CN117772423B

CN117772423B - Copper-sulfur flotation separation combined inhibitor and method for copper-sulfur flotation by using same under lime-free condition

Info

Publication number: CN117772423B
Application number: CN202410211493.7A
Authority: CN
Inventors: 贺壮志; 肖巧斌; 丘世澄; 郝光兆; 王中明; 谭欣; 刘方; 刘书杰; 吴世鹏; 孙小朋; 王靖波
Original assignee: BGRIMM Technology Group Co Ltd
Current assignee: BGRIMM Technology Group Co Ltd
Priority date: 2024-02-27
Filing date: 2024-02-27
Publication date: 2024-05-31
Anticipated expiration: 2044-02-27
Also published as: CN117772423A

Abstract

The application provides a copper-sulfur flotation separation combined inhibitor and a method for carrying out copper-sulfur flotation by using the same under lime-free conditions, and relates to the technical field of mineral separation. The copper-sulfur flotation separation combined inhibitor comprises the following components: inhibitors a and B; the inhibitor A comprises sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate, and the mass ratio of the inhibitor A to the sodium humate is (2-5) to (1-3) to 1; the inhibitor B comprises sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, and the mass ratio of the inhibitor B to the sodium persulfate is 1 (1-3) (3-6) in sequence. Under the condition of no lime, the stable and strong selective inhibition effect on sulfur-containing minerals can be realized by adding the copper-sulfur flotation separation combined inhibitor in sections.

Description

Copper-sulfur flotation separation combined inhibitor and method for copper-sulfur flotation by using same under lime-free condition

Technical Field

The application relates to the technical field of mineral separation, in particular to a copper-sulfur flotation separation combined inhibitor and a method for carrying out copper-sulfur flotation by using the same under lime-free conditions.

Background

Lime is widely used as a copper-sulfur flotation separation inhibitor in the copper-sulfur flotation process, but the application of lime has the following disadvantages:

1. Lime is produced by a high-temperature calcination process, and a large amount of energy consumption and carbon emission are accompanied in the production process, so that the problems of environmental pollution and the like are caused;

2. In the mineral processing industrial production of lime, special equipment is needed to prepare lime milk, so that the cost of manpower and material resources is increased, and certain potential safety hazards are brought;

3. The lime milk is easy to scale in the use process, so that the pipeline is easy to be blocked, the equipment maintenance cost is increased, and meanwhile, the fluctuation of the lime addition amount is caused, so that the ore dressing production index is unstable;

4. The large amount of lime is used, so that flotation foam is easy to be sticky, gangue minerals are easy to be mixed in the foam to influence the grade of copper concentrate, and meanwhile, the foam is difficult to convey and filter;

5. Lime can improve the pH value and hardness of tailings and beneficiation wastewater, and environmental protection problems can be caused by directly stacking the tailings and discharging the beneficiation wastewater;

6. The subsequent floatation comprehensive recovery of sulfur-containing minerals requires adding a large amount of sulfuric acid for activation, and the sulfuric acid is used as an easy-to-poison chemical reagent, so that the potential safety hazards of storage and use of the sulfuric acid are increased.

At present, research on copper-sulfur flotation separation inhibitors under lime-free conditions is more, such as oxidizing agents including hydrogen peroxide, potassium permanganate and the like, but the sulfur inhibition effect is unstable and the applicability is poor. The oxidant is easy to be interfered by factors such as ore pulp pH, gangue minerals and the like to fail in a complex ore pulp environment, and particularly in large-scale industrial production, the production index fluctuation is large, so that industrial application cannot be realized.

Therefore, it is of great importance to find a copper-sulfur flotation separation inhibitor which is free of lime and can be applied industrially, and a use method thereof.

Disclosure of Invention

The application aims to provide a copper-sulfur flotation separation combined inhibitor and a method for carrying out copper-sulfur flotation under lime-free conditions, wherein the copper-sulfur flotation separation combined inhibitor is added in a segmented way by matching with a specific collector to respectively form a method for carrying out copper-sulfur flotation under lime-free conditions of two stages of enhanced sulfur inhibition and enhanced separation, so that stable and efficient copper-sulfur separation effects are realized, and the aims of stabilizing and optimizing indexes are fulfilled, thereby solving the problems.

In order to achieve the above purpose, the application adopts the following technical scheme:

The first aspect of the application provides a copper-sulfur flotation separation combination inhibitor comprising: inhibitors a and B;

The inhibitor A comprises sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate;

the mass ratio of the sodium hydroxide to the calcium hypochlorite to the calcium chloride to the sodium humate in the inhibitor A is (2-5): (2-5): (1-3): 1;

the inhibitor B comprises sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate;

The mass ratio of the sodium hydroxide to the ammonium hydroxide to the sodium metabisulfite to the sodium persulfate in the inhibitor B is 1 (1-3): 3-6.

Optionally, the mass ratio of the sodium hydroxide, the calcium hypochlorite, the calcium chloride and the sodium humate in the inhibitor A is (2.5-4): 1-2): 1;

The mass ratio of the sodium hydroxide to the ammonium hydroxide to the sodium metabisulfite to the sodium persulfate in the inhibitor B is 1 (1-2): (3.5-5): (3.5-5).

The second aspect of the application provides a method for copper-sulfur flotation by using the copper-sulfur flotation separation combination inhibitor under lime-free condition, which comprises the following steps:

adding the inhibitor A, the collector A and the foaming agent into ore pulp of the copper-sulfur raw ore, and carrying out copper-sulfur roughing to obtain copper-sulfur roughing concentrate and copper-sulfur roughing tailings;

Adding the inhibitor A into the copper-sulfur roughing concentrate, and carrying out copper-sulfur mixing and concentrating to obtain copper-sulfur bulk concentrate;

Adding active carbon, the inhibitor B, the collector B and the foaming agent into copper-sulfur bulk concentrate, and carrying out copper-sulfur separation roughing to obtain copper roughing concentrate and roughing sulfur-containing products;

Adding the inhibitor B into the copper roughing concentrate, and carrying out copper concentration to obtain copper concentrate;

the collector A comprises one or more of butyl xanthate, amyl xanthate, sodium butyrate and ammonium butyrate;

The collector B comprises one or more of ethionine, ethionamide, no. 25 black drug, nigrosine and ethionamide.

Optionally, the lime-free condition is a method for copper-sulfur flotation using the copper-sulfur flotation separation combination inhibitor, at least one of the following conditions being satisfied:

A. The dosage of the inhibitor A in the copper-sulfur coarse selection is 100-1000g/t of raw ore;

B. The dosage of the inhibitor A in the copper-sulfur mixing and refining is 10-100g/t of raw ore;

C. the dosage of the inhibitor B in the copper-sulfur separation coarse process is 50-500g/t of raw ore;

D. the dosage of the inhibitor B in the copper refining is 5-25g/t of raw ore;

E. The consumption of the collector A is 40-100g/t of raw ore;

F. the dosage of the activated carbon is 50-200g/t of raw ore;

G. the dosage of the collector B is 5-50g/t of raw ore.

1) Grinding and pulping the copper-sulfur raw ore to obtain ore pulp, wherein the grinding fineness is-0.074 mm and accounts for 50-85%, and the mass concentration of the ore pulp is 30-45%;

2) The foaming agent comprises one or more of pinitol oil, 2-methyl-1-propanol and 4-methyl-2-pentanol.

a. The consumption of the foaming agent in the copper-sulfur roughing is 5-50g/t of raw ore;

b. the consumption of the foaming agent in the copper-sulfur separation coarse selection is 2-20g/t of raw ore.

i. the number of roughing copper and sulfur is 1 or more;

adding the collector A into the copper-sulfur roughing tailings to perform copper-sulfur mixed scavenging, wherein the times of copper-sulfur mixed scavenging are multiple times;

the number of times of mixing and carefully selecting the copper and the sulfur is multiple times;

iv, separating and roughing copper and sulfur for 1 or more times;

v, adding the collecting agent B into the roughing sulfur-containing product to perform copper separation scavenging, wherein the times of copper separation scavenging are multiple times;

the number of copper beneficiations is multiple.

