CN111715409B - Combined lead inhibitor of micro-fine particle galena and application thereof - Google Patents

Combined lead inhibitor of micro-fine particle galena and application thereof Download PDF

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CN111715409B
CN111715409B CN202010620619.8A CN202010620619A CN111715409B CN 111715409 B CN111715409 B CN 111715409B CN 202010620619 A CN202010620619 A CN 202010620619A CN 111715409 B CN111715409 B CN 111715409B
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lead
inhibitor
galena
flotation
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CN111715409A (en
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魏茜
焦芬
覃文庆
杨聪仁
刘维
韩俊伟
董留洋
崔艳芳
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Central South University
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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
    • 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
    • B03D1/018—Mixtures of inorganic and organic compounds
    • 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
    • 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
    • B03D2201/04—Frothers
    • 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
    • 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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Abstract

The invention discloses a combined lead inhibitor for fine-grained galena and application thereof, wherein active components of the combined lead inhibitor comprise polymaleic acid, water glass and carboxyethyl cellulose, and the mass ratio of the polymaleic acid to the water glass to the carboxyethyl cellulose is (1-6) - (2-5) - (0.25-2). The invention combines the organic inhibitor polymaleic acid, the carboxyethyl cellulose and the inorganic inhibitor water glass according to a certain mass ratio, and can reduce the dosage of the medicament compared with the dosage when the medicament is used alone and obviously enhance the inhibition performance through the synergistic action among the medicaments. The combined inhibitor can efficiently and selectively inhibit coarse and medium grade galena, has a good inhibition effect on micro-fine galena, does not basically influence the flotation of chalcopyrite, and achieves the aim of selective separation. The combined inhibitor is prepared by combining water-soluble micromolecule carboxylic acid, a macromolecular organic substance CEC and a conventional inhibitor, is simple in preparation and easy to implement industrially, and simultaneously HPMA is an excellent water treatment agent and can complex heavy metal ions in mineral processing wastewater, so that the difficulty of wastewater recycling is greatly reduced.

Description

Combined lead inhibitor of micro-fine particle galena and application thereof
Technical Field
The invention belongs to the field of mineral processing, and particularly relates to a combined lead inhibitor for micro-fine galena and application thereof.
Background
The complex copper-lead-zinc multi-metal sulphide ore has complex ore properties and is densely symbiotic with useful minerals, so the complex ore dressing process flow is selected according to the properties of raw ores when the complex copper-lead-zinc multi-metal sulphide ore is processed. The beneficiation process flow generally comprises a preferential flotation process, a partial mixed flotation process, a copper-lead-zinc mixed flotation process and the like. Because chalcopyrite and galena have very similar floatability, the copper-lead separation process after copper-lead mixed flotation is most widely used, the process can obtain copper-lead mixed concentrate through mixed flotation under the condition of coarse grinding, then carry out copper-lead separation, and recleaning zinc and sulfur from tailings. In the process of separating the copper-lead bulk concentrates, according to the principle of inhibiting more and less floating, the lead-inhibiting floating copper is the most main method for flotation separation of the copper-lead bulk concentrates, so that the main factors influencing the flotation separation of chalcopyrite and galena are the high-efficiency dissociation of the two minerals and the selective inhibition of the galena.
Generally, the useful minerals in the ore have uneven embedded granularity, and after a section of grinding, partial copper and lead minerals are not completely dissociated, so that the separation of copper and lead is not facilitated, and the mutual metal content in the concentrate is often higher. Therefore, before copper-lead separation, copper-lead separation is often performed after regrinding the copper-lead bulk concentrate. The chalcopyrite and the galena have very similar self-induction and collector-induced flotation characteristics, so that the difficulty of copper-lead separation is high. The galena has low hardness and good brittleness, three-phase cleavage develops, most of the galena can be crushed to-19 mu m at lower regrinding fineness, the floatability of the micro-fine galena can be changed, the rheological property of ore pulp is changed, and the separation of copper and lead is not favorable. For the inhibition of galena, a great deal of research is carried out at home and abroad, but the traditional lead inhibitors have certain limitations, at present, the mainstream lead inhibitors at home are potassium dichromate, sulfites, polysaccharides, humic acid salts and the like, and the traditional inhibitors have no inhibition effect on the galena with micro-fine particles (-19 mu m). Therefore, the separation of copper and lead is not complete, and the crux is that the fine-particle lead ore is difficult to inhibit, so that the mutual content of metals in the concentrate is high.
