Sulfur mineral inhibitor and flotation separation method for copper-molybdenum-sulfur mixed flotation concentrate

Abstract

The invention discloses a sulfur mineral inhibitor and a flotation separation method of copper-molybdenum-sulfur mixed flotation concentrate, and relates to the technical field of mineral separation. The sulfur mineral inhibitor comprises polyglutamic acid and galactomannan; the separation method comprises the following steps: grinding ore and pulping; carrying out copper-molybdenum-sulfur bulk flotation on the ore pulp to obtain copper-sulfur bulk flotation concentrate and tailings; the pH value of the copper-sulfur mixed flotation concentrate is adjusted to 10-11, the copper-sulfur inhibitor, the first collecting agent and the foaming agent are added into the copper-sulfur mixed flotation concentrate, and copper-molybdenum concentrate and sulfur-containing tailings are obtained through roughing, concentration and scavenging; and the copper-molybdenum concentrate is subjected to one-time roughing, two-time scavenging and three-time concentration after two-time open-circuit flotation to obtain copper concentrate and molybdenum concentrate. According to the method, the recovery rate of copper is increased through the synergistic effect and the step-by-step and step-by-step technology, the floatability of sulfur is inhibited, meanwhile, adsorption of collecting agent groups on the surface of sulfur can be reduced, the inhibition effect on sulfur minerals is good, copper recovery is facilitated, and the quality of copper is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of ore dressing, and in particular, to a sulfur mineral inhibitor and a flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate. Background Art

[0002] As the main copper-containing mineral, chalcopyrite usually coexists with sulfide minerals such as pyrite and molybdenite, forming a copper-molybdenum-sulfur mixed sulfide deposit. The effective separation of copper, molybdenum, and sulfur is of great significance for the efficient development of copper resources. At present, for low-grade associated copper-molybdenum-sulfur resources, a bulk flotation process is often adopted, that is, a large amount of activator and sulfide ore collector are added to recover copper simultaneously, resulting in difficulty in effectively separating molybdenum and sulfur after bulk flotation.

[0003] At present, there have been many reports on the copper-molybdenum-sulfur bulk flotation separation process, but there are few reports on the separation of copper and sulfur after copper-molybdenum-sulfur bulk flotation from the perspective of the combination of flotation reagents and processes. Therefore, it is of great significance to find a new type of sulfur mineral inhibitor and an efficient and simple short-process technology to achieve efficient separation after copper-molybdenum-sulfur bulk flotation.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The first object of the present invention is to provide a sulfur mineral inhibitor, which selectively adsorbs on the surface of pyrite through the synergistic action of -COOH, -SH, amide group and -OH to form a thin film, increasing the hydrophilicity of the pyrite surface, promoting the inhibition of sulfur, and at the same time reducing the adsorption of collector groups on the surface of sphalerite through targeted coordination, so as to achieve effective separation of copper and sulfur.

[0006] The second object of the present invention is to provide a flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate, which uses the above-mentioned sulfur mineral inhibitor for flotation separation.

[0007] The present invention is implemented as follows:

[0008] The present invention provides a sulfur mineral inhibitor, which comprises polyglutamic acid and galactomannan.

[0009] In some preferred embodiments, the mass ratio of the polyglutamic acid to the galactomannan is (3 - 8):(2 - 9).

[0010] The present invention also provides a flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate using a sulfur mineral inhibitor, which comprises the following steps:

[0011] (1) Grinding the copper-molybdenum-sulfur raw ore and adding water to prepare a pulp;

[0012] (2) Conducting one rough selection and three scavenging selections on the pulp to obtain copper-molybdenum-sulfur bulk flotation concentrate and tailings;

[0013] (3) Adjust the pH value of the copper-molybdenum-sulfur bulk flotation concentrate to 7-9, add the sulfur mineral depressant, the first collector and the frother thereto, and obtain copper-molybdenum concentrate and sulfur-containing tailings through roughing, cleaning and three-stage scavenging.

[0014] (4) Conduct two-stage open-circuit flotation on the copper-molybdenum concentrate. After mixing the two-stage flotation concentrates, conduct one roughing, two scavengings and three cleanings to obtain final copper concentrate and molybdenum concentrate.