⑴ The copper-sulfur mixed scavenging comprises first copper-sulfur mixed scavenging and second copper-sulfur mixed scavenging, wherein the consumption of the collector A in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging is respectively and independently 5-20g/t of raw ore;

⑵ The copper separation scavenging comprises first copper separation scavenging and second copper separation scavenging, and the consumption of the collector B in the first copper separation scavenging and the second copper separation scavenging is respectively and independently 3-15g/t of raw ore.

Optionally, the copper-sulfur mixed beneficiation comprises a first copper-sulfur mixed beneficiation and a second copper-sulfur mixed beneficiation;

the dosage of the inhibitor A in the first copper-sulfur mixing and refining is 10-50g/t of raw ore;

the dosage of the inhibitor A in the second copper-sulfur mixing and refining is 5-30g/t of raw ore.

Optionally, the copper beneficiation comprises a first copper beneficiation, a second copper beneficiation, and a third copper beneficiation;

The dosage of the inhibitor B in the first copper refining is 3-20g/t of raw ore;

The dosage of the inhibitor B in the second copper refining is 2-15g/t of raw ore;

The dosage of the inhibitor B in the third copper concentrate is 1-10g/t of raw ore.

Compared with the prior art, the application has the beneficial effects that:

the combined inhibitor for copper-sulfur flotation separation provided by the application can realize stable and strong selective inhibition effect on sulfur-containing minerals through sectional addition.

According to the method for carrying out copper-sulfur flotation under lime-free conditions by using the copper-sulfur flotation separation combination inhibitor, the copper-sulfur flotation separation combination inhibitor is added in a sectional manner by matching with a specific collector, the effects of strengthening sulfur inhibition and strengthening separation are realized in different flotation stages, and the stable and efficient separation of copper and sulfur is ensured; meanwhile, the method avoids the large-scale use of the traditional lime inhibitor, solves the related problems of production, safety, environmental protection and the like brought by the traditional lime inhibitor, and has good economic and environmental protection benefits and application prospects.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.

FIG. 1 is a flow chart of a method for copper-sulfur flotation under lime-free conditions using the copper-sulfur flotation separation combination inhibitor;

Fig. 2 is a flow chart of a method for copper sulfur flotation using inhibitor lime in comparative example 20.

Detailed Description

The term as used herein:

"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.

When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.

In these examples, the parts and percentages are by mass unless otherwise indicated.

"Parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g, 2.689g, or the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. or the mass of the A component is aK, the mass of the B component is bK (K is any number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.

"And/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).

Currently, the lime-free inhibitor in the prior art is respectively a pH regulator, an organic inhibitor and an oxidant, wherein the pH regulator is such as sodium hydroxide, and has high cost and poor effect; organic inhibitors such as sodium humate, which have poor selectivity and are liable to inhibit copper; oxidizing agents such as calcium hypochlorite, sodium metabisulfite, sodium persulfate, and the like, which are prone to failure in complex pulp, affect the effectiveness. Although some of these lime-free inhibitors replace lime, they have drawbacks that result in poor applicability.

Accordingly, an embodiment of the present application provides a copper sulfur flotation separation combination inhibitor comprising: inhibitors a and B;

Optionally, the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride, and sodium humate in inhibitor a may be 2:2:3:1, 3:2:3:1, 4:2:3:1, 5:2:3:1, 2:3:3:1, 2:4:3:1, 2:5:3:1, 2:2:1:1, 2:2:2:1, or (2-5): (2-5): any value between (1-3): 1;

Optionally, the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite, and sodium persulfate in inhibitor B may be any value between 1:1:3:3, 1:1:4:3, 1:1:5:3, 1:1:6:3, 1:1:3:6, 1:3:6, 1:1:5:5, 1:3:4:5, 1:2:3:6, or 1 (1-3): 3-6.

In some alternative embodiments, the mass ratio of the sodium hydroxide, the calcium hypochlorite, the calcium chloride, and the sodium humate in the inhibitor A is (2.5-4): 1-2): 1;

Optionally, the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride, and sodium humate in inhibitor a may be 2.5:2.5:1:1, 2.5:3.5:1:1, 3.5:2.5:1:1, 4:2.5:2:1, 2.5:4:1:1, 2.5:2.5:2:1, 2.5:3:1:1, or any value between (2.5-4): (2.5-4): (1-2): 1;

Optionally, the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite, and sodium persulfate in inhibitor B may be any value between 1:1:3.5:3.5, 1:1:3.5:4, 1:1:4:3.5, 1:1:3.5:5, 1:1:5:3.5:3.5, 1:2:3.5:3.5, or1 (1-2): 3.5-5.

In some alternative embodiments, the mass ratio of the sodium hydroxide, the calcium hypochlorite, the calcium chloride, and the sodium humate in the inhibitor a is 3:3:1:1; the mass ratio of the sodium hydroxide to the ammonium hydroxide to the sodium metabisulfite to the sodium persulfate in the inhibitor B is 1:1:4:4.

The copper-sulfur flotation separation combined inhibitor provided by the application does not need to be added with lime, the sodium hydroxide in the inhibitor A provides OH ^-, the calcium hypochlorite is used as an oxidant to provide Ca ²⁺, and the calcium chloride is used for supplementing Ca ²⁺, so that the surfaces of pyrite, pyrrhotite and other sulfur-containing minerals can be oxidized in weak alkaline ore pulp to generate hydrophilic matters Fe (OH) ₂ and Fe (OH) ₃ or insoluble matters Ca (OH) ₂ and CaSO ₄, and the collector A is prevented from being adsorbed on the mineral surfaces, so that the inhibition effect is achieved; sodium humate in the inhibitor A is used as an organic matter, can be selectively adsorbed on the surface of sulfur-containing minerals, prevents the collector from being adsorbed on the surface of the sulfur-containing minerals, and has a strong sulfur inhibition effect. The inhibitor A adopts the combination of the pH regulator, the inorganic inhibitor and the organic inhibitor, and can form a strong inhibition effect on sulfur-containing minerals such as pyrite, pyrrhotite and the like under the interference of gangue minerals.

