CN114950742B - Galena flotation inhibitor and flotation separation method - Google Patents
Galena flotation inhibitor and flotation separation method Download PDFInfo
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- CN114950742B CN114950742B CN202210676878.1A CN202210676878A CN114950742B CN 114950742 B CN114950742 B CN 114950742B CN 202210676878 A CN202210676878 A CN 202210676878A CN 114950742 B CN114950742 B CN 114950742B
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- flotation
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- molybdenum
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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
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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
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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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
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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
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- 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
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Abstract
The invention relates to the technical field of flotation separation, in particular to a galena flotation inhibitor and a flotation separation method. The galena flotation inhibitor comprises a component A, humate and thioglycolate; the component A comprises at least one of compounds with a structure shown as a formula (I);wherein R is 1 Any one selected from hydrogen, C1-C3 alkyl and C1-C3 substituted alkyl; r is R 2 And R is 3 Each independently selected from any one of hydrogen, halogen, hydroxy, amino, and mercapto. The galena floatation inhibitor has the advantages of strong selectivity, good inhibition effect, small dosage, low toxicity and the like; the inhibitor is used in the process of quality improvement and lead reduction of the molybdenum rough concentrate, and can improve the recovery rate and grade of the molybdenum rough concentrate.
Description
Technical Field
The invention relates to the technical field of flotation separation, in particular to a galena flotation inhibitor and a flotation separation method.
Background
The polymetallic sulphide ore is the most main mineral resource for extracting nonferrous metals, and refers to the ore of which at least two or more than two kinds of sulfides such as copper, lead, zinc, iron and the like are densely symbiotic in the ore. Currently, the majority of the separation and separation of polymetallic sulphide ores is carried out by flotation. And (3) carrying out flotation separation by adopting a mode of manually adding a flotation reagent. In the polymetallic sulphide ores, because the floating properties of certain minerals are very similar, the minerals are very fine to be embedded, the structure is complex, the oxidation is serious, the mud content is high, and the like, so that the recycling is difficult.
Molybdenum is a rare metal with the advantages of high strength, high temperature resistance, abrasion resistance, corrosion resistance and the like, can improve the strength, toughness, corrosion resistance, abrasion resistance and heat resistance of steel as an additive, and is widely applied to the fields of metallurgy, machinery, military industry, aerospace, chemical industry, electric light sources and the like. However, the single molybdenum ore resources are fewer, the molybdenum ore resources are often associated with sulphide ores such as chalcopyrite, galena, pyrite and the like, wherein the galena is very easy to synchronously enrich with the molybdenite due to the floatability similar to the molybdenite, the floated molybdenum concentrate often contains higher lead, the quality of the molybdenum concentrate is reduced, and the comprehensive recycling of the molybdenum resources is difficult, so that the efficient development and the utilization of the molybdenum ore resources are in need of a galena inhibitor with good selectivity, and the galena and the molybdenite are effectively separated.
Currently, the common selective inhibitors used to inhibit galena are mainly: dichromate, phosphoxk, carboxymethyl cellulose, water glass, sulfurous acid and salts thereof, etc., which are used in large amounts and have poor selective inhibition effect, or dichromate has good inhibition effect on lead ores, but has serious pollution and huge harm to the environment.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a galena floatation inhibitor, which solves the problems of poor separation effect, poor selective inhibition effect, large dosage, high toxicity, serious pollution and the like in the prior art in whole or in part.
A second object of the present invention is to provide a flotation separation method comprising using a galena flotation suppressant as described above, which method enables an efficient separation of galena from other minerals, enabling a reduction in the grade of lead in the minerals.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a galena flotation inhibitor, which comprises a component A, humate and thioglycolate;
the component A comprises at least one of compounds with a structure shown as a formula (I);
wherein R is 1 Any one selected from hydrogen, C1-C3 alkyl and C1-C3 substituted alkyl;
R 2 and R is 3 Each independently selected from any one of hydrogen, halogen, hydroxy, amino, and mercapto.
The invention also provides a flotation separation method comprising adding the galena flotation suppressant as described above to the pulp.