[0015] In some preferred embodiments, the first collector includes polystyrene-co-butyl acrylate and xanthate.

[0016] In some preferred embodiments, in step (1), it includes at least one of the following features (1) to (2):

[0017] (1) The copper content in the copper-molybdenum-sulfur raw ore is 0.4-0.8%, the molybdenum content is 0.1-0.2, and the sulfur content is 4.23-8.26%.

[0018] (2) After the grinding of the copper-molybdenum-sulfur raw ore, -0.074mm accounts for 70%-82%, and the concentration of the pulp is 30%-40%.

[0019] In some preferred embodiments, in step (2), the process of the copper-molybdenum-sulfur bulk flotation includes: adjusting the pH value of the pulp to 9-11, adding the sulfur mineral depressant, the first collector and the frother thereto, and obtaining the copper-molybdenum-sulfur bulk flotation concentrate and the tailings through one roughing and three scavengings.

[0020] In some preferred embodiments, in step (2), it includes at least one of the following features (1) to (3):

[0021] (1) The process of the roughing includes: adding 100-200 g / t of the sulfur mineral depressant, 100-300 g / t of the first collector and 20-50 g / t of the frother to the pulp, and obtaining roughing concentrate and roughing tailings through one roughing.

[0022] (2) The three-stage scavenging includes: adding 50-300 g / t of the sulfur mineral depressant and 50-150 g / t of the first collector to the roughing tailings, and obtaining scavenging concentrate and scavenging tailings through three-stage scavenging.

[0023] (3) The roughing concentrate and the scavenging concentrate are mixed to obtain the copper-molybdenum-sulfur bulk flotation concentrate.

[0024] In some preferred embodiments, in step (3), it includes at least one of the following features (1) to (4):

[0025] (1) The rough selection process includes: adding 30 - 50 g / t of the first collector, 100 - 300 g / t of the sulfide ore inhibitor, and 10 - 30 g / t of the frother to the copper - sulfur bulk flotation mixed ore, and obtaining the rough - selected concentrate and the rough - selected tailings through one - stage rough selection;

[0026] (2) The cleaning includes: sequentially performing cleaning I, cleaning II, and cleaning III on the rough - selected concentrate to obtain the cleaned concentrate and the cleaned tailings. In cleaning I, the addition amount of the sulfur mineral inhibitor is 50 - 100 g / t, and in cleaning II, the addition amount of the sulfur mineral inhibitor is 10 - 20 g / t;

[0027] (3) The three - stage stepped scavenging includes: sequentially performing three - stage stepped scavenging on the rough - selected tailings to obtain the scavenged concentrate and the scavenged tailings. In the first - stage stepped scavenging, adding the first collector which is polystyrene - co - n - butyl acrylate and xanthate, with a dosage of 20 - 30 g / t; in the second - stage stepped scavenging, adding the second collector allyl thiourea, with a dosage of 10 - 20 g / t; in the third - stage stepped scavenging, adding the third collector methyl 3 - thiomethylpropionate, with a dosage of 30 - 40 g / t; adding 30 - 50 g / t of molybdenum activator before the third - stage stepped scavenging;

[0028] (4) Mixing the cleaned concentrate and the scavenged concentrate to obtain the copper - molybdenum concentrate, and mixing the cleaned tailings and the scavenged tailings to obtain the sulfur - containing tailings.

[0029] In some preferred embodiments, in step (4), the rough selection process includes: adding 100 - 200 g / t of the sulfur mineral inhibitor to the flotation concentrate.

[0030] The present invention has the following beneficial effects:

[0031] (1) The sulfur mineral inhibitor provided by the present invention is composed of glutamic acid and galactomannan, which can effectively separate copper and sulfur minerals. The synergistic effect of glutamic acid and galactomannan, with mannose as the main chain and galactose as the side chain, selectively adsorbs on the Fe atoms on the surfaces of pyrite and chalcopyrite by combining with - COOH. Especially the presence of mannose can form a stable π bond with the iron in pyrite and a δ bond with the iron in chalcopyrite. The selective adsorption of the inhibitor on the surfaces of chalcopyrite and pyrite realizes the efficient separation of chalcopyrite and pyrite.