The sodium hydroxide and the ammonium hydroxide in the inhibitor B can dissolve acid-base buffer pair NH ₃-NH⁺ generated in ore pulp, can maintain the pH value of the ore pulp for a long time under the condition of no interference of gangue minerals, and maintain the hydroxylation degree of the surfaces of sulfur-containing minerals such as pyrite, pyrrhotite and the like, so that the surfaces of the sulfur-containing minerals reach a hydrophilic effect; sodium metabisulfite and sodium persulfate have stable oxidation effect on sulfur-containing minerals under weak alkaline environment to achieve inhibition effect. The inhibitor B adopts a pH regulator, an acid-base buffer and an inorganic inhibitor, and has stable and selective inhibition effect on sulfur-containing minerals such as pyrite, pyrrhotite and the like under the condition of no interference of gangue minerals. The inhibitor A and the inhibitor B are matched for use and added in sections, so that a stable and strong selective inhibition effect on sulfur-containing minerals such as pyrite, pyrrhotite and the like is formed, and the problems related to production, safety, environmental protection and the like caused by the traditional lime inhibitor are solved.

At present, no lime inhibitor in the prior art generally adopts a mineral separation process of the lime inhibitor, so that the applicability is poor.

Accordingly, in a second aspect, the present application provides a method for copper-sulfur flotation using the combined inhibitor for copper-sulfur flotation separation under lime-free conditions, comprising the steps of:

In the application, the inhibitor A and the collector A are matched to form a floatation effect for strengthening sulfur inhibition in the presence of gangue minerals, so that the recovery rate of copper is ensured while partial sulfur-containing minerals are inhibited; after the interference of gangue minerals and part of sulfur-containing minerals is eliminated, the floatation effect of strengthening copper-sulfur separation is formed by the cooperation of the inhibitor B and the collector B, and the grade of copper concentrate is ensured. The combined inhibitor achieves the stable and efficient copper-sulfur flotation separation effect under the synergistic effect of strengthening sulfur inhibition and strengthening separation.

In some alternative embodiments, the lime-free condition is a method of copper sulfur flotation using the copper sulfur flotation separation combination inhibitor that satisfies at least one of the following conditions:

Optionally, the dosage of the inhibitor A in the copper-sulfur roughing can be 100g/t of raw ore, 150g/t of raw ore, 200g/t of raw ore, 300g/t of raw ore, 400g/t of raw ore, 500g/t of raw ore, 600g/t of raw ore, 700g/t of raw ore, 800g/t of raw ore, 900g/t of raw ore, 1000g/t of raw ore or any value between 100 and 1000g/t of raw ore;

Optionally, the dosage of the inhibitor A in the copper-sulfur mixed refining can be 10g/t of raw ore, 20g/t of raw ore, 25g/t of raw ore, 30g/t of raw ore, 40g/t of raw ore, 50g/t of raw ore, 60g/t of raw ore, 70g/t of raw ore, 80g/t of raw ore, 90g/t of raw ore, 100g/t of raw ore or any value between 10 and 100g/t of raw ore;

Optionally, the dosage of the inhibitor B in the copper-sulfur separation coarse selection can be 50g/t of raw ore, 60g/t of raw ore, 70g/t of raw ore, 80g/t of raw ore, 90g/t of raw ore, 100g/t of raw ore, 150g/t of raw ore, 200g/t of raw ore, 300g/t of raw ore, 400g/t of raw ore, 500g/t of raw ore or any value between 50 and 500g/t of raw ore;

D. the dosage of the inhibitor B in the copper refining is 5-25g/t of raw ore;

Alternatively, the inhibitor B may be used in the copper beneficiation in an amount of 5g/t of raw ore, 6g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 20g/t of raw ore, 25g/t of raw ore, or any value between 5 and 25g/t of raw ore;

E. The consumption of the collector A is 40-100g/t of raw ore;

Alternatively, the collector A may be used in an amount of 40g/t of raw ore, 50g/t of raw ore, 60g/t of raw ore, 70g/t of raw ore, 80g/t of raw ore, 90g/t of raw ore, 100g/t of raw ore, or any value between 40 and 100g/t of raw ore;

F. the dosage of the activated carbon is 50-200g/t of raw ore;

alternatively, the amount of activated carbon may be 50g/t of raw ore, 60g/t of raw ore, 70g/t of raw ore, 80g/t of raw ore, 90g/t of raw ore, 100g/t of raw ore, 150g/t of raw ore, 200g/t of raw ore, or any value between 50 and 200g/t of raw ore;

The method is characterized in that activated carbon is added in the copper-sulfur separation coarse selection, so that interference of the inhibitor A and the inhibitor A on subsequent flotation operation can be eliminated, and conditions are created for enhanced separation flotation;

G. the dosage of the collector B is 5-50g/t of raw ore.

Alternatively, the collector B may be used in an amount of 5g/t of raw ore, 6g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 20g/t of raw ore, 25g/t of raw ore, 40g/t of raw ore, 50g/t of raw ore, or any value between 5 and 50g/t of raw ore.

The collector B belongs to a short-chain collector and has good copper selectivity.

Optionally, the fineness of grinding may be any value between 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 50-85% of-0.074 mm, and the mass concentration of pulp may be any value between 30%, 31%, 32%, 35%, 38%, 40%, 42%, 45% or 30-45%;

it should be noted that, because the copper-sulfur raw ore presents large blocks or particles, which is unfavorable for the subsequent flotation process, the copper-sulfur raw ore needs to be ground;

a. the consumption of the foaming agent in the copper-sulfur coarse selection is 5-50g/t of raw ore;

Optionally, the consumption of the foaming agent in the copper-sulfur coarse selection can be any value between 5g/t of raw ore, 6g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 20g/t of raw ore, 25g/t of raw ore, 40g/t of raw ore, 50g/t of raw ore or 5-50g/t of raw ore;

Alternatively, the amount of the foaming agent selected from the copper-sulfur separation coarse may be 2g/t of raw ore, 3g/t of raw ore, 5g/t of raw ore, 6g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 20g/t of raw ore or any value between 2 and 20g/t of raw ore.

i. the number of roughing copper and sulfur is 1 or more;

alternatively, the number of roughings of copper and sulfur may be 1,2, 3, 4,5, 6, 7, 8, 9, 10, 20, 30, 40 or any integer value equal to or greater than 1;

the copper-sulfur roughing concentrate obtained after copper-sulfur roughing is a foam product;

Optionally, the number of times of the copper-sulfur mixed scavenging can be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 20 times, 30 times, 40 times or any integer value greater than or equal to 2;

the copper-sulfur mixed scavenging method is characterized in that copper-sulfur roughing tailings are subjected to copper-sulfur mixed scavenging for a plurality of times, so that lead floatation time is enough, copper recovery rate is ensured, and copper-sulfur mixed scavenging middlings obtained through the plurality of times of copper-sulfur mixed scavenging can be sequentially returned to the previous operation for grading;

Alternatively, the number of copper-sulfur mixing beneficiation can be 2,3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or any integer value greater than or equal to 2;

iv, separating and roughing copper and sulfur for 1 or more times;

Alternatively, the number of copper sulfur separation roughings may be 1,2,3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40 or any integer value equal to or greater than 1;

alternatively, the number of copper separation sweeps may be 2,3, 4, 5,6, 7, 8, 9, 10, 20, 30, 40, or any integer value equal to or greater than 2;

the number of copper beneficiations is multiple.