Compared with the prior art, the invention has the beneficial effects that:
(1) The galena floatation inhibitor provided by the invention can be selectively adsorbed on the surface of galena, so that the hydrophilicity of the surface of the galena is increased, and the difference of the hydrophilicity and the hydrophobicity of the surface of the galena and other minerals is increased, thereby realizing the effective separation of the galena. The galena floatation inhibitor has the advantages of good selectivity, strong inhibition capability, good stability, wide application range, small dosage, environmental protection, low toxicity, safe use and the like, and can be widely applied to the floatation separation process of galena and other minerals.
(2) The flotation separation method provided by the invention comprises the steps of adding the galena flotation inhibitor into ore pulp; the method has good separation effect, simple operation and reduced environmental pollution; particularly for the flotation separation of molybdenum and lead, the method has good selectivity and inhibition capability, and can effectively improve the recovery rate and grade of molybdenum concentrate concentration.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a flotation process provided by the invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following describes a galena flotation suppressor and a flotation separation method according to embodiments of the present invention.
In some embodiments of the invention there is provided a galena flotation suppressant comprising component a, humate and thioglycolate;
component a includes at least one of the compounds having a structure as shown in formula (I);
wherein R is 1 Any one selected from hydrogen, C1-C3 alkyl and C1-C3 substituted alkyl;
R 2 and R is 3 Each independently selected from any one of hydrogen, halogen, hydroxy, amino, and mercapto.
The compound of the component A having the above specific structure has a front-line track shape matching with that of galena, and thus can be selectively adsorbed on the surface of galena.
Humate can chelate lead ions on the surface of minerals, and is beneficial to separation of galena and other minerals.
The thioglycolate contains a sulfhydryl group and a carboxyl group, wherein the sulfhydryl group has reducibility and hydrophile properties, can be firmly adsorbed on the surfaces of mineral particles, and can be adsorbed with minerals by virtue of the carboxyl group, so that a hydrophilic film is formed between the minerals and the medicament to prevent the collector from being adsorbed on the surfaces of the minerals, thereby inhibiting the flotation of sulfur-containing minerals.
According to the invention, through the synergistic combination of the component A with a specific structure, humate and thioglycolate, the high-selectivity adsorption on the surface of galena can be realized, and the hydrophilicity of the surface of the galena is increased, so that the difference of the hydrophilicity and hydrophobicity of other minerals and the surface of the galena is increased, and the effective separation of the galena is realized.
The galena floatation inhibitor provided by the invention has the characteristics of good selectivity, strong inhibition capability, good stability, low toxicity, environment friendliness, safer use and the like, can be widely used in the floatation process of minerals, and does not cause harm to human bodies and the environment.
In some embodiments of the invention, R 1 Selected from any one of hydrogen and C1-C3 straight chain or branched alkyl.
In some embodiments of the present invention, a method for preparing a compound having a structure as shown in formula (I) includes: reacting an amino mercaptan compound with glyoxylic acid in an organic solvent to obtain a compound with a structure shown as a formula (I);
the structural formula of the amino mercaptan compound is as follows:
the structural formula of the glyoxylic acid is as follows:
in some embodiments of the invention, the aminothiol compound is beta-mercaptoethylamine or cysteine.
In some embodiments of the invention, the molar ratio of amine-based thiol compound to glyoxylic acid is 1:1.1 to 1.3; typically, but not by way of limitation, the molar ratio of the aminothiol compound to glyoxylic acid is 1:1.1, 1:1.2 or 1:1.3, etc.
In some embodiments of the invention, the volume molar ratio of organic solvent to aminothiol compound is from 2 to 50mL/mmol; preferably, the volume molar ratio of the organic solvent to the aminothiol compound is 2 to 10mL/mmol.
In some embodiments of the invention, the organic solvent comprises a mass ratio of 1: 5-5: 1 alcohol and pyridine; typically, but not by way of limitation, the mass ratio of alcohol to pyridine is 1: 5. 2: 5. 3: 5. 4: 5. 1:1. 2: 1. 3: 1. 3: 2. 4: 1. 4: 3. 4:5 or 5:1, etc.