[0032] (2) The stepped flotation process adopted for copper - molybdenum - sulfur separation in the present invention performs selective stepped dosing and multiple rough - selection open - circuit tests, realizing the efficient recovery of copper and reducing the dosage of reagents at the same time. Detailed implementation manners

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. For those not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are followed. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0034] The first aspect of the present invention provides a sulfur mineral inhibitor, comprising polyglutamic acid and galactomannan.

[0035] The sulfur mineral inhibitor provided by the present invention can achieve effective separation of copper-molybdenum minerals after activation with copper sulfate. Polyglutamic acid is an anionic polymer, and the carboxylate groups (-COO-) on its molecular chain can form stable chelates with metal ions (such as Fe 2+ ) on the surface of sulfur minerals (such as pyrite), covering the surface of sulfur minerals, thereby hindering the adsorption of collectors and reducing their floatability. Galactomannan is a non-ionic polysaccharide, and its hydroxyl groups (-OH) can be adsorbed on the surface of sulfur minerals through hydrogen bonding to form a hydrophilic film, further inhibiting the floating of sulfur minerals. The effects of these two inhibitors on copper-molybdenum minerals are relatively small. Due to the large difference in their surface chemical properties, it is difficult to form a similar adsorption layer, thus achieving efficient separation of copper-molybdenum and sulfur.

[0036] In some specific embodiments of the present invention, the mass ratio of the polyglutamic acid to the galactomannan is (3-8):(2-9), such as any value among 3:2, 3:3, 3:4, 3:5, 3:6, 3:7, 4:2, 4:3, 4:4, 4:5, 4:6, 5:2, 5:3, 5:4, 5:5, 6:2, 6:3, 6:4, 7:2, 7:3, 8:2 or the range value composed of any two of these values.

[0037] The second aspect of the present invention provides a flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate using the above sulfur mineral inhibitor, comprising the following steps:

[0038] (1) Grinding the copper-molybdenum-sulfur raw ore and adding water to prepare a pulp;

[0039] (2) Conducting one rough selection and three scavenging selections on the pulp to obtain a copper-molybdenum-sulfur bulk flotation concentrate and tailings;

[0040] (3) Adjusting the pH value of the copper-molybdenum-sulfur bulk flotation concentrate to 7-9, adding the sulfur mineral inhibitor, a first collector, and a frother thereto, and obtaining a copper-molybdenum concentrate and a sulfur-containing tailings through rough selection, cleaning, and three-stage scavenging selections;

[0041] (4) Conducting two open-circuit flotation operations on the copper-molybdenum concentrate. After mixing the two flotation concentrates, conducting one rough selection, two scavenging selections, and three cleaning selections to obtain the final copper concentrate and molybdenum concentrate.

[0042] In some specific embodiments of the present invention, the first collector comprises polystyrene-co-butyl acrylate and xanthate, wherein the mass ratio of the polystyrene-co-butyl acrylate to the xanthate is 1-3:5-9, such as any one value or a range value composed of any two point values among 1:5, 1:6, 1:7, 1:8, 1:9, 2:5, 2:6, 2:7, 2:8, 3:5, 3:6, 3:7.

[0043] The first collector enhances the selective adsorption of copper-molybdenum minerals through synergistic effects and simultaneously inhibits the flotation of sulfur minerals. Polystyrene-co-butyl acrylate (PS-co-PBA) is a hydrophobic polymer. Its benzene ring structure can undergo hydrophobic interactions with the surfaces of non-polar copper-molybdenum minerals (such as molybdenite and chalcopyrite), while the butyl acrylate chain segment provides certain spatial flexibility and adsorption stability, enabling it to form a dense hydrophobic film on the mineral surface. Meanwhile, xanthate (such as ethyl xanthate), as a traditional collector of thiocompounds, can chemically adsorb with metal ions (such as Cu 2+ , Mo 4+ ) on the surfaces of copper-molybdenum minerals to form a hydrophobic metal xanthate film. The combination of the two not only enhances the hydrophobicity of copper-molybdenum minerals but also, due to the steric hindrance effect of the polymer, reduces the competitive adsorption of sulfur minerals (such as pyrite) on the collector, thereby optimizing the separation effect.