Alternatively, the number of copper beneficiations can be 2,3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or any integer value greater than or equal to 2.

optionally, the usage amount of the collector A in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging can be any value between 5g/t raw ore, 6g/t raw ore, 7g/t raw ore, 8g/t raw ore, 9g/t raw ore, 10g/t raw ore, 15g/t raw ore, 20g/t raw ore or 5-20g/t raw ore respectively and independently;

Alternatively, the amount of the collector B used in the first copper separation sweep and the second copper separation sweep may be 3g/t of raw ore, 4g/t of raw ore, 5g/t of raw ore, 6g/t of raw ore, 7g/t of raw ore, 8g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 15g/t of raw ore, or any value between 3 and 15g/t of raw ore, respectively.

The roughing sulfur-containing product is subjected to copper separation and scavenging for a plurality of times, so that the copper flotation time is enough, and the copper content in the sulfur-containing product is reduced.

In some alternative embodiments, the copper-sulfur mixed beneficiation comprises a first copper-sulfur mixed beneficiation and a second copper-sulfur mixed beneficiation;

optionally, the amount of the inhibitor A in the first copper-sulfur mixed refining can be 10g/t of raw ore, 20g/t of raw ore, 25g/t of raw ore, 40g/t of raw ore, 50g/t of raw ore or any value between 10 and 50g/t of raw ore;

Alternatively, the inhibitor A in the second copper-sulfur mixed refining may be used in an amount of 5g/t of raw ore, 6g/t of raw ore, 7g/t of raw ore, 8g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 20g/t of raw ore, 25g/t of raw ore, 30g/t of raw ore, or any value between 5 and 30g/t of raw ore.

In some alternative embodiments, the copper beneficiation comprises a first copper beneficiation, a second copper beneficiation, and a third copper beneficiation;

Alternatively, the inhibitor B may be used in the first copper concentrate in an amount of 3g/t of raw ore, 4g/t of raw ore, 5g/t of raw ore, 6g/t of raw ore, 7g/t of raw ore, 8g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 15g/t of raw ore, 20g/t of raw ore, or any value between 3 and 20g/t of raw ore;

alternatively, the inhibitor B may be used in the second copper concentrate in an amount of 2g/t of raw ore, 4g/t of raw ore, 5g/t of raw ore, 6g/t of raw ore, 7g/t of raw ore, 8g/t of raw ore, 9g/t of raw ore, 10g/t of raw ore, 15g/t of raw ore, or any value between 2 and 15g/t of raw ore;

Alternatively, the inhibitor B may be used in the third copper concentrate in an amount of 1g/t of ore concentrate, 2g/t of ore concentrate, 4g/t of ore concentrate, 5g/t of ore concentrate, 6g/t of ore concentrate, 7g/t of ore concentrate, 8g/t of ore concentrate, 9g/t of ore concentrate, 10g/t of ore concentrate, or any value between 1 and 10g/t of ore concentrate.

It should be noted that, the general idea of the method for performing copper-sulfur flotation under lime-free conditions by using the copper-sulfur flotation separation combination inhibitor provided by the application can be summarized as follows: grinding and pulping copper-sulfur raw ores to obtain ore pulp, and floating the ore pulp, wherein the floating is divided into an enhanced sulfur suppression stage and an enhanced separation stage.

The step of strengthening the sulfur suppression stage comprises the following steps: adding an inhibitor A, a collector A and a foaming agent into ore pulp, performing roughing to obtain copper-sulfur roughing concentrate and copper-sulfur roughing tailings, adding the inhibitor A into the copper-sulfur roughing concentrate to perform concentration I and concentration II to obtain copper-sulfur mixed concentrate, adding the collector A into the copper-sulfur roughing tailings to perform scavenging I and scavenging II to obtain copper-sulfur mixed scavenging middlings and tailings, and sequentially returning the copper-sulfur mixed scavenging middlings to the previous operation for grading.

The step of the enhanced separation stage comprises: adding active carbon, an inhibitor B, a collector B and a foaming agent into copper-sulfur bulk concentrate for separation roughing to obtain copper roughing concentrate and roughing sulfur-containing products, adding the inhibitor B into the copper roughing concentrate for separation refining I, separation refining II and separation refining III to obtain copper concentrate, adding the collector B into the roughing sulfur-containing products for separation refining I and separation refining II to obtain copper separation refining and sulfur-containing products, and sequentially returning the copper separation refining to the previous operation for refining.

A specific flow chart is shown in fig. 1.

The inhibitor A provided by the application has the main effects of inhibiting part of sulfur which is difficult to inhibit, creating a proper pulp environment for the inhibitor B, exerting strong inhibition force in the reinforced inhibition stage and strong selectivity in the reinforced separation stage, effectively inhibiting sulfur after passing through the two stages, and having stable effect.

Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. 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.

Example 1

This embodiment provides a copper sulfur flotation separation combination inhibitor comprising: inhibitors a and B;

The inhibitor A comprises the following raw materials: sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate, inhibitor B comprises the following raw materials: sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, and does not contain lime;

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 2:2:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:5:5.

The embodiment also provides a method for copper-sulfur flotation by using a combined inhibitor for copper-sulfur flotation separation under lime-free conditions, which comprises the following steps:

Grinding and pulping copper-sulfur raw ores to obtain ore pulp, wherein the grinding fineness is 60% of-0.074 mm, the mass concentration of the ore pulp is 35%, the copper content in the copper-sulfur raw ores is 0.51%, and the sulfur content is 7.84%;

Adding the inhibitor A, the collector A butyl xanthate and the foaming agent pinitol oil into ore pulp, and carrying out copper-sulfur roughing to obtain copper-sulfur roughing tailings and copper-sulfur roughing concentrate, wherein the dosage of the inhibitor A is 600g/t of raw ore, the dosage of the collector A butyl xanthate is 50g/t of raw ore, and the dosage of the foaming agent pinitol oil is 25g/t of raw ore;

Adding a collector A butyl xanthate into the copper-sulfur roughing tailings to perform first copper-sulfur mixed scavenging and second copper-sulfur mixed scavenging to obtain copper-sulfur mixed scavenging middlings, and sequentially returning the copper-sulfur mixed scavenging middlings to the previous operation for separating, wherein the dosage of the collector A butyl xanthate in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging is 10g/t of raw ore;

adding an inhibitor A into the copper-sulfur roughing concentrate to perform first copper-sulfur mixed concentration and second copper-sulfur mixed concentration respectively to obtain copper-sulfur mixed concentrate, wherein the dosage of the inhibitor A in the first copper-sulfur mixed concentration is 30g/t of raw ore, and the dosage of the inhibitor A in the second copper-sulfur mixed concentration is 20g/t of raw ore;

Adding active carbon, the inhibitor B, a collector B xanthate and foaming agent pinitol oil into the copper-sulfur mixed concentrate, and carrying out copper-sulfur separation roughing to obtain roughing sulfur-containing products and copper roughing concentrate, wherein the dosage of the active carbon is 100g/t of raw ore, the dosage of the inhibitor B is 200g/t of raw ore, the dosage of the collector B xanthate is 30g/t of raw ore, and the dosage of the foaming agent pinitol oil is 15g/t of raw ore;

Adding a collector B xanthate into the roughing sulfur-containing product to perform first copper separation scavenging and second copper separation scavenging respectively to obtain copper separation scavenging ore, and sequentially returning the copper separation scavenging ore to the previous operation for grading, wherein the dosage of the collector B xanthate in the first copper separation scavenging and the second copper separation scavenging is 5g/t of raw ore;

adding inhibitor B into the copper roughing concentrate to perform first copper concentration, second copper concentration and third copper concentration respectively to obtain copper concentrate, wherein the dosage of the inhibitor B in the first copper concentration is 15g/t of raw ore, the dosage of the inhibitor B in the second copper concentration is 7g/t of raw ore, and the dosage of the inhibitor B in the third copper concentration is 5g/t of raw ore.