Aiming at the symptom of incomplete copper-lead separation, a high-efficiency combined lead inhibitor is screened, the inhibition of the micro-fine galena is enhanced, and the method has important significance for realizing high-efficiency deep flotation separation of lead-zinc sulfide ores.
Disclosure of Invention
The invention aims to provide a high-efficiency, green, economic and environment-friendly combined lead inhibitor for micro-fine galena and application thereof, which are used for solving the problems of incomplete micro-fine lead inhibition in a copper-lead flotation separation system, high lead content in a copper concentrate product, large medicament dosage and low lead recovery rate.
The combined lead inhibitor for the microfine galena comprises active components including polymaleic acid (HPMA), water glass (SSL) and carboxyethyl cellulose (CEC) in a mass ratio of (1-6) to (2-15) to (0.25-2).
The combination inhibitor is a combination of aqueous solutions of active ingredients, wherein the mass concentration of the polymaleic acid aqueous solution is 1-2%, the mass concentration of the water glass aqueous solution is 2-5%, and the mass concentration of the carboxyethyl cellulose aqueous solution is 0.25-0.5%; the mass ratio of the 3 kinds of aqueous solution added into the ore pulp is as follows: the polymaleic acid aqueous solution comprises (3-1) an aqueous sodium silicate solution and (3-1) an aqueous carboxyethyl cellulose solution and (4-1).
The polymaleic acid HPMA is a micromolecular polycarboxylic acid, and the molecular weight is 400-800; the molecular weight of the carboxyethyl cellulose is 8-10 ten thousand, and the substitution degree is 0.8-0.9; the modulus of the water glass is 2.5-3.0.
The combined lead inhibitor of the micro-fine galena is applied to the flotation of lead-containing sulphide ores.
A method for flotation of lead-containing sulfide ore by using a combined lead inhibitor of micro-fine galena comprises the following steps:
1) crushing raw ore, performing wet ball milling to obtain ore pulp, and performing copper-lead mixed flotation on the ore pulp to obtain copper-lead mixed concentrate;
2) regrinding the copper-lead bulk concentrate obtained in the step 1) to obtain reground copper-lead bulk concentrate, and then adding activated carbon, a combined inhibitor, a collecting agent and a foaming agent into the bulk concentrate to perform flotation to obtain copper concentrate and lead concentrate.
In the step 1), ball milling is carried out until the fineness is-0.074 mm, and the fineness accounts for 70-80%.
In the step 2), the mixture is ground again until the fineness is-0.045 mm and accounts for 70-95%; the flotation process comprises the steps of primary coarse cleaning, secondary cleaning and tertiary fine cleaning; collecting agent is Z-200, and foaming agent is terpineol oil.
The roughing process comprises the following steps: stirring the activated carbon at 2000-10000 g/t (for ore feeding) for 5-10 min; adding 2000-6000 g/t of lead combined inhibitor (for feeding ore), and stirring for 3-5 min; adding a collecting agent Z-20020-200 g/t (for ore feeding), and stirring for 2-3 min; adding 10-100 g/t (for feeding) of foaming agent pine oil, and stirring for 1-2 min; and (4) carrying out flotation for 3-4 min.
The scavenging process comprises the following steps: adding Z-2007-100 g/t (mineral feeding) for the first scavenging, stirring for 2-3 min, and performing flotation for 1-3 min; adding Z-2005-50 g/t (for feeding ore) in the second scavenging, stirring for 2-3 min, and performing flotation for 1-2 min;
the fine selection process comprises the following steps: adding 100-1000 g/t of lead combined inhibitor (for ore feeding) for first selection, stirring for 3-5 min, and performing flotation for 2-3 min; adding 50-500 g/t of lead combined inhibitor (for ore feeding) for the second selection, stirring for 3-5 min, and performing flotation for 1-2 min; and (4) flotation reagent is not added in the third concentration, and blank flotation is carried out for 0.5-1 min.