[0044] In some specific embodiments of the present invention, in step (1), the copper-molybdenum-sulfur raw ore contains 0.4-0.8% copper, 0.1-0.2% molybdenum, and 4.23-8.26% sulfur;

[0045] In some specific embodiments of the present invention, in step (1), after the grinding of the copper-molybdenum-sulfur raw ore, -0.074 mm (particle size less than 0.074 mm) accounts for 70%-82%; the concentration of the pulp is 30%-40%.

[0046] In some specific embodiments of the present invention, in step (2), the process of the bulk flotation of copper-molybdenum-sulfur includes: adjusting the pH value of the pulp to 9-11, adding the sulfur mineral inhibitor, the first collector, and the frother, and obtaining the bulk flotation concentrate of copper-molybdenum-sulfur and the tailings through one roughing and three scavengings.

[0047] In some specific embodiments of the present invention, in step (2), the process of the roughing includes: adding 100-200 g / t of the sulfur mineral inhibitor, 100-300 g / t of the first collector, and 20-50 g / t of the frother to the pulp, and obtaining the roughing concentrate and the roughing tailings through one roughing.

[0048] In different embodiments, in step (2), during rough selection, the addition amount of the inhibitor can be any value among 100 g / t, 120 g / t, 150 g / t, 180 g / t, 200 g / t or a range value composed of any two of these values; the addition amount of the first collector can be any value among 100 g / t, 150 g / t, 200 g / t, 250 g / t, 300 g / t or a range value composed of any two of these values; the dosage of the frother can be any value among 20 g / t, 30 g / t, 40 g / t, 50 g / t or a range value composed of any two of these values.

[0049] In some specific embodiments of the present invention, in step (2), the three-stage scavenging includes: adding 50 - 300 g / t of the sulfur mineral inhibitor and 50 - 150 g / t of the first collector to the roughing tailings, and obtaining scavenging concentrate and scavenging tailings after three-stage scavenging;

[0050] In different embodiments, in step (2), during the three-stage scavenging, the addition amount of the sulfur mineral inhibitor can be any value among 50 g / t, 100 g / t, 150 g / t, 200 g / t, 250 g / t, 300 g / t or a range value composed of any two of these values; the addition amount of the first collector can be any value among 50 g / t, 100 g / t, 150 g / t or a range value composed of any two of these values.

[0051] In some specific embodiments of the present invention, in step (2), the roughing concentrate and the scavenging concentrate are mixed to obtain the copper-molybdenum-sulfur bulk flotation concentrate.

[0052] In some specific embodiments of the present invention, in step (3), the process of roughing includes: adding 30 - 50 g / t of the first collector, 100 - 300 g / t of the sulfide mineral inhibitor and 10 - 30 g / t of the frother to the copper-sulfur bulk flotation mixed ore, and obtaining roughing concentrate and roughing tailings after one-stage roughing;

[0053] In different embodiments, in step (3), during roughing, the addition amount of the first collector can be any value among 30 g / t, 40 g / t, 50 g / t or a range value composed of any two of these values; the addition amount of the sulfur mineral inhibitor is any value among 100 g / t, 150 g / t, 200 g / t, 250 g / t, 300 g / t or a range value composed of any two of these values; the addition amount of the frother is any value among 10 g / t, 20 g / t, 30 g / t or a range value composed of any two of these values.

[0054] In some specific embodiments of the present invention, in step (3), the beneficiation includes: successively performing beneficiation I, beneficiation II, and beneficiation III on the rough concentrate to obtain the beneficiated concentrate and beneficiated tailings. In beneficiation I, the addition amount of the sulfur mineral inhibitor is 50 - 100 g / t, and in beneficiation II, the addition amount of the sulfur mineral inhibitor is 10 - 20 g / t.

[0055] In some specific embodiments of the present invention, in step (3), the three-stage scavenging includes: successively performing three-stage scavenging on the rough tailings to obtain the scavenged concentrate and scavenged tailings. In the first-stage scavenging, the first collector added is polystyrene - co - n - butyl acrylate and xanthate, and the dosage is 20 - 30 g / t; in the second-stage scavenging, the second collector added is allyl thiourea, and the dosage is 10 - 20 g / t; in the third-stage scavenging, the third collector added is methyl 3 - thiomethylpropionate, and the dosage is 30 - 40 g / t; 30 - 50 g / t of molybdenum activator is added before the third-stage scavenging.