Example 2

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 4:4:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:3:3.

This example also provides a method for copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation under lime-free conditions, differing from example 1 in that: the inhibitor a of example 1 was replaced with the inhibitor a of this example, and the inhibitor B of example 1 was replaced with the inhibitor B of this example.

Example 3

wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 4:4:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:4:4.

Example 4

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:3:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:5:5.

Example 5

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 5:5:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:5:5.

Grinding and pulping copper-sulfur raw ores to obtain ore pulp, wherein the grinding fineness is 75% of-0.074 mm, the mass concentration of the ore pulp is 33%, the copper content in the copper-sulfur raw ores is 0.37%, and the sulfur content is 6.51%;

Adding the inhibitor A, the collector A amyl xanthate and the foaming agent 2-methyl-1-propanol into ore pulp, and carrying out copper-sulfur roughing to obtain copper-sulfur roughing tailings and copper-sulfur roughing concentrate, wherein the dosage of the inhibitor A is 800g/t of raw ore, the dosage of the collector A amyl xanthate is 40g/t of raw ore, and the dosage of the foaming agent 2-methyl-1-propanol is 20g/t of raw ore;

Adding a collector A amyl xanthate into the copper-sulfur roughing tailings to perform first copper-sulfur mixed scavenging and second copper-sulfur mixed scavenging to obtain copper-sulfur mixed scavenging middlings, and sequentially returning the copper-sulfur mixed scavenging middlings to the previous operation for separating, wherein the dosage of the collector A amyl xanthate in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging is respectively 10g/t raw ore and 5g/t raw ore;

Adding an inhibitor A into the copper-sulfur roughing concentrate to perform first copper-sulfur mixed concentration, second copper-sulfur mixed concentration and third copper-sulfur mixed concentration respectively to obtain copper-sulfur mixed concentrate, wherein the dosage of the inhibitor A in the first copper-sulfur mixed concentration is 40g/t of raw ore, the dosage of the inhibitor A in the second copper-sulfur mixed concentration is 20g/t of raw ore, and the dosage of the inhibitor A in the third copper-sulfur mixed concentration is 10g/t of raw ore;

Adding active carbon, the inhibitor B, collector B ethyl thiourethane and foamer 2-methyl-1-propanol into the copper-sulfur mixed concentrate, and carrying out copper-sulfur separation roughing to obtain roughing sulfur-containing products and copper roughing concentrate, wherein the dosage of the active carbon is 80g/t of raw ore, the dosage of the inhibitor B is 150g/t of raw ore, the dosage of the collector B ethyl thiourethane is 25g/t of raw ore, and the dosage of the foamer 2-methyl-1-propanol is 10g/t of raw ore;

Adding collector B ethyl thiourethane into the roughing sulfur-containing product to perform first copper separation scavenging and second copper separation scavenging respectively to obtain copper separation scavenging ore, and sequentially returning the copper separation scavenging ore to the previous operation for separation, wherein the dosage of the collector B ethyl thiourethane in the first copper separation scavenging and the second copper separation scavenging is 6g/t raw ore and 4g/t raw ore respectively;

Adding inhibitor B into the copper roughing concentrate to perform first copper concentration, second copper concentration and third copper concentration respectively to obtain copper concentrate, wherein the dosage of the inhibitor B in the first copper concentration is 10g/t of raw ore, the dosage of the inhibitor B in the second copper concentration is 8g/t of raw ore, and the dosage of the inhibitor B in the third copper concentration is 6g/t of raw ore.

Example 6

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:5:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:4:6.

Grinding and pulping copper-sulfur raw ores to obtain ore pulp, wherein the grinding fineness is 65% of-0.074 mm, the mass concentration of the ore pulp is 37%, the copper content in the copper-sulfur raw ores is 0.73%, and the sulfur content is 10.68%;

Adding the inhibitor A, the collector A sodium butyrate black drug and the foaming agent 4-methyl-2-amyl alcohol into ore pulp, and carrying out copper-sulfur roughing to obtain copper-sulfur roughing tailings and copper-sulfur roughing concentrate, wherein the dosage of the inhibitor A is 1000g/t of raw ore, the dosage of the collector A sodium butyrate black drug is 80g/t of raw ore, and the dosage of the foaming agent 4-methyl-2-amyl alcohol is 40g/t of raw ore;

Adding a collector sodium A black drug into the copper-sulfur roughing tailings to perform first copper-sulfur mixed scavenging and second copper-sulfur mixed scavenging to obtain copper-sulfur mixed scavenging middlings, and sequentially returning the copper-sulfur mixed scavenging middlings to the previous operation for separating, wherein the dosage of the collector sodium A black drug in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging is 20g/t raw ore and 15g/t raw ore respectively;

Adding active carbon, the inhibitor B, a collecting agent B25# black drug and a foaming agent 4-methyl-2-amyl alcohol into copper-sulfur mixed concentrate, and carrying out copper-sulfur separation roughing to obtain a roughing sulfur-containing product and a copper roughing concentrate, wherein the dosage of the active carbon is 150g/t of raw ore, the dosage of the inhibitor B is 300g/t of raw ore, the dosage of the collecting agent B25# black drug is 40g/t of raw ore, and the dosage of the foaming agent 4-methyl-2-amyl alcohol is 10g/t of raw ore;

Adding a collecting agent B25# black drug into the roughing sulfur-containing product to perform first copper separation scavenging and second copper separation scavenging respectively to obtain copper separation scavenging ore, and sequentially returning the copper separation scavenging ore to the previous operation for grading, wherein the using amount of the collecting agent B25# black drug in the first copper separation scavenging and the second copper separation scavenging is 7g/t of raw ore and 5g/t of raw ore respectively;

Adding inhibitor B into the copper roughing concentrate to perform first copper concentration, second copper concentration and third copper concentration respectively to obtain copper concentrate, wherein the dosage of the inhibitor B in the first copper concentration is 10g/t of raw ore, the dosage of the inhibitor B in the second copper concentration is 10g/t of raw ore, and the dosage of the inhibitor B in the third copper concentration is 5g/t of raw ore.

Example 7

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 5:2:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:5:4.

