defects of the above are that the copper and molybdenum are separated due to the large difference of floatability of the copper and molybdenum, the copper and molybdenum are not well collected in actual production, pyrite and other gangue minerals are easily mixed with the copper and molybdenum, the concentrate grade is low, the recovery rate is low due to weak collecting capacity with good selectivity, and the resource waste is caused.
Therefore, developing a collector capable of recovering copper and molybdenum at the same time and efficiently recovering copper and molybdenum resources is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a collecting agent, and a preparation method and application thereof. The collector adopts the combination of N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene and diesel oil, has good selectivity to copper molybdenum ore and strong collecting capability, and can recover copper molybdenum.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a collector comprising a combination of propionitrile N, N-diethyl dithiocarbamate, methyl isobutyl carbinol, alkylphenol ethoxylates and diesel fuel.
According to the invention, through the cooperative use of the N, N-diethyl dithiocarbamic acid propionitrile ester, the methyl isobutyl carbinol, the alkylphenol polyoxyethylene and the diesel, the collector has good selectivity on copper-molybdenum ores, can recover copper-molybdenum, and avoids inclusion of other minerals such as pyrite; the N, N-diethyl dithiocarbamic acid propionitrile ester has good copper sulfide flotation selectivity, diesel oil has good molybdenum selectivity, methyl isobutyl carbinol can prevent the solidification of the collector, alkylphenol ethoxylates can improve the fluidity, the solubility and the dispersibility of the collector, and the flotation of copper-molybdenum minerals is facilitated.
As a preferable technical scheme of the invention, the collecting agent comprises 65-75 parts by weight of N, N-diethyl dithiocarbamic acid propionitrile ester, 5-10 parts by weight of methyl isobutyl carbinol, 1-3 parts by weight of alkylphenol ethoxylate and 20-25 parts by weight of diesel oil.
Preferably, the collector includes 65 to 75 parts by weight of propionitrile N, N-diethyl dithiocarbamate, for example, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, etc.
In the invention, the weight part of the N, N-diethyl dithio-propionitrile carbamate is less than 65 parts, the collecting capacity is weakened, and the recovery rate of copper-molybdenum concentrate is reduced; more than 75 parts, the collector has poor solubility, fluidity and dispersibility, and is unfavorable for the recovery of copper-molybdenum concentrate.
Preferably, the collector includes 5 to 10 parts by weight of methyl isobutyl carbinol, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.
In the invention, the weight part of the methyl isobutyl carbinol is less than 5 parts, and the solubility, the fluidity and the dispersibility of the collecting agent are poor; more than 10 parts, the proportion of other components decreases, and the collecting ability becomes weak.
Preferably, the collector includes 1 to 3 parts by weight of alkylphenol ethoxylates, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.
In the invention, the alkylphenol ethoxylates have the weight part of less than 1 part, and the solubility, the fluidity and the dispersibility of the collector are poor; greater than 3 parts results in a large amount of froth flotation, and the flotation process is difficult to control.
Preferably, the collector includes 20 to 25 parts by weight of diesel oil, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, etc.
In the invention, the diesel oil is less than 20 parts, the solubility, fluidity and dispersibility of the collector are poor, and the recovery rate of molybdenum is low; more than 25 parts, the foam is fragile and the collecting ability becomes weak.
Preferably, the alkylphenol ethoxylates comprise any one or a combination of at least two of nonylphenol ethoxylates, octylphenol ethoxylates and dodecylphenol ethoxylates.
Preferably, the polymerization degree of ethylene oxide in the alkylphenol ethoxylates is 8 to 12, and for example, 8, 9, 10, 11, 12, etc. are possible.
In a second aspect, the present invention provides a method of preparing a collector as described in the first aspect, the method comprising the steps of:
and mixing the N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene and diesel according to the formula amount to obtain the collector.
Preferably, the mixing is followed by agitation.
Preferably, the stirring time is 20-40 min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, etc.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl methyl alcohol and alkylphenol polyoxyethylene according to the formula amount, adding diesel oil, and stirring for 20-40 min to obtain the collector.
In a third aspect, the present invention provides a copper molybdenum ore collector comprising a collector as described in the first aspect.