The 'g/t' in the invention refers to the addition amount of the medicament relative to the feeding of the copper-lead bulk concentrate, for example, the addition amount of the ethionine Z-200 is 50g/t, which refers to the fact that the ethionine Z-20050g is required to be added for treating 1 ton of feeding ore.
The principle of the invention is as follows:
sodium carboxyethyl cellulose (CEC) is an anionic polymer and is an effective inhibitor and flocculant for calcareous magnesiosilicate, carbonate and argillaceous gangue. Carboxyl groups of CEC are dissociated in a solution and negatively charged, and thus can exert a dispersing effect on minerals. On one hand, the CEC promotes the oxidation of the galena surface, the CEC is chemically adsorbed on the galena surface to generate the carboxyethyl cellulose lead, a large amount of hydroxyl contained in the CEC can generate hydrogen bonding between water molecules, a hydration film is formed on the galena surface, and the galena is strongly inhibited. The adsorption effect of CEC and the surface of the chalcopyrite is weaker, and the flotation of the chalcopyrite is not influenced. On the other hand, in the flotation pulp obtained after the regrinding of the copper-lead bulk concentrate, chalcopyrite and galena mainly exist in a medium-fine particle grade form, and researches show that CEC with different molecular weights and different substitution degrees have different influences on the agglomeration and dispersion behaviors of minerals, so that the addition of CEC can selectively agglomerate the galena with a fine particle grade, prevent the galena with fine particles from being mechanically entrained into the chalcopyrite concentrate, and further strengthen the inhibition on the galena with fine particles.
The main functional group in the molecular structure of polymaleic acid (HPMA) is carboxyl, which can react with the surface of mineral, in the molecular structure, a large number of polar groups are arranged on a hydrocarbon skeleton with a small proportion as possible, the polar groups are positioned at two ends of the molecule or are distributed in the whole molecule, part of the polarity reacts based on the surface of mineral, and the rest polar groups face outwards to form a hydrophilic adsorption layer, so that the surface of mineral is strongly hydrophilic or the adsorption of a collecting agent is hindered, thereby achieving the inhibiting effect. And HPMA has stronger complexing ability to metal ions, generates soluble complex and has better scale inhibition, dispersion and corrosion inhibition performance. On the one hand, polymaleic acid is selectively and chemically adsorbed on the surface of galena through carboxyl, and the rest of carboxyl is hydrophilic outwards, so that the surface of the galena is coated with a hydrophilic film, and the galena is hydrophilic. On the other hand, as the HPMA has stronger metal ion complexing ability, the HPMA promotes the dissolution of lead ions on the surface of the galena, and the dissolved lead ions play a role in connecting CEC and HPMA with the surface of the galena, so that a great amount of inhibitor hydrophilic films are overlapped and wrapped on the surface of the galena, the collecting agent cannot be further adsorbed on the surface of the galena, and the galena is strongly inhibited.
Water glass (SSL) in Cu-Fe-Si-S-H2O system, Si (OH)3 -Is the predominant form of Si present in Pb-Si-S-H2O system, PbSiO4And Si (OH)3 -Is the main existing form of Si, therefore, SSL selectively inhibits chalcopyrite and galena because it generates hydrophilic substance PbSiO on the galena surface4And the adsorption on the surface of the chalcopyrite is weak, so that the selective inhibition effect on the galena can be generated. Meanwhile, SSL is a dispersing agent, so that the viscosity of ore pulp is effectively reduced, fine-fraction entrainment is reduced, the action probability of an inhibitor and micro-fine-fraction galena is increased, and the inhibition of the fine-fraction galena is facilitated.
The organic inhibitors CEC, HPMA and the inorganic inhibitor SSL are combined into the lead inhibitor according to a certain proportion, and the defects of large medicament dosage, poor inhibition effect on micro-fine-grade lead and the like when CEC, HPMA and SSL are used independently are overcome through the synergistic effect among the combined inhibitors. On the other hand, SSL selectively adsorbs to the galena surface to generate a hydrophilic substance PbSiO4Meanwhile, SSL can play a role in dispersion, greatly reduce the viscosity of flotation pulp, increase the action probability of inhibitors CEC and HPMA and the micro-fine galena and facilitate the selective inhibition of the micro-fine galena. When the galena, the inhibitor and the collecting agent act together, the galena and the inhibitor act mainly, and when the chalcopyrite, the inhibitor and the collecting agent act together, the chalcopyrite and the collecting agent act mainly. Therefore, the combined inhibitor can selectively inhibit coarse and medium grade galena, has a good inhibiting effect on fine grade galena (-19 mu m), and basically has no influence on the flotation recovery of chalcopyrite.