Grinding and pulping copper-sulfur raw ores to obtain ore pulp, wherein the grinding fineness is 70% of-0.074 mm, the mass concentration of the ore pulp is 40%, the copper content in the copper-sulfur raw ores is 0.65%, and the sulfur content is 5.44%;

Adding the inhibitor A, the collector A, the ammonium butyrate black drug and the foaming agent 4-methyl-2-amyl alcohol into ore pulp, and carrying out copper-sulfur roughing to obtain copper-sulfur roughing tailings and copper-sulfur roughing concentrate, wherein the dosage of the inhibitor A is 500g/t of raw ore, the dosage of the collector A, the ammonium butyrate black drug is 60g/t of raw ore, and the dosage of the foaming agent 4-methyl-2-amyl alcohol is 20g/t of raw ore;

Adding a collector A ammonium black drug into the copper-sulfur roughing tailings to perform first copper-sulfur mixed scavenging and second copper-sulfur mixed scavenging to obtain copper-sulfur mixed scavenging middlings, and sequentially returning the copper-sulfur mixed scavenging middlings to the previous operation for separating, wherein the dosage of the collector A ammonium black drug in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging is 15g/t raw ore and 7g/t raw ore respectively;

Adding an inhibitor A into the copper-sulfur roughing concentrate to perform first copper-sulfur mixed concentration and second copper-sulfur mixed concentration respectively to obtain copper-sulfur mixed concentrate, wherein the dosage of the inhibitor A in the first copper-sulfur mixed concentration is 20g/t of raw ore, and the dosage of the inhibitor A in the second copper-sulfur mixed concentration is 10g/t of raw ore;

Adding active carbon, the inhibitor B, a collector nigrosine and a foaming agent 4-methyl-2-amyl alcohol into the copper-sulfur mixed concentrate, and carrying out copper-sulfur separation roughing to obtain a roughing sulfur-containing product and a copper roughing concentrate, wherein the dosage of the active carbon is 90g/t of raw ore, the dosage of the inhibitor B is 400g/t of raw ore, the dosage of the collector nigrosine is 50g/t of raw ore, and the dosage of the foaming agent 4-methyl-2-amyl alcohol is 20g/t of raw ore;

Adding a collector B nigrosine medicine into the roughing sulfur-containing product to perform first copper separation scavenging and second copper separation scavenging respectively to obtain copper separation scavenging ore, and sequentially returning the copper separation scavenging ore to the previous operation for separation, wherein the dosage of the collector B nigrosine medicine in the first copper separation scavenging and the second copper separation scavenging is 15g/t of raw ore and 10g/t of raw ore respectively;

Adding inhibitor B into the copper roughing concentrate to perform first copper concentration, second copper concentration and third copper concentration respectively to obtain copper concentrate, wherein the dosage of the inhibitor B in the first copper concentration is 12g/t of raw ore, the dosage of the inhibitor B in the second copper concentration is 6g/t of raw ore, and the dosage of the inhibitor B in the third copper concentration is 3g/t of raw ore.

Example 8

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 2.5:4.5:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:4.5:3.5.

grinding and pulping copper-sulfur raw ores to obtain ore pulp, wherein the grinding fineness is 55% of-0.074 mm, the mass concentration of the ore pulp is 42%, the copper content in the copper-sulfur raw ores is 1.03%, and the sulfur content is 4.86%;

adding the inhibitor A, the collector A butyl xanthate and the foaming agent 4-methyl-2-amyl alcohol into ore pulp, and carrying out copper-sulfur roughing to obtain copper-sulfur roughing tailings and copper-sulfur roughing concentrate, wherein the dosage of the inhibitor A is 300g/t of raw ore, the dosage of the collector A butyl xanthate is 80g/t of raw ore, and the dosage of the foaming agent 4-methyl-2-amyl alcohol is 30g/t of raw ore;

Adding a collector A ammonium black drug into the copper-sulfur roughing tailings to perform first copper-sulfur mixed scavenging and second copper-sulfur mixed scavenging to obtain copper-sulfur mixed scavenging middlings, and sequentially returning the copper-sulfur mixed scavenging middlings to the previous operation for separating, wherein the dosage of the collector A ammonium black drug in the first copper-sulfur mixed scavenging and the second copper-sulfur mixed scavenging is 20g/t raw ore and 15g/t raw ore respectively;

Adding active carbon, the inhibitor B, the collector ethionine and the foaming agent pinitol oil into the copper-sulfur mixed concentrate, and carrying out copper-sulfur separation roughing to obtain a roughing sulfur-containing product and a copper roughing concentrate, wherein the dosage of the active carbon is 200g/t of raw ore, the dosage of the inhibitor B is 100g/t of raw ore, the dosage of the collector ethionine is 40g/t of raw ore, and the dosage of the foaming agent pinitol oil is 15g/t of raw ore;

adding collector B ethion into the roughing sulfur-containing product to perform first copper separation scavenging and second copper separation scavenging respectively to obtain copper separation scavenging ore, and sequentially returning the copper separation scavenging ore to the previous operation for grading, wherein the dosage of the collector B ethion in the first copper separation scavenging and the second copper separation scavenging is 15g/t raw ore and 5g/t raw ore respectively;

Adding inhibitor B into the copper roughing concentrate to perform first copper concentration, second copper concentration and third copper concentration respectively to obtain copper concentrate, wherein the dosage of the inhibitor B in the first copper concentration is 8g/t of raw ore, the dosage of the inhibitor B in the second copper concentration is 4g/t of raw ore, and the dosage of the inhibitor B in the third copper concentration is 2g/t of raw ore.

Example 9

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:3:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:4:4.

Example 10

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:4:2:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:2:4:3.

Example 11

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:3:3:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:3:3:3.

Comparative example 1

This comparative example provides a copper sulfur flotation separation combination inhibitor comprising: inhibitors a and B;

the inhibitor A comprises the following raw materials: sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, inhibitor B comprises the following raw materials: sodium hydroxide, calcium hypochlorite, calcium chloride, and sodium humate, and does not contain lime;

the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor A is 3:3:1:1, and the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor B is 1:1:4:4.

This comparative example also provides a method for copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation under lime-free conditions, differing from example 1 in that: the inhibitor a of example 1 was replaced with the inhibitor a of this comparative example, and the inhibitor B of example 1 was replaced with the inhibitor B of this comparative example.

Comparative example 2

Wherein the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor A is 1:1:4:4, and the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor B is 3:3:1:1.

Comparative example 3

The inhibitor A comprises the following raw materials: sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate, inhibitor B comprises the following raw materials: sodium hydroxide, calcium hypochlorite, calcium chloride, and sodium humate, and does not contain lime;

wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:3:1:1, and the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor B is 3:3:1:1.

Comparative example 4

The inhibitor A comprises the following raw materials: sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, inhibitor B comprises the following raw materials: sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, and does not contain lime;

wherein the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor A is 1:1:4:4, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:4:4.

Comparative example 5

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 6:6:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:7:7.

Comparative example 6

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 6:7:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:2:2.

Comparative example 7

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 1:1:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:7:8.

Comparative example 8

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 0.5:1:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:1.5:2.

Comparative example 9

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 1:6:1:1, and the mass ratio of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:1:2:7.

Comparative example 10

The inhibitor A comprises the following raw materials: sodium hydroxide, calcium hypochlorite and calcium chloride, inhibitor B comprises the following raw materials: sodium hydroxide, ammonium hydroxide, and sodium metabisulfite, and does not contain lime;

wherein the mass ratio of sodium hydroxide, calcium hypochlorite and calcium chloride in the inhibitor A is 3:3:1, and the mass ratio of sodium hydroxide, ammonium hydroxide and sodium metabisulfite in the inhibitor B is 1:1:4.