In some embodiments of the invention, the alcohol comprises one or more of a C1-C10 saturated alcohol and/or a C1-C10 unsaturated alcohol.
In some embodiments of the invention, the alcohol comprises one or more of methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, tert-pentanol, and hexanol.
In some embodiments of the invention, the temperature of the reaction is from 5 to 50 ℃; the reaction time is 0.5-72 h; typical, but not limiting, temperatures for the reaction are, for example, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, or 50 ℃, etc.; typical, but not limiting, times for the reaction are, for example, 0.5h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, or 70h, etc.
The preparation method of the compound with the structure shown in the formula (I) is simple to operate, wide in preparation raw material source, mild in reaction condition, stable in product quality, high in product yield and suitable for large-scale industrial production.
In some embodiments of the invention, component a comprises one or both of the compounds having a structure as shown in formula (II) or formula (III);
in some specific embodiments of the invention, the galena flotation suppressant comprises a compound having a structure as shown in formula (II), humate, and thioglycolate; alternatively, it includes a compound having a structure as shown in formula (III), humate and thioglycolate; alternatively, the compound is a compound having a structure shown in formula (II), a compound having a structure shown in formula (III), humate and thioglycolate.
In some embodiments of the invention, the mass ratio of component a, humate and thioglycolate is 1:0.5 to 1:0.2 to 1; typical but non-limiting, for example, component a, humate and thioglycolate at a mass ratio of 1:1: 1. 1:0.9:0.2, 1:0.7:0.2, 1:0.5:0.2, 1:0.9:0.3, 1:0.7:0.3, 1:0.5:0.3, 1:0.9:0.4, 1:0.7:0.4, 1:0.5:0.4, 1:0.9:0.5, 1:0.7:0.5, 1:0.5:0.5, 1:0.9:0.6, 1:0.7:0.6, 1:0.5:0.6, 1:0.9:0.7, 1:0.7:0.7, 1:0.5:0.7, 1:0.9:0.8, 1:0.7:0.8, 1:0.5:0.8, 1:0.9:0.9, 1:0.7:0.9, 1:0.5:0.9, 1:0.9: 1. 1:0.7:1 or 1:0.5:1, etc.
The components A, humate and thioglycolate in the lead ore flotation inhibitor are scientifically proportioned, so that the components are matched with each other, and the flotation separation effect is more excellent.
In some embodiments of the invention, the humate comprises sodium humate and/or potassium humate; preferably, the humate comprises sodium humate.
In some embodiments of the invention, the thioglycolate includes one or more of sodium thioglycolate, potassium thioglycolate, and ammonium thioglycolate and lithium thioglycolate; preferably, the thioglycolate comprises sodium thioglycolate.
In some embodiments of the invention, the galena flotation inhibitor is a liquid formulation; in the liquid preparation, the content of the galena floatation inhibitor is 10-35 wt%; typically, but not by way of limitation, the galena flotation suppressant is present in the liquid formulation in an amount of 10wt%, 15wt%, 20wt%, 25wt%, 30wt% or 35wt%, etc.
In some embodiments of the invention there is also provided a flotation separation process comprising adding the above galena flotation suppressant to a pulp.
In some embodiments of the invention, the mineral content in the pulp is 5wt% to 45wt%; preferably, the mineral content in the pulp is 15-25 wt%.
In some embodiments of the invention, the content of mineral particles having a particle size of 0.074mm or less in the mineral is 60wt% or more.
In some embodiments of the invention, the galena flotation inhibitor is used in an amount of 50 to 1500g/t, based on solids content, relative to the mineral in the pulp; preferably, the galena flotation inhibitor is used in an amount of 1000g/t relative to the minerals in the pulp, based on the solids content.
In some embodiments of the invention, a flotation separation process comprises the steps of:
(A) Carrying out flotation treatment on ore feeding for 5 times to obtain fifth molybdenum-concentrating middling; regrinding the fifth molybdenum concentrate middlings, adding water glass into the regrinded fifth molybdenum concentrate middlings, and carrying out pulp mixing to obtain ore pulp containing the fifth molybdenum concentrate middlings;
(B) And (3) adding galena floatation inhibitors into the ore pulp in the step (A) for floatation to obtain molybdenum concentrate.