Compared with the traditional lead inhibitor, the invention has the beneficial technical effects that:
(1) according to the principle of mixed medication, the organic inhibitor polymaleic acid, the carboxyethyl cellulose and the inorganic inhibitor water glass are combined according to a certain mass ratio, and the dosage of the medicament is reduced compared with that of the medicament used alone and the inhibition performance is obviously enhanced through the synergistic effect among the medicaments. The combined inhibitor can efficiently and selectively inhibit coarse and medium grade galena, has a good inhibition effect on micro-fine galena, does not basically influence the flotation of chalcopyrite, and achieves the aim of selective separation.
(2) The traditional galena inhibitor dichromate is extremely toxic and has great harm to the environment and human body. And the traditional lead inhibitors such as dichromate, sodium humate, sodium sulfite, ferrochrome lignin and the like have the inhibiting effect on galena, but have poor inhibiting effect on micro-fine lead. The combined inhibitor has wide sources, is green and environment-friendly, is easy to biodegrade, and has low medicament cost.
(3) The novel combined inhibitor is prepared by combining water-soluble micromolecule carboxylic acid HPMA, a high molecular organic substance CEC and a conventional inhibitor, is simple in preparation and easy to implement industrially, and simultaneously, the HPMA is an excellent water treatment agent and can complex heavy metal ions in mineral processing wastewater, so that the difficulty of wastewater recycling is greatly reduced.
(4) When the inhibitor is used for flotation separation of copper-lead bulk concentrates, copper concentrates with copper grade of more than 19 percent, lead grade of less than 5 percent and copper operation recovery rate of more than 90 percent can be obtained; the lead concentrate grade is more than 58 percent, the lead recovery rate is more than 95 percent, the copper-lead separation efficiency is effectively improved, and the mutual content of copper and lead in the concentrate is reduced.
Drawings
FIG. 1 Process flow diagram of example 1;
figure 2 process flow diagram of example 2.
Detailed Description
Example 1
The copper-lead bulk concentrate sample is taken from ore pulp at an overflow port of a regrind mill before copper-lead separation operation in a certain ore dressing plant of the Temple of DongSheng of inner Mongolia. The copper-lead alloy concentrate sample contained 8.56% copper and 38.67% lead. Wherein copper and lead are mainly present in the form of chalcopyrite and galena. Contains a small amount of pyrite, and a small amount of quartz, talc, mica and other gangue minerals. The granularity composition of the copper-lead bulk concentrate is shown in table 1, and as can be seen from table 1, the regrinding fineness of-0.045 mm accounts for 82.10%, obviously, the proportion of-19 mu m galena is 48.60%, and the effective inhibition of the micro-fine galena is the difficulty of copper-lead separation of the ore. The grain size composition of the copper-lead bulk concentrate is shown in table 1.
TABLE 1 copper-lead bulk concentrate granulometric composition%
Figure BDA0002565044990000051
The flotation test process flow and the chemical system in the embodiment are shown in fig. 1, and the flotation adopts a full-flow closed-circuit test, which is concretely as follows:
in this example, the lead inhibitor was a 2% by mass polymaleic acid water HPMA solution (relative molecular weight 400 to 500), a 2% water glass (modulus 2.5) SSL aqueous solution, and a 0.5% carboxyethyl cellulose CEC (molecular weight 9 ten thousand, degree of substitution 0.9) aqueous solution, which were added together at a ratio of 1.5:2: 1.