Comparative example 11

The inhibitor A comprises the following raw materials: sodium hydroxide, calcium hypochlorite and sodium humate, inhibitor B comprises the following raw materials: sodium hydroxide, ammonium hydroxide, and sodium persulfate, and does not contain lime;

Wherein the mass ratio of sodium hydroxide, calcium hypochlorite and sodium humate in the inhibitor A is 3:3:1, and the mass ratio of sodium hydroxide, ammonium hydroxide and sodium persulfate in the inhibitor B is 1:1:4.

Comparative example 12

the inhibitor A comprises the following raw materials: sodium hydroxide, calcium chloride and sodium humate, the inhibitor B comprises the following raw materials: sodium hydroxide, sodium metabisulfite and sodium persulfate, and does not contain lime;

wherein the mass ratio of sodium hydroxide, calcium chloride and sodium humate in the inhibitor A is 3:1:1, and the mass ratio of sodium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:4:4.

Comparative example 13

The inhibitor A comprises the following raw materials: calcium hypochlorite, calcium chloride and sodium humate, inhibitor B comprises the following raw materials: ammonium hydroxide, sodium metabisulfite and sodium persulfate, and does not contain lime;

Wherein the mass ratio of calcium hypochlorite, calcium chloride and sodium humate in the inhibitor A is 3:1:1, and the mass ratio of ammonium hydroxide, sodium metabisulfite and sodium persulfate in the inhibitor B is 1:4:4.

Comparative example 14

the inhibitor A comprises the following raw materials: sodium hydroxide and sodium humate, inhibitor B comprises the following raw materials: sodium hydroxide and sodium persulfate, and does not contain lime;

Wherein the mass ratio of sodium hydroxide to sodium humate in the inhibitor A is 3:1, and the mass ratio of sodium hydroxide to sodium persulfate in the inhibitor B is 1:4.

Comparative example 15

the inhibitor A comprises the following raw materials: calcium hypochlorite and calcium chloride, inhibitor B comprises the following raw materials: ammonium hydroxide and sodium metabisulfite, and no lime is included;

wherein the mass ratio of calcium hypochlorite to calcium chloride in the inhibitor A is 3:1, and the mass ratio of ammonium hydroxide to sodium metabisulfite in the inhibitor B is 1:4.

Comparative example 16

the inhibitor A comprises the following raw materials: sodium hydroxide and calcium hypochlorite, inhibitor B comprises the following raw materials: sodium hydroxide and ammonium hydroxide, and does not contain lime;

Wherein the mass ratio of sodium hydroxide to calcium hypochlorite in inhibitor A is 3:3, and the mass ratio of sodium hydroxide to ammonium hydroxide in inhibitor B is 1:1.

Comparative example 17

the inhibitor A comprises the following raw materials: calcium chloride and sodium humate, inhibitor B comprises the following raw materials: sodium metabisulfite and sodium persulfate, and does not contain lime;

Wherein the mass ratio of the calcium chloride to the sodium humate in the inhibitor A is 1:1, and the mass ratio of the sodium metabisulfite to the sodium persulfate in the inhibitor B is 4:4.

Comparative example 18

Wherein, the inhibitor A is sodium humate and the inhibitor B is sodium persulfate.

Comparative example 19

wherein, the inhibitor A is calcium chlorate and the inhibitor B is ammonium hydroxide.

Comparative example 20

The comparative example provides a copper-sulfur flotation method by using lime as a copper-sulfur flotation separation inhibitor, which comprises the following steps:

Adding the inhibitor lime, the collector butyl xanthate and the foaming agent pinitol oil into ore pulp, and carrying out copper roughing to obtain copper roughing tailings and copper roughing concentrate, wherein the dosage of the inhibitor lime is 3000g/t of raw ore, the dosage of the collector butyl xanthate is 50g/t of raw ore, and the dosage of the foaming agent pinitol oil is 25g/t of raw ore;

Adding a collecting agent butyl xanthate into the copper roughing tailings to perform first copper scavenging and second copper scavenging to obtain copper scavenging ore, and sequentially returning the copper scavenging ore to the previous operation for grading, wherein the using amount of the collecting agent butyl xanthate in the first copper scavenging and the second copper scavenging is respectively 10g/t of raw ore and 10g/t of raw ore;

Adding inhibitor lime into the copper roughing concentrate to perform first copper concentration, second copper concentration and third copper concentration respectively to obtain copper concentrate, wherein the dosage of the inhibitor lime in the first copper concentration is 1000g/t of raw ore, and the dosage of the inhibitor lime in the second copper concentration is 500g/t of raw ore; the inhibitor lime is used in the third copper concentration in an amount of 300g/t of raw ore.

The specific flow of this comparative example is shown in FIG. 2.

Comparative example 21

This comparative example provides a copper sulphur flotation process which differs from example 1 in that: the collector B used in the copper-sulfur separation roughing and copper separation scavenger of example 1 was replaced with butyl xanthate.

Comparative example 22

This comparative example provides a copper sulphur flotation process which differs from example 1 in that: the collector a used in the copper-sulfur roughing and copper-sulfur mixed scavenging in example 1 was replaced with a xanthate.

Comparative example 23

This comparative example provides a copper sulphur flotation process which differs from example 1 in that: the collector A used in the copper-sulfur roughing and copper-sulfur mixed scavenging in the example 1 is replaced by the ethylene yellow medicine; the collector B used in the copper-sulfur separation roughing and copper separation scavenger of example 1 was replaced with butyl xanthate.

Comparative example 24

This comparative example provides a copper sulphur flotation process which differs from example 1 in that: the collector a used in the copper-sulfur roughing and copper-sulfur mixed scavenging in example 1 was replaced with ethionine; the collector B used in the copper-sulfur separation roughing and copper separation scavenger of example 1 was replaced with a butylamino black drug.

The product properties of the copper concentrates produced in examples 1 to 10 and comparative examples 1 to 23 were examined and the results are shown in Table 1.

TABLE 1 Performance data

From the data in Table 1, it can be derived:

(1) According to the embodiments 1-11 provided by the application, copper concentrate with Cu content of more than 22% and Cu recovery rate of more than 86% can be obtained by adopting the copper-sulfur flotation separation combination inhibitor and the flotation method for copper-sulfur raw ore;

(2) Compared with comparative examples 1-4 and 9-11 provided by the application, because the raw materials adopted by the inhibitor A in comparative examples 1 and 2 are sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, and the raw materials adopted by the inhibitor B are sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate, the sulfur inhibition effect in the mixed flotation stage is weakened, the sulfur inhibition effect in the separation flotation stage is enhanced, and the optimal sulfur inhibition effect cannot be exerted by being matched with a specific collector, so that the Cu content in copper concentrate is reduced, and the Cu recovery rate is reduced;

(3) Compared with comparative examples 3 and 4, examples 1-4 and 9-11 provided by the application have the advantages that the raw materials adopted by the inhibitor B in the comparative example 3 are sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate, so that the sulfur inhibition effect in the separation flotation process is stronger, the Cu content in copper concentrate is increased, and the Cu recovery rate is greatly reduced; because the raw materials adopted by the inhibitor A in the comparative example 4 are sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate, the sulfur inhibition effect in the mixed flotation process is weaker, the index of separation flotation is affected, and the Cu content in copper concentrate is greatly reduced;