In some embodiments of the invention, the amount of water glass used in step (A) is less than or equal to 2kg/t relative to the fifth molybdenum concentrate.
In some embodiments of the invention, the flotation separation process, step (a), the regrind fifth molybdenum concentrate has a mineral particle content of 70wt% to 90wt% in the mineral having a particle size of 0.038mm or less.
In some embodiments of the invention, the flotation separation method, step (B), the flotation time is 2 to 5 minutes; preferably, the flotation time is 4 minutes.
In some embodiments of the invention, the flotation separation process, step (B), the galena inhibitor is used in an amount of 1.5kg/t or less relative to the fifth molybdenum beneficiated middlings.
In some embodiments of the invention, the flotation separation process, step (a), the feed ore comprises a molybdenum concentrate; preferably, in the molybdenum rough concentrate, the content of molybdenum is 5-20wt% and the content of lead is 0.01-2wt%.
The invention does not strictly limit the molybdenum content and the lead content in the molybdenum rough concentrate, and belongs to the molybdenum rough concentrate.
In some embodiments of the invention, the preparation of the fifth molybdenum beneficiated middlings comprises the steps of:
(A) Adding water glass into the molybdenum rough concentrate, and performing size mixing to obtain ore pulp containing the molybdenum rough concentrate; adding galena floatation inhibitors into ore pulp containing molybdenum rough concentrate, and carrying out floatation to obtain first molybdenum concentration middlings and tailings;
(B) Adding galena floatation inhibitor into the first molybdenum concentrate middlings for floatation to obtain a second molybdenum concentrate middlings and middlings F;
(C) Adding galena floatation inhibitor into the second molybdenum concentrate middlings for floatation to obtain a third molybdenum concentrate middlings and middlings G;
(D) Adding galena floatation inhibitor into the third molybdenum concentrate middlings for floatation to obtain fourth molybdenum concentrate middlings and middlings H;
(E) Adding water glass into the fourth molybdenum concentrate, and then performing size mixing to obtain ore pulp containing the fourth molybdenum concentrate; and adding galena floatation inhibitor into ore pulp containing the fourth molybdenum concentrate, and carrying out floatation to obtain a fifth molybdenum concentrate and middling I.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared in step (a) for a period of time ranging from 4 to 8 minutes, preferably for a period of 6 minutes.
In some embodiments of the invention, the fifth molybdenum beneficiation middlings are prepared, in step (A), the amount of water glass relative to the molybdenum concentrate is less than or equal to 7kg/t, and the amount of galena flotation inhibitor relative to the molybdenum concentrate is less than or equal to 6kg/t; preferably, the amount of lead ore floatation inhibitors relative to the molybdenum rough concentrate is less than or equal to 1kg/t.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared in step (a) with a molybdenum concentrate having a mineral particle size of less than 0.074mm in an amount of 60wt% to 90wt%.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared, and in step (a), the slurry comprising the molybdenum concentrate has a pH of from 6 to 11; preferably, the pulp containing the molybdenum rough concentrate has a pH of 9 to 11.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared in step (B) for a period of time ranging from 2 to 5 minutes, preferably for a period of time ranging from 4 minutes.
In some embodiments of the invention, the fifth molybdenum-beneficiated middlings are prepared, and the galena flotation inhibitor in step (B) is used in an amount of 4kg/t or less relative to the first molybdenum-beneficiated middlings; preferably, the lead ore floatation inhibitor is used in an amount of less than or equal to 1kg/t relative to the first molybdenum beneficiated middlings.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared in step (C) for a period of time ranging from 2 to 5 minutes, preferably for a period of time ranging from 4 minutes.
In some embodiments of the invention, the fifth molybdenum-concentrating middlings are prepared, and the galena flotation inhibitor in step (C) is used in an amount of 4kg/t or less relative to the second molybdenum-concentrating middlings; preferably, the lead ore floatation inhibitor is used in an amount of less than or equal to 1kg/t relative to the second molybdenum beneficiated middlings.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared in step (D) for a period of time ranging from 2 to 5 minutes, preferably for a period of time ranging from 4 minutes.