[0056] In some specific embodiments of the present invention, in step (3), the beneficiated concentrate and the scavenged concentrate are mixed to obtain the copper - molybdenum concentrate, and the beneficiated tailings and the scavenged tailings are mixed to obtain the sulfur - containing tailings.

[0057] In some specific embodiments of the present invention, in step (4), the process of the roughing includes: adding 100 - 200 g / t of the sulfur mineral inhibitor to the flotation concentrate, such as any value among 100 g / t, 120 g / t, 150 g / t, 180 g / t, 200 g / t or the range value composed of any two of these values.

[0058] In some specific embodiments of the present invention, in step (4), no reagents are added during the two - stage roughing and three - stage beneficiation.

[0059] In the present invention, the addition amount of the reagent is relative to the amount of the original ore dry ore.

[0060] The features and properties of the present invention are further described in detail below in conjunction with the embodiments.

[0061] Example 1

[0062] This example provides a method for flotation separation of copper - molybdenum - sulfur bulk flotation concentrate. The mineral raw material in this example is a copper - molybdenum - sulfur polymetallic ore in a certain place in Gansu. The main metal mineral composition is: chalcopyrite, molybdenite, pyrite, native gold, native silver, and the gangue minerals are mainly quartz, feldspar, etc. The average grades of the main valuable elements copper and molybdenum in the ore are 1.5% and 0.5% respectively. It mainly includes the following steps:

[0063] (1) Reagent preparation:

[0064] Preparation of sulfur mineral inhibitor: Mix polyglutamic acid (PGA) and galactomannan (GM) in a mass ratio of 1:2, put them into a mechanical ball mill with a ball-to-material ratio of 5:1, set the rotation speed at 300 rpm, and mix for 40 min. The purity of polyglutamic acid (PGA) is ≥95%, and the carboxyl content is 4.8 mmol / g; the purity of galactomannan (GM) is ≥90%, and the content of β-D-mannose is ≥85%.

[0065] Preparation of the first collector: Mix polystyrene-co-butyl acrylate (PS-co-BA) and butyl xanthate (BX) in a mass ratio of 1:2. The copolymer molecular weight of polystyrene-co-butyl acrylate (PS-co-BA) is 5000 - 8000, and the sulfur content of butyl xanthate (BX) is ≥24 wt%.

[0066] (2) Grinding and pulp conditioning: Grind the original ore to 78% passing 0.074 mm, and add water to adjust the pulp concentration to 20%.

[0067] (3) Bulk flotation of copper, molybdenum and sulfur: Adjust the pH of the pulp to 9.5 with sodium bicarbonate, add 100 g / t of sulfur mineral inhibitor, 100 g / t of the first collector, and 20 g / t of frother for one roughing to obtain rough concentrate and rough tailings. Add 50 g / t of sulfur mineral inhibitor and 50 g / t of the first collector to the rough tailings, and perform three scavengings to obtain scavenged concentrate and scavenged tailings. Mix the rough concentrate and the scavenged concentrate to obtain copper-molybdenum bulk flotation concentrate.

[0068] (4) Separation operation of copper, molybdenum and sulfur: Adjust the pH value of the copper-molybdenum-sulfur bulk flotation concentrate to 8, add 150 g / t of the sulfur mineral inhibitor, 35 g / t of the first collector and 15 g / t of frother thereto, and perform one roughing to obtain rough concentrate and rough tailings; conduct cleaning I, cleaning II and cleaning III on the rough concentrate in sequence to obtain the cleaned concentrate and cleaned tailings. In cleaning I, the addition amount of the sulfur mineral inhibitor is 60 g / t, and in cleaning II, the addition amount of the sulfur mineral inhibitor is 20 g / t; conduct three-stage scavengings on the rough tailings in sequence to obtain scavenged concentrate and scavenged tailings. In the first-stage scavenging, add the first collector which is polystyrene-co-butyl acrylate and xanthate with a dosage of 20 g / t; in the second-stage scavenging, add the second collector allyl isothiourea with a dosage of 15 g / t; in the third-stage scavenging, add the third collector methyl 3-thiomethylpropionate with a dosage of 30 g / t; add 40 g / t of molybdenum activator before the third-stage scavenging and stir for 3 min; mix the cleaned concentrate and the scavenged concentrate to obtain copper-molybdenum concentrate, and mix the cleaned tailings and the scavenged tailings to obtain sulfur-containing tailings.