(4) Compared with comparative examples 5-9, the examples 1-4 and 9-11 provided by the application have the advantages that as the proportion of the raw materials of sodium hydroxide and calcium hypochlorite of the inhibitor A is increased in comparative example 5, the sulfur inhibition effect of the calcium hypochlorite is stronger, and the proportion of the raw materials of sodium metabisulfite and sodium persulfate of the inhibitor B is increased, so that the overall sulfur inhibition effect is enhanced, the Cu content in copper concentrate is increased, and the Cu recovery rate is reduced; in comparative example 6, the ratio of the raw materials of sodium hydroxide and calcium hypochlorite of inhibitor A is increased, wherein the sulfur inhibition effect of the calcium hypochlorite is stronger, and the ratio of the raw materials of sodium metabisulfite and sodium persulfate of inhibitor B is reduced, so that the sulfur inhibition effect in the mixed flotation stage is enhanced, the sulfur inhibition effect in the separation flotation stage is reduced, and further the Cu content in the copper concentrate is reduced, and the Cu recovery rate is reduced; in comparative example 7, the proportion of the raw materials of calcium chloride and sodium humate of the inhibitor A is increased, wherein the sulfur inhibition effect of the sodium humate is stronger, and the proportion of the raw materials of sodium metabisulfite and sodium persulfate of the inhibitor B is increased, so that the overall sulfur inhibition effect is enhanced, and further the Cu content in copper concentrate is increased, and the Cu recovery rate is greatly reduced; in comparative example 8, the ratio of the raw materials of calcium chloride and sodium humate of inhibitor A is increased, wherein the sulfur inhibition effect of sodium humate is stronger, the ratio of sodium metabisulfite and sodium persulfate of inhibitor B is reduced, so that the sulfur inhibition effect in the mixed flotation stage is enhanced, the sulfur inhibition effect in the separation flotation stage is weakened, and further the Cu content in copper concentrate is greatly reduced, and the Cu recovery rate is greatly reduced; in comparative example 9, the sodium hydroxide proportion of the raw material of the inhibitor A is reduced, the calcium hypochlorite proportion is increased, the sodium metabisulfite proportion of the raw material of the inhibitor B is reduced, and the sodium persulfate proportion is increased, so that the sulfur inhibition effect in the mixed flotation stage is enhanced, the sulfur inhibition effect in the separation flotation stage is slightly weakened, and further the Cu content in the copper concentrate is slightly reduced, and the Cu recovery rate is greatly reduced;

(5) Comparing examples 1-4 and 9-11 provided by the application with comparative examples 10-19, the overall sulfur inhibition effect is reduced due to the lack of 1-3 of sodium hydroxide, calcium hypochlorite, calcium chloride and sodium humate as raw materials for inhibitor A and 1-3 of sodium hydroxide, ammonium hydroxide, sodium metabisulfite and sodium persulfate as raw materials for inhibitor B in comparative examples 10-19, and the Cu content in copper concentrate is greatly reduced;

(6) The present application provides examples 1-4 and 9-11 with a higher Cu content of the copper concentrate than comparative example 20, a slightly higher Cu recovery than comparative example 20, and a lower amount of inhibitor in examples 1-4 and 9-11 than comparative example 20 (lime is used as a combined inhibitor for copper-sulfur flotation separation). Therefore, the application shows that the copper-sulfur flotation separation combined inhibitor provided by the application is efficient, can completely replace lime, and realizes stable and efficient separation of copper and sulfur in copper-sulfur raw ores;

(7) Compared with comparative examples 21-24, in the example 1 provided by the application, the collector B adopts butyl xanthate, so that the sulfur inhibition effect in the separation flotation stage is weakened, and the Cu content in copper concentrate is greatly reduced; in comparative example 22, the collector a used the yellow reagent, which resulted in effective suppression of sulfur in the mixed flotation stage, but no effective recovery of copper, which resulted in a significant reduction in Cu recovery in the copper concentrate; in comparative example 23, the collector a adopts the ethylxanthate, the collector B adopts the butylxanthate, so that sulfur can be effectively inhibited in the mixed flotation stage, but copper can not be effectively recovered, the sulfur inhibition effect in the separation flotation stage is weakened, and further the Cu content in copper concentrate is greatly reduced, and the Cu recovery rate is greatly reduced; in comparative example 23, the collector a used ethyl thiourethane and the collector B used butyl ammonium black drug resulted in effective sulfur inhibition in the mixed flotation stage, but copper was not recovered effectively, and the sulfur inhibition effect in the separation flotation stage was reduced, thereby resulting in a significant reduction in Cu content in the copper concentrate and a significant reduction in Cu recovery.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application 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 application.

Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims

1. A method for copper sulfur flotation using a copper sulfur flotation separation combination inhibitor under lime-free conditions, the copper sulfur flotation separation combination inhibitor comprising: inhibitors a and B;

The mass ratio of the sodium hydroxide to the ammonium hydroxide to the sodium metabisulfite to the sodium persulfate in the inhibitor B is 1 (1-3) (3-6);

the method comprises the following steps:

The collector B comprises one or more of ethionine, 25# black, nigrosine and ethionine;

the dosage of the inhibitor A in the copper-sulfur coarse selection is 100-1000g/t of raw ore;

The dosage of the inhibitor A in the copper-sulfur mixing and refining is 10-100g/t of raw ore;

the dosage of the inhibitor B in the copper-sulfur separation coarse process is 50-500g/t of raw ore;

The dosage of the inhibitor B in the copper refining is 5-25g/t of raw ore.

2. The method for copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation according to claim 1, wherein the mass ratio of the sodium hydroxide, the calcium hypochlorite, the calcium chloride and the sodium humate in the inhibitor a is (2.5-4): 1-2:1;

3. The method of lime-free copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation according to claim 1, wherein at least one of the following conditions is satisfied:

A. the consumption of the collector A is 40-100g/t of raw ore;

B. the dosage of the activated carbon is 50-200g/t of raw ore;

C. The dosage of the collector B is 5-50g/t of raw ore.

4. The method of lime-free copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation according to claim 1, wherein at least one of the following conditions is satisfied:

5. The method of lime-free copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation according to claim 4, wherein at least one of the following conditions is satisfied:

6. A method for copper sulphur flotation using a combined inhibitor of copper sulphur flotation separation according to any one of the claims 1-5, characterized in that at least one of the following conditions is fulfilled:

i. the number of roughing copper and sulfur is 1 or more;

iv, separating and roughing copper and sulfur for 1 or more times;

the number of copper beneficiations is multiple.

7. The method of lime-free copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation according to claim 6, wherein at least one of the following conditions is satisfied:

8. The method of performing copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation under lime-free conditions of claim 6, wherein the copper sulfur mixed beneficiation comprises a first copper sulfur mixed beneficiation and a second copper sulfur mixed beneficiation;

9. The method of lime-free copper sulfur flotation using a combined inhibitor of copper sulfur flotation separation according to claim 6, wherein the copper beneficiation comprises a first copper beneficiation, a second copper beneficiation, and a third copper beneficiation;