In some embodiments of the invention, the fifth molybdenum-concentrating middlings are prepared, and the galena flotation inhibitor in step (D) is used in an amount of 4kg/t or less relative to the third molybdenum-concentrating middlings; preferably, the lead ore floatation inhibitor is used in an amount of less than or equal to 1kg/t relative to the third molybdenum beneficiation middlings.
In some embodiments of the invention, the fifth molybdenum concentrate is prepared in step (E) for a period of time ranging from 2 to 5 minutes, preferably for a period of time ranging from 4 minutes.
In some embodiments of the invention, the fifth molybdenum-concentrating middlings are prepared, and in step (E), the water glass is used in an amount of less than or equal to 5kg/t relative to the fourth molybdenum-concentrating middlings, and the galena flotation inhibitor is used in an amount of less than or equal to 3kg/t relative to the fourth molybdenum-concentrating middlings; preferably, the lead ore floatation inhibitor is used in an amount of less than or equal to 1kg/t relative to the fourth molybdenum beneficiated middlings.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The preparation method of the galena floatation inhibitor provided by the embodiment comprises the following steps:
25mmol of beta-mercaptoethylamine was dissolved in 100mL of a mass ratio of 5:2, 28mmol of glyoxylic acid is added thereto at 20 ℃ in a mixed solvent of ethanol and pyridine, stirred for 2 hours, and then an off-white precipitate is separated by filtration, washed with ethanol, and finally white powder a is obtained.
3g of white powder a, 3g of sodium humate and 3g of sodium thioglycolate are added into 50mL of water, and uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 15.2%.
Example 2
The preparation method of the galena floatation inhibitor provided by the embodiment comprises the following steps:
20mmol of cysteine was dissolved in 100mL of water at a mass ratio of 4:2 to a mixed solvent of isopropyl alcohol and pyridine, 25mmol of glyoxylic acid was added thereto at 40 ℃ and stirred for 3 hours, and then an off-white precipitate was separated by filtration and washed with ethanol to finally obtain white powder b.
3g of white powder b, 1.5g of sodium humate and 1g of sodium thioglycolate are added into 40mL of water, and the mixture is uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 12.1%.
Example 3
The preparation method of the galena floatation inhibitor provided by the embodiment comprises the following steps:
25mmol of beta-mercaptoethylamine was dissolved in 250mL of a mass ratio of 5:2 to a mixed solvent of ethanol and pyridine, 25mmol of glyoxylic acid was added thereto at 5℃and stirred for 5 hours, and then an off-white precipitate was separated by filtration and washed with ethanol to finally obtain a white powder c.
3g of white powder c, 2.5g of sodium humate and 1g of sodium thioglycolate are added into 50mL of water, and the mixture is uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 11.5%.
Example 4
The preparation method of the galena floatation inhibitor provided by the embodiment comprises the following steps:
15mmol of beta-mercaptoethylamine was dissolved in 50mL of a mass ratio of 1:2, 18mmol of glyoxylic acid was added thereto at 50 c, stirred for 1.2h, and then an off-white precipitate was separated by filtration, washed with ethanol, and finally white powder d was obtained.
3g of white powder d, 2.5g of sodium humate and 0.6g of sodium thioglycolate are taken and added into 50mL of water, and the mixture is uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 10.9%.
Example 5
The preparation method of the galena floatation inhibitor provided by the embodiment comprises the following steps:
10mmol of beta-mercaptoethylamine was dissolved in 60mL of a mass ratio of 2:2, 12mmol of glyoxylic acid is added thereto at 20 ℃ and stirred for 2 hours, and then an off-white precipitate is separated by filtration and washed with ethanol to finally obtain white powder e.
3g of white powder e, 2g of sodium humate and 0.6g of sodium thioglycolate are added into 50mL of water, and uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 10.0%.
Comparative example 1
The inhibitor provided in this comparative example is fosinox, which is formulated as follows:
8g of NaOH is dissolved in 92g of water to obtain 8% NaOH aqueous solution; take 5.7g P 2 S 5 Dissolving in the 8% NaOH aqueous solution to obtain 105.7g of P with the mass percentage of 5.39% 2 S 5 A solution; the mass percentage of the P is 5.39% of 105.7g 2 S 5 402g of water was added to the solution to obtain 1.07% by mass of P 2 S 5 An aqueous solution.