Separating and roughing copper and lead: the concentration of the ore pulp is 27 percent; 2000g/t of active carbon (for feeding), and stirring for 4 min; HPMA + SSL + CEC 3000g/t (for feeding ore), stirring for 5 min; z-200120g/t (for feeding), stirring for 2 min; 80g/t (for feeding ore) of pine oil, and stirring for 1 min; performing flotation for 5 min;
separating and selecting copper and lead: 300g/t (for feeding ore) of HPMA + SSL + CEC, stirring for 5min, and floating for 3 min;
separating and concentrating copper and lead: HPMA + SSL + CEC 100g/t (for feeding), stirring for 5min, and floating for 3 min;
separating and selecting copper and lead: adding no flotation reagent, performing blank concentration, and performing flotation for 2 min;
and (3) copper-lead separation and scavenging: z-20040g/t (for feeding), stirring for 2min, and performing flotation for 2 min;
and (2) separating copper and lead and scavenging: z-20020g/t (for feeding), stirring for 2min, and performing flotation for 1.5 min;
after the flotation process is carried out for six times, the quality and the grade of the concentrate and the tailings obtained in each test are basically unchanged, and the stabilized concentrate and tailings are sampled and analyzed. The test results are shown in 5 in FIG. 2#As shown.
Comparative example 1
The process flow is essentially the same as in example 1, except that potassium dichromate is used as the inhibitor
Roughing: 3000g/t (mineral feeding)
Selecting one: 300g/t (mineral feeding)
Selecting two: 100g/t (mineral feeding)
The flotation results are shown in table 2# 1.
Comparative example 2
The process is essentially the same as in example 1, except that polymaleic acid is used as the inhibitor
Roughing: 3000g/t (mineral feeding)
Selecting one: 300g/t (mineral feeding)
Selecting two: 100g/t (mineral feeding)
The flotation results are shown in # 2 of table 2.
Comparative example 3
The process flow is essentially the same as in example 1, except that the inhibitor is water glass
Roughing: 3000g/t (mineral feeding)
Selecting one: 300g/t (mineral feeding)
Selecting two: 100g/t (mineral feeding)
The flotation results are shown in # 3 in table 2.
Comparative example 4
The process flow is essentially the same as in example 1, except that the inhibitor is a polyethyl cellulose
Roughing: 3000g/t (mineral feeding)
Selecting one: 300g/t (mineral feeding)
Selecting two: 100g/t (mineral feeding)
The flotation results are shown in # 4 in table 2.
Table 2 test 1# Experiment 5#Results of the full-run closed-circuit test%
Figure BDA0002565044990000071
From table 2 it can be seen that the reduction of lead content in the copper concentrate of the combined inhibitor with respect to the single inhibitor is very significant, even with a reduction of 3 percentage points with respect to the lead content in the copper concentrate with respect to potassium dichromate, indicating that the combined inhibitor of the present invention has a very good lead inhibiting effect.
Example 2
The complex copper-lead-zinc-silver-tin polymetallic ore in Xinjiang comprises 0.21% of copper, 1.41% of Pb, 3.35% of zinc, 4.71% of sulfur, 127.3g/t of silver and 0.079% of tin in raw ore, wherein the main metal minerals in the ore comprise pyrite, galena, sphalerite, arsenopyrite and a small amount of chalcopyrite, pyrrhotite and cassiterite, the gangue minerals are mainly quartz, and then muscovite, chlorite, dolomite and the like. The ore is rich in silver, lead and zinc, and has high economic value. According to the scheme exploration test result, the scheme of 'copper-lead mixed flotation-copper-lead mixed concentrate separation' is determined, and the separation process flow is shown in figure 2. The grinding fineness of the raw ore is-0.074 mm and accounts for 70%, a one-coarse-two-scavenging-three-fine process flow is adopted to obtain copper-lead bulk concentrate and copper-lead mixed floating tailings, middlings are returned sequentially, after the flotation process is executed for six times, the quality and the grade of the flotation concentrate and the flotation tailings obtained in each test are basically unchanged, and the stabilized copper-lead bulk concentrate and the copper-lead mixed floating tailings are sampled and analyzed.
The test flow and the reagent system of the copper-lead mixed flotation in the embodiment are shown in figure 2, and the flotation adopts a full-flow closed-circuit test, which is concretely as follows:
copper and lead mixed flotation roughing: zinc sulfate 1000g/t, sodium sulfite 1000g/t, 25#20g/t of heiyao;
and (3) carrying out mixed flotation and scavenging on copper and lead: 25#Heiyao 4g/t
And (2) carrying out mixed flotation and scavenging on copper and lead: 25#Heiyao 4g/t
Copper-lead mixed flotation and concentration I: 400g/t of zinc sulfate and 400g/t of sodium sulfite;
and (2) copper-lead mixed flotation and concentration II: zinc sulfate is 200g/t, and the dosage of sodium sulfite is 200 g/t;
and thirdly, copper-lead mixed flotation and concentration: and (4) adding no flotation reagent, and performing blank concentration.