In a fourth aspect, the present invention provides the use of a collector as described in the first aspect in a copper molybdenum ore flotation process.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
the collector provided by the invention has the advantages that the selectivity of the prepared collector to copper-molybdenum ores is high, the collecting capability is strong, the copper and molybdenum can be collected simultaneously, the copper grade in copper-molybdenum concentrate is more than 24%, the molybdenum grade is more than or equal to 0.42%, the copper recovery rate is more than 88%, and the molybdenum recovery rate is more than 72%, so that the defects that the grade of copper-molybdenum concentrate is difficult to improve, the molybdenum recovery rate is lower and the like in the traditional collector adopting esters, xanthates or hydrocarbon oils are overcome, the raw material sources are wide, and the preparation process is simple.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The various starting materials of the present invention are commercially available, or may be prepared according to methods conventional in the art, unless specifically indicated.
Example 1
The invention provides a collector which comprises 72 parts of N, N-diethyl dithiocarbamic acid propionitrile ester, 8 parts of methyl isobutyl carbinol, 1 part of alkylphenol ethoxylate (NP-10) and 23 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 30min to obtain the collector.
Example 2
The invention provides a collector which comprises 70 parts of N, N-diethyl dithiocarbamic acid propionitrile ester, 9 parts of methyl isobutyl carbinol, 1.5 parts of alkylphenol ethoxylate (NP-10) and 25 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 20min to obtain the collector.
Example 3
The invention provides a collector which comprises 75 parts of N, N-diethyl dithiocarbamic acid propionitrile ester, 10 parts of methyl isobutyl carbinol, 1 part of alkylphenol ethoxylate (NP-10) and 20 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 25min to obtain the collector.
Example 4
The invention provides a collector which comprises 65 parts of N, N-diethyl dithiocarbamic acid propionitrile ester, 5 parts of methyl isobutyl carbinol, 3 parts of alkylphenol ethoxylate (OP-8) and 20 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (OP-8) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 40min to obtain the collector.
Example 5
The present invention provides a collector differing from example 1 only in that the collector comprises greater than 75 parts by weight of propionitrile N, N-diethyl dithiocarbamate; the other components and the amounts were the same as in example 1. The collector comprises 80 parts of N, N-diethyl dithio-carbamic acid propionitrile ester, 8 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene (NP-10) and 23 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 30min to obtain the collector.
Example 6
The present invention provides a collector which differs from example 1 only in that the weight part of methyl isobutyl carbinol in the collector is more than 10 parts; the other components and the amounts were the same as in example 1. The collector comprises 72 parts of N, N-diethyl dithio-carbamic acid propionitrile ester, 15 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene (NP-10) and 23 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 30min to obtain the collector.
Example 7
The invention provides a collector, which is different from the embodiment 1 only in that the weight part of alkylphenol ethoxylate in the collector is more than 3 parts; the other components and the amounts were the same as in example 1. The collector comprises 72 parts of N, N-diethyl dithio-carbamic acid propionitrile ester, 8 parts of methyl isobutyl carbinol, 5 parts of alkylphenol polyoxyethylene (NP-10) and 23 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 30min to obtain the collector.
Example 8
The present invention provides a collector which differs from example 1 only in that the weight part of diesel oil in the collector is more than 25 parts; the other components and the amounts were the same as in example 1. The collector comprises 72 parts of N, N-diethyl dithio-carbamic acid propionitrile ester, 8 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene (NP-10) and 30 parts of diesel oil.
The invention provides a preparation method of a collector, which comprises the following specific steps:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) according to the formula amount under normal temperature and normal pressure, adding diesel oil, and stirring for 30min to obtain the collector.
Comparative example 1
This comparative example provides a collector that differs from example 1 only in that there is no diesel fuel in the collector; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 2
This comparative example provides a collector which differs from example 1 only in that there is no methyl isobutyl carbinol in the collector; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 3
This comparative example provides a collector which differs from example 1 only in that there is no alkylphenol ethoxylate (NP-10) in the collector; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 4
This comparative example provides a collector which differs from example 1 only in that 72 parts of propionitrile N, N-diethyldithiocarbamate are replaced with 72 parts of ethyl-thiourethane; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 5
This comparative example provides a collector which differs from example 1 only in that 8 parts of methyl isobutyl carbinol is replaced with 8 parts of alpha-terpene alcohol in the collector; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 6
This comparative example provides a collector which differs from example 1 only in that 1 part of alkylphenol ethoxylate (NP-10) is replaced with 1 part of fatty alcohol ethoxylate; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 7
This comparative example provides a collector which differs from example 1 only in that 23 parts of diesel oil are replaced with 23 parts of kerosene in the collector; the other components and amounts were the same as in example 1.
This comparative example provides a method of preparing a collector, the specific procedure being the same as in example 1.