Comparative example 2
The preparation method of the inhibitor provided by the comparative example comprises the following steps:
25mmol of 1, 2-ethanedithiol was dissolved in 100mL of a mass ratio of 3:2, 28mmol of glyoxylic acid is added thereto at 20 ℃ in a mixed solvent of ethanol and pyridine, stirred for 2 hours, and then an off-white precipitate is separated by filtration, washed with ethanol, and finally white powder f is obtained.
3g of white powder f, 2.5g of sodium humate and 1g of sodium thioglycolate are added into 50mL of water, and the mixture is uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 11.5%.
The chemical formula of the white powder f is:
comparative example 3
The preparation method of the inhibitor provided by the embodiment comprises the following steps:
25mmol of beta-mercaptoethanol was dissolved in 100mL of a mass ratio of 5:2 to a mixed solvent of ethanol and pyridine, 28mmol of glyoxylic acid was added thereto at 20℃and stirred for 12 hours, and then an off-white precipitate was separated by filtration and washed with ethanol to finally obtain white powder g.
3g of white powder g, 2.5g of sodium humate and 1g of sodium thioglycolate are added into 50mL of water, and the mixture is uniformly mixed to obtain the galena flotation inhibitor aqueous solution with the mass fraction of 11.5%.
The chemical structural formula of the white powder g is:
comparative example 4
The inhibitor provided in this comparative example is sodium humate, which is commercially available. The manufacturer is North Ore chemical technology (Cantonese).
Comparative example 5
The inhibitor provided in this comparative example is sodium thioglycolate, which is commercially available. The manufacturer is Allatin, and the purity of the product is 95%.
Comparative example 6
The preparation method of the inhibitor provided by the comparative example comprises the following steps:
2g of sodium humate and 0.6g of sodium thioglycolate are added into 50mL of water, and the inhibitor aqueous solution with the mass fraction of 4.9% is obtained after uniform mixing.
Test example 1
The inhibitor of examples 1-5 and comparative examples 1-6 was used to carry out experiments of upgrading and reducing impurity molybdenum on the molybdenum rough concentrate.
Molybdenum rough concentrate is taken as ore feeding, the molybdenum content in the molybdenum rough concentrate is 14.59 weight percent, the lead content is 0.56 weight percent, and 60 weight percent of ore grains with the fineness of less than 0.074mm are used for ore grinding. Adding water glass into the molybdenum rough concentrate, and performing pulp mixing to obtain ore pulp containing the molybdenum rough concentrate, wherein the pH value of the ore pulp containing the molybdenum rough concentrate is 10.2, and the mineral content in the ore pulp is 20wt%; the amount of water glass relative to the molybdenum rough concentrate was 1kg/t.
11 parts of ore pulp containing 250g of molybdenum rough concentrate were taken, and each of the ore pulp was added with the inhibitors of example 1, example 2, example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 and comparative example 6, respectively, and subjected to flotation treatment for 6 minutes, to obtain a first molybdenum concentrate and a tailings, each of which was used in an amount of 1000g/t relative to the molybdenum rough concentrate.
Adding an inhibitor into the first molybdenum concentrate middlings for flotation treatment for 4min to obtain second molybdenum concentrate middlings and middlings F; the amount of each inhibitor was 1kg/t relative to the first molybdenum concentrate.
Adding an inhibitor into the middlings of the second molybdenum concentration for flotation treatment for 4min to obtain middlings and middlings G of the third molybdenum concentration; the amount of each inhibitor was 1kg/t relative to the second molybdenum concentrate.
Adding an inhibitor into the third molybdenum-concentrating middlings for flotation treatment for 4min to obtain fourth molybdenum-concentrating middlings and middlings H; the amount of each inhibitor was 1kg/t relative to the third molybdenum concentrate.