The foam product of the copper-lead mixed flotation concentration III is copper-lead bulk concentrate, the copper-lead separation lead combination inhibitor provided by the invention is applied to the flotation separation of the copper-lead bulk concentrate, the copper content is 5.61%, the lead content is 44.50%, and the granularity composition of the copper-lead bulk concentrate is shown in Table 3.
In this example, the lead inhibitor is added after mixing an aqueous solution of polymaleic acid (with a relative molecular weight of 400 to 500) having a mass concentration of 1.0%, an aqueous solution of water glass (modulus 2.5) having a mass concentration of 2.0%, and an aqueous solution of carboxyethyl cellulose (with a molecular weight of 9 ten thousand and a degree of substitution of 0.9) in an amount of 2:2: 1.
Regrinding the copper-lead bulk concentrate: grinding to obtain 82.52% with-0.045 mm fineness, and feeding the copper-lead mixed concentrate;
separating and roughing copper and lead: 2500g/t of active carbon (for feeding), and stirring for 5 min; HPMA + SSL + CEC3500g/t (for feeding ore), stirring for 6 min; z-200100 g/t (for raw ore), stirring for 2 min; 20g/t of pine oil (for raw ore), and stirring for 1 min; performing flotation for 3 min;
separating and selecting copper and lead: HPMA + SSL + CEC 200g/t (for feeding), stirring for 6min, and floating for 3 min;
separating and concentrating copper and lead: HPMA + SSL + CEC 150g/t (for feeding), stirring for 6min, and floating for 3 min;
separating and selecting copper and lead: adding no flotation agent, performing blank concentration, and performing flotation for 2 min.
And (3) copper-lead separation and scavenging: z-2008 g/t (for raw ore), stirring for 2min, and performing flotation for 2 min;
and (2) separating copper and lead and scavenging: z-2004 g/t (for raw ore), stirring for 2min, and floating for 2 min.
After the flotation process is carried out for six times, the quality and the grade of the concentrate and the tailings obtained in each test are basically unchanged, and the stabilized concentrate and tailings are sampled and analyzed. The test results are shown in 5 of Table 4#As shown.
Comparative example 1
The process flow is essentially the same as in example 1, except that potassium dichromate is used as the inhibitor
Roughing: 3500g/t (mineral feeding)
Selecting one: 200g/t (mineral feeding)
Selecting two: 150g/t (mineral feeding)
The flotation results are shown in table 4 as # 1.
Comparative example 2
The process is essentially the same as in example 1, except that polymaleic acid is used as the inhibitor
Roughing: 3500g/t (mineral feeding)
Selecting one: 200g/t (mineral feeding)
Selecting two: 150g/t (mineral feeding)
The flotation results are shown in # 2 in table 4.
Comparative example 3
The process flow is essentially the same as in example 1, except that the inhibitor is water glass
Roughing: 3500g/t (mineral feeding)
Selecting one: 200g/t (mineral feeding)
Selecting two: 150g/t (mineral feeding)
The flotation results are shown in # 3 in table 4.
Comparative example 4
The process flow is essentially the same as in example 1, except that the inhibitor is a polyethyl cellulose
Roughing: 3500g/t (mineral feeding)
Selecting one: 200g/t (mineral feeding)
Selecting two: 150g/t (mineral feeding)
The flotation results are shown in # 4 in table 4.
TABLE 3 composition of particle size of copper-lead bulk concentrate%
Figure BDA0002565044990000101
TABLE 4 run 1# Experiment 5#Results of the full-run closed-circuit test%
Figure BDA0002565044990000102
From table 4, it can be seen that the combined inhibitor has a very significant reduction in lead content in the copper concentrate relative to the single inhibitor, and even if the lead content in the copper concentrate relative to potassium dichromate is reduced by 3 percentage points, the taste of the copper concentrate is significantly better than that of the single inhibitor, indicating that the combined inhibitor of the present invention has a very good lead inhibition effect.