[0069] (5) Copper-molybdenum separation operation: The copper-molybdenum concentrate is subjected to two open-circuit flotation processes. After the two flotation concentrates are mixed, 100 g / t of the sulfur mineral inhibitor is added to the flotation concentrate, followed by one rough selection, two scavenging selections, and three cleaning selections to obtain the final copper concentrate and molybdenum concentrate.

[0070] Example 2

[0071] This example provides a flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate. The mineral raw material in this example is a copper-molybdenum-sulfur polymetallic ore in a certain place in Gansu. The main metal mineral compositions are: chalcopyrite, molybdenite, pyrite, native gold, and native silver. The gangue minerals are mainly quartz, feldspar, etc. The average grades of the main valuable elements copper and molybdenum in the ore are 0.65% and 0.53% respectively. The main steps include the following:

[0072] (1) Reagent preparation:

[0073] Preparation of sulfur mineral inhibitor: Polyglutamic acid (PGA) and galactomannan (GM) are mixed in a mass ratio of 3:2, placed in a mechanical ball mill with a ball-to-material ratio of 5:1, and the rotation speed is set at 300 rpm for 40 minutes. The purity of polyglutamic acid (PGA) is ≥95%, and the carboxyl content is 4.8 mmol / g; the purity of galactomannan (GM) is ≥90%, and the β-D-mannose content is ≥85%.

[0074] Preparation of the first collector: Polystyrene-co-butyl acrylate (PS-co-BA) and butyl xanthate (BX) are mixed in a mass ratio of 1:1. The copolymer molecular weight of polystyrene-co-butyl acrylate (PS-co-BA) is 5000 - 8000, and the sulfur content of butyl xanthate (BX) is ≥24 wt%.

[0075] (2) Grinding and pulp conditioning: The raw ore is ground to 78% passing 0.074 mm, and water is added to adjust the pulp concentration to 20%.

[0076] (3) Copper-molybdenum-sulfur bulk flotation: The pH of the pulp is adjusted to 9.5 with sodium bicarbonate, 100 g / t of sulfur mineral inhibitor, 100 g / t of the first collector, and 20 g / t of foaming agent are added, and one rough selection is carried out to obtain the rough concentrate and the rough tailings. 50 g / t of sulfur mineral inhibitor and 50 g / t of the first collector are added to the rough tailings, and after three scavenging selections, the scavenging concentrate and the scavenging tailings are obtained. The rough concentrate and the scavenging concentrate are mixed to obtain the copper-molybdenum bulk flotation concentrate.

[0077] (4) Copper-molybdenum-sulfur separation operation: Adjust the pH value of the copper-molybdenum-sulfur bulk flotation concentrate to 8, add 150 g / t of the sulfur mineral inhibitor, 35 g / t of the first collector, and 15 g / t of the frother thereto, and obtain a rougher concentrate and a rougher tailing through one-stage roughing; conduct cleaning I, cleaning II, and cleaning III on the rougher concentrate in sequence to obtain the cleaned concentrate and the cleaned tailing. In cleaning I, the addition amount of the sulfur mineral inhibitor is 60 g / t; in cleaning II, the addition amount of the sulfur mineral inhibitor is 20 g / t; conduct three-stage scavenging on the rougher tailing in sequence to obtain a scavenged concentrate and a scavenged tailing. In the first-stage scavenging, the first collector added is polystyrene-co-butyl acrylate and xanthate, and the dosage is 20 g / t; in the second-stage scavenging, the second collector allyl isothiourea is added, and the dosage is 15 g / t; in the third-stage scavenging, methyl 3-thiomethylpropionate serving as the third collector is added, and the dosage is 30 g / t; add 40 g / t of a molybdenum activator before the third-stage scavenging and stir for 3 min; mix the cleaned concentrate and the scavenged concentrate to obtain a copper-molybdenum concentrate, and mix the cleaned tailing and the scavenged tailing to obtain a sulfur-containing tailing.