Comparative example 8
This comparative example provides a collector that is butyl xanthate.
Comparative example 9
This comparative example provides a collector that is kerosene.
The collectors provided by the examples and comparative examples of the invention perform tests on copper-molybdenum ore flotation: after grinding a copper-molybdenum ore raw ore (Cu content is 0.56 percent and Mo content is 0.012 percent) to the mass percentage of-0.074 mm grain grade material, adding a pH regulator, a collector and a foaming agent to perform primary roughing, secondary scavenging and tertiary concentration treatment, wherein the mass percentage of the rough concentrate ground to the mass percentage of-0.045 mm grain grade material is 90 percent when concentration is performed.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the table, the collector provided by the invention can recover copper and molybdenum by compounding N, N-diethyl dithio-carbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol ethoxylates and diesel oil. Under the condition of ensuring high copper grade and copper recovery rate, the molybdenum grade in the copper-molybdenum concentrate is more than or equal to 0.42%, and the molybdenum recovery rate is more than 72%.
As is clear from the comparison of examples 1 to 4 with examples 5 to 8, the recovery effect of the copper-molybdenum ore is better in the specific content ranges of the N, N-diethyl-dithio-carbamic acid propionitrile ester, the methyl isobutyl carbinol, the alkylphenol ethoxylate and the diesel oil.
As is clear from comparison of example 1 and comparative examples 1 to 9, the collector adopts a combination of N, N-diethyl dithio-carbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene and diesel oil, and the grade and recovery rate of copper and molybdenum in copper-molybdenum concentrate obtained by flotation are improved. When one of the components is removed or replaced by other agents, the grade of copper and molybdenum in the copper and molybdenum concentrate or the recovery rate of copper and molybdenum is reduced.
In conclusion, the collector provided by the invention forms a specific proportion by the N, N-diethyl dithiocarbamic acid propionitrile ester, the methyl isobutyl carbinol, the alkylphenol polyoxyethylene and the diesel oil, not only can recover copper and molybdenum, and improve the grade and recovery rate of copper and molybdenum, but also has wide raw material sources, simple preparation process and good application prospect.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (8)
1. The copper-molybdenum ore collector is characterized by comprising, by weight, 65-75 parts of N, N-diethyl dithio-carbamic acid propionitrile ester, 5-10 parts of methyl isobutyl carbinol, 1-3 parts of alkylphenol ethoxylates and 20-25 parts of diesel oil.
2. The copper molybdenum ore collector of claim 1, wherein the alkylphenol ethoxylates comprise any one or a combination of at least two of nonylphenol ethoxylate, octylphenol ethoxylate, or dodecylphenol ethoxylate.
3. The copper-molybdenum ore collector of claim 1, wherein the alkylphenol ethoxylates have a polymerization degree of ethylene oxide of 8-12.
4. A method for preparing the copper-molybdenum ore collector according to any one of claims 1 to 3, comprising the steps of:
and mixing the N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene and diesel oil according to the formula amount to obtain the copper-molybdenum ore collector.
5. The method of claim 4, wherein the mixing is followed by stirring.
6. The method according to claim 5, wherein the stirring time is 20 to 40 minutes.
7. The preparation method according to claim 4, characterized in that the preparation method comprises the steps of:
mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl methyl alcohol and alkylphenol polyoxyethylene according to the formula amount, adding diesel oil, and stirring for 20-40 min to obtain the copper-molybdenum ore collector.
8. Use of the copper-molybdenum ore collector of any one of claims 1-3 in a copper-molybdenum ore flotation process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2254931C2 (en) * | 2003-07-28 | 2005-06-27 | Открытое акционерное общество "Горно-металлургическая компания "Норильский никель" | Method of concentration of sulfide copper-nickel ores |
| CN103350034A (en) * | 2013-06-29 | 2013-10-16 | 西北矿冶研究院 | Method for reducing freezing point of azothion ester collecting agent |
| CN104324813A (en) * | 2014-09-05 | 2015-02-04 | 昆明冶金研究院 | Composite collecting agent for bulk floatation of copper sulfide molybdenum ores |
| CN108057525A (en) * | 2017-11-27 | 2018-05-22 | 西北矿冶研究院 | Flotation collector for improving associated gold of low-grade copper ore and copper-molybdenum ore and preparation method thereof |
| CN108435437B (en) * | 2018-05-09 | 2021-04-20 | 北京矿冶科技集团有限公司 | Low-alkalinity high-selectivity copper-molybdenum flotation collector and preparation method thereof |
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