Claims (10)

1. The combined lead inhibitor for the microfine-sized galena is characterized in that active components comprise polymaleic acid, water glass and carboxyethyl cellulose, and the mass ratio of the polymaleic acid to the water glass to the carboxyethyl cellulose is (1-6) - (2-5) - (0.25-2).
2. The combined lead inhibitor for the microfine size fraction galena according to claim 1, wherein the combined inhibitor is a combination of aqueous solutions of active ingredients, wherein the mass concentration of the aqueous solution of polymaleic acid is 1 to 2%, the mass concentration of the aqueous solution of water glass is 2 to 5%, and the mass concentration of the aqueous solution of carboxyethyl cellulose is 0.25 to 0.5%; the mass ratio of the 3 kinds of aqueous solution added into the ore pulp is as follows: the polymaleic acid aqueous solution comprises (3-1) an aqueous sodium silicate solution and (3-1) an aqueous carboxyethyl cellulose solution and (4-1).
3. The combined lead inhibitor for the microfine sized galena according to claim 2, wherein the polymaleic acid HPMA is a small-molecular polycarboxylic acid having a molecular weight of 400 to 800; the molecular weight of the carboxyethyl cellulose is 8-10 ten thousand, and the substitution degree is 0.8-0.9; the modulus of the water glass is 2.5-3.0.
4. Use of the combined lead inhibitor of the microfine galena according to any one of claims 1 to 3 in flotation of lead-containing sulfide ores.
5. A method for the flotation of lead-containing sulfide ores by using the combined lead depressant for microfine galena according to claim 4, comprising the following steps:
1) crushing raw ore, performing wet ball milling to obtain ore pulp, and performing copper-lead mixed flotation on the ore pulp to obtain copper-lead mixed concentrate;
2) regrinding the copper-lead bulk concentrate obtained in the step 1) to obtain reground copper-lead bulk concentrate, and then adding activated carbon, a combined inhibitor, a collecting agent and a foaming agent into the bulk concentrate to perform flotation to obtain copper concentrate and lead concentrate.
6. The method for floating lead-containing sulfide ores by using the combined lead inhibitor for the microfine galena as claimed in claim 5, wherein in the step 1), the mixture is ball-milled until the fineness of-0.074 mm accounts for 70-80%.
7. The method for floating lead-containing sulfide ores by using the combined lead inhibitor of the micro-fine galena as claimed in claim 5, wherein in the step 2), the ores are ground again until the fineness is-0.045 mm, and the fineness is 70-95%; the flotation process comprises the steps of primary coarse cleaning, secondary cleaning and tertiary fine cleaning; collecting agent is Z-200, and foaming agent is terpineol oil.
8. The method for flotation of lead-containing sulfide ores by using the combined lead inhibitor for the microfine galena as claimed in claim 7, wherein the roughing process comprises the following steps: stirring the activated carbon at a ratio of 2000-10000 g/t for 5-10 min; adding 2000-6000 g/t of lead combination inhibitor, and stirring for 3-5 min; adding a collecting agent Z-20020-200 g/t, and stirring for 2-3 min; adding 10-100 g/t of a foaming agent, namely pine oil, and stirring for 1-2 min; and (4) carrying out flotation for 3-4 min.
9. The method for the flotation of lead-containing sulfide ores by using the combined lead inhibitor for the microfine galena as claimed in claim 7, wherein the scavenging process comprises: adding Z-2007-100 g/t for the first scavenging, stirring for 2-3 min, and floating for 1-3 min; and adding Z-2005-50 g/t for second scavenging, stirring for 2-3 min, and performing flotation for 1-2 min.
10. The method for flotation of lead-containing sulfide ores by using the combined lead depressant for micro-fine galena as claimed in claim 7, wherein the concentration process comprises: adding 100-1000 g/t of lead combination inhibitor for first selection, stirring for 3-5 min, and floating for 2-3 min; adding 50-500 g/t of lead combined inhibitor for the second selection, stirring for 3-5 min, and performing flotation for 1-2 min; and (4) flotation reagent is not added in the third concentration, and blank flotation is carried out for 0.5-1 min.
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