[0078] (5) Copper-molybdenum separation operation: Conduct two-stage open-circuit flotation on the copper-molybdenum concentrate. After mixing the two-stage flotation concentrates, add 100 g / t of the sulfur mineral inhibitor to the flotation concentrate, and conduct one-stage roughing, two-stage scavenging, and three-stage cleaning to obtain a final copper concentrate and a molybdenum concentrate.

[0079] Comparative Example 1

[0080] This comparative example provides a flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate. This Comparative Example 1 is the same as Example 2 in other conditions, and the only difference is that: in this comparative example, lime is used as the sulfur mineral inhibitor, and only butyl xanthate is used as the collector.

[0081] The copper and molybdenum recovery results obtained in Examples 1-2 and Comparative Example 1 are shown in Table 1.

[0082] Table 1. Comparison results of copper and molybdenum recoveries

[0083]

[0084]

[0085] According to the results, it can be seen from the experimental results in Table 1 that both Example 1 and Example 2 are significantly superior to Comparative Example 1 in terms of copper-molybdenum recovery rate and concentrate grade, which fully proves the effectiveness of the new composite reagent combination and the optimized flotation process. In terms of copper recovery rate, the mixed flotation concentrate stage of Example 1 and 2 reached 93.00% and 92.00% respectively, and the final concentrate stage remained at a high level of 89.00% and 88.69%, while Comparative Example 1 was only 90.00% and 87.69% respectively. The performance of molybdenum recovery rate is also outstanding. The recovery rates of Example 1 and 2 in the mixed flotation concentrate stage are 87.00% and 87.55%, and 84.00% and 83.69% in the final concentrate stage, which are significantly higher than 84.55% and 80.36% of Comparative Example 1. In addition, the data of concentrate grade further corroborates this advantage. The final copper concentrate grades of Example 1 and 2 reached 26.7% and 25.87% respectively, and the molybdenum concentrate grades were 1.5% and 1.42%, while the copper and molybdenum grades of Comparative Example 1 were only 24.32% and 1.25%. These differences are mainly attributed to the limitations of the combination of traditional lime inhibitor and single xanthate collector in Comparative Example 1, which has poor effects in sulfur mineral inhibition and selective collection. In contrast, the polyamino acid and galactomannan composite inhibitor, as well as the polystyrene-co-butyl acrylate and butyl xanthate composite collector used in Example 1 and 2, not only enhance the inhibition ability of sulfur minerals, but also improve the selective adsorption efficiency of copper-molybdenum minerals. Therefore, the experimental results clearly show that the optimized reagent system and flotation process can significantly improve the comprehensive indexes of copper-molybdenum separation, providing a reliable technical solution for the efficient recovery of complex polymetallic ores.

[0086] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A sulfur mineral inhibitor, characterized in that, It includes polyglutamic acid and galactomannan.

2. The sulfur mineral inhibitor according to claim 1, characterized in that, The mass ratio of the polyglutamic acid to the galactomannan is (3 - 8):(2 - 9).

3. A method for flotation separation of copper-molybdenum-sulfur bulk flotation concentrate using a sulfur mineral inhibitor as described in claim 1 or 2, characterized in that, It includes the following steps: (1) Grind the copper-molybdenum-sulfur raw ore and add water to obtain pulp. (2) Conduct one rough selection and three scavenging selections on the pulp to obtain copper-molybdenum-sulfur bulk flotation concentrate and tailings. (3) Adjust the pH value of the copper-molybdenum-sulfur bulk flotation concentrate to 7 - 9, add the sulfur mineral inhibitor, the first collector, and the frother thereto, and obtain copper-molybdenum concentrate and sulfur-containing tailings through rough selection, cleaning, and three-stage scavenging selections. (4) Conduct two open-circuit flotation operations on the copper-molybdenum concentrate. After mixing the two flotation concentrates, conduct one rough selection, two scavenging selections, and three cleaning selections to obtain the final copper concentrate and molybdenum concentrate.