Adding water glass into the fourth molybdenum concentrate, and then performing size mixing to obtain ore pulp containing the fourth molybdenum concentrate; adding an inhibitor into ore pulp containing the fourth molybdenum concentrate for flotation treatment for 4min to obtain a fifth molybdenum concentrate and middling I; the consumption of the water glass relative to the fourth molybdenum concentration middlings is 1kg/t; the amount of each inhibitor was 0.5kg/t relative to the fourth molybdenum concentrate.
Regrinding the fifth molybdenum concentrate, wherein ore particles with fineness less than 0.038mm in the regrind fifth molybdenum concentrate account for 85%, and adding sodium silicate into the regrind fifth molybdenum concentrate for pulping to obtain ore pulp containing the fifth molybdenum concentrate; the dosage of the water glass relative to the ore in the fifth molybdenum concentration is 1kg/t; adding an inhibitor into ore pulp containing the middlings of the fifth molybdenum concentration for flotation treatment for 4min to obtain molybdenum concentrate and middlings J; the amount of each inhibitor was 0.5kg/t relative to the fifth molybdenum concentrate.
The flotation process of the invention is adopted for flotation performance comparison, the flotation process of the invention is shown in figure 1, and the obtained flotation results are shown in table 1.
TABLE 1
As can be seen from the results in table 1, the galena flotation inhibitors of examples 1 to 5 of the present invention have good effects in the molybdenum-lead flotation separation process, compared to the use of the conventional inhibitors of minox, sodium humate and sodium thioglycolate. The content of lead is obviously reduced in the flotation process, the grade of lead in concentrate obtained by roughing can be as low as 0.019%, and the recovery rate of molybdenum can be as high as more than 87.97%.
Therefore, the galena floatation inhibitor provided by the invention has the advantages of good selectivity and strong inhibition capability, can effectively replace conventional medicaments such as phosphoxwell and the like in the molybdenum-lead floatation process, and can be widely applied to the molybdenum-lead floatation separation process, thereby improving the comprehensive utilization rate of ore resources.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. An galena flotation inhibitor, which is characterized by comprising a component A, humate and thioglycolate;
the component A comprises at least one of compounds with a structure shown as a formula (I);
wherein R is 1 Any one selected from hydrogen, C1-C3 alkyl and C1-C3 substituted alkyl;
R 2 and R is 3 Each independently selected from any one of hydrogen, halogen, hydroxy, amino, and mercapto.
2. The galena flotation suppressant according to claim 1, wherein component a comprises one or both of compounds having a structure as shown in formula (II) or formula (III);
3. the galena flotation suppressant according to claim 1, wherein the mass ratio of component a, the humate and the thioglycolate is 1:0.5 to 1:0.2 to 1.
4. A galena flotation suppressant according to claim 1 or 3, wherein the humate comprises sodium and/or potassium humate;
and/or, the thioglycolate includes one or more of sodium thioglycolate, potassium thioglycolate, ammonium thioglycolate, and lithium thioglycolate.
5. The galena flotation suppressant of claim 1, wherein the galena flotation suppressant is a liquid formulation; the content of the galena floatation inhibitor in the liquid preparation is 10-35 wt%.
6. A flotation separation process comprising adding to a slurry a galena flotation suppressant according to any one of claims 1 to 5.
7. The flotation separation process according to claim 6, wherein the mineral content of the pulp is between 5wt% and 45wt%.
8. The flotation separation method according to claim 7, wherein the content of mineral particles having a particle diameter of 0.074mm or less in the mineral is 60wt% or more.
9. The flotation separation process according to claim 6, wherein the galena flotation suppressant is used in an amount of 50 to 1500g/t, based on solids content, relative to the minerals in the pulp.
10. The flotation separation process according to claim 6, comprising the steps of:
(A) Carrying out flotation treatment on ore feeding for 5 times to obtain fifth molybdenum-concentrating middling; regrinding the fifth molybdenum concentrate middlings, adding water glass into the regrinded fifth molybdenum concentrate middlings, and performing pulp mixing to obtain ore pulp containing the fifth molybdenum concentrate middlings;
(B) And (3) adding the galena floatation inhibitor into the ore pulp in the step (A) for floatation to obtain molybdenum concentrate.
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