4. The flotation separation method of a copper-molybdenum-sulfur bulk flotation concentrate according to claim 3, characterized in that, The first collector includes polystyrene-co-butyl acrylate and xanthate.

5. The flotation separation method of a copper-molybdenum-sulfur bulk flotation concentrate according to claim 4, characterized in that, The mass ratio of the polystyrene-co-butyl acrylate to the xanthate is 1 - 3:5 - 9.

6. The flotation separation method of a copper-molybdenum-sulfur bulk flotation concentrate according to claim 3, characterized in that, In step (1), it includes at least one of the following features (1) to (2): (1) The copper content in the copper-molybdenum-sulfur raw ore is 0.4 - 0.8%, the molybdenum content is 0.1 - 0.2, and the sulfur content is 4.23 - 8.26%. (2) After the grinding of the copper-molybdenum-sulfur raw ore, -0.074mm accounts for 70% - 82%, and the concentration of the pulp is 30% - 40%.

7. A flotation separation method for copper-molybdenum-sulfur bulk flotation concentrate according to claim 3, characterized in that, In step (2), the process of the copper-molybdenum-sulfur bulk flotation includes: adjust the pH value of the pulp to 9 - 11, add the sulfur mineral inhibitor, the first collector, and the frother thereto, and obtain the copper-molybdenum-sulfur bulk flotation concentrate and the tailings through one rough selection and three scavenging selections.

8. A method for flotation separation of copper-molybdenum-sulfur bulk flotation concentrate according to claim 7, characterized in that, In step (2), it includes at least one of the following features (1) to (3): (1) The process of the rough selection includes: add 100 - 200g / t of the sulfur mineral inhibitor, 100 - 300g / t of the first collector, and 20 - 50g / t of the frother to the pulp, and obtain rough selection concentrate and rough selection tailings through one rough selection. (2) The three scavenging selections include: add 50 - 300g / t of the sulfur mineral inhibitor and 50 - 150g / t of the first collector to the rough selection tailings, and obtain scavenging selection concentrate and scavenging selection tailings through three scavenging selections. (3) The rough selection concentrate and the scavenging selection concentrate are mixed to obtain the copper-molybdenum-sulfur bulk flotation concentrate.

9. The flotation separation method of a copper-molybdenum-sulfur bulk flotation concentrate according to claim 3, characterized in that, In step (3), it includes at least one of the following features (1) to (4): (1) The process of the rough selection includes: add 30 - 50g / t of the first collector, 100 - 300g / t of the sulfide mineral inhibitor, and 10 - 30g / t of the frother to the copper-sulfur bulk flotation mixed ore, and obtain rough selection concentrate and rough selection tailings through one rough selection. (2) The cleaning includes: conduct cleaning I, cleaning II, and cleaning III on the rough selection concentrate in sequence to obtain the cleaning concentrate and cleaning tailings. In cleaning I, the addition amount of the sulfur mineral inhibitor is 50 - 100g / t, and in cleaning II, the addition amount of the sulfur mineral inhibitor is 10 - 20g / t. (3) The three-stage scavenging of the steps includes: sequentially subjecting the rougher tailings to three-stage scavenging to obtain the scavenged concentrate and the scavenged tailings. In the first-stage scavenging I, the first collector, namely polystyrene-co-n-butyl acrylate and xanthate, is added with a dosage of 20 - 30 g / t; in the second-stage scavenging II, the second collector, namely allyl thiourea, is added with a dosage of 10 - 20 g / t; in the third-stage scavenging III, the third collector, namely methyl 3-thiomethylpropionate, is added with a dosage of 30 - 40 g / t; and 30 - 50 g / t of molybdenum activator is added before the third-stage scavenging III. (4) The selected concentrate and the scavenged concentrate are mixed to obtain the copper-molybdenum concentrate, and the selected tailings and the scavenged tailings are mixed to obtain the sulfur-containing tailings.

10. The flotation separation method of a copper-molybdenum-sulfur bulk flotation concentrate according to claim 3, characterized in that, In step (4), the process of the roughing includes: adding 100 - 200 g / t of the sulfur mineral inhibitor to the flotation concentrate.

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