阅读说明：本技术 一种铜钼混合精矿浮选分离药剂制度及其应用 (Copper-molybdenum bulk concentrate flotation separation reagent system and application thereof ) 是由 赵开乐 闫武 于 2019-09-04 设计创作，主要内容包括：本发明公开了一种铜钼混合精矿浮选分离药剂制度及其应用；铜钼混合精矿浮选分离药剂制度包括铜钼浮选分离过程中的铜矿物抑制剂、钼矿物捕收剂以及起泡剂。其中,所述的铜矿物抑制剂按重量份计,包括：氢氧化钠3-7份、双氧水3-6份、硫代乙醇酸钠15-25份、二乙烯三胺五乙酸五钠2-5份、适量水；所述的钼矿物捕收剂按重量份计,包括：煤油20-30份、叔十二硫醇5-10份；起泡剂为2-己醇。本发明的抑制剂及捕收剂选择性吸附能力强,协同作用性能优异,起泡剂基团活性强,形成的泡沫脆而密实,矿化效果好。本发明铜钼浮选分离药剂制度可大幅度提高复杂难分离铜钼混合精矿中钼矿物和铜矿物的可浮性差异,有效降低铜钼互含,分离指标优异,且采用的药剂无毒无害,对环境影响小。(the invention discloses a copper-molybdenum bulk concentrate flotation separation chemical system and application thereof; the flotation separation agent system of the copper-molybdenum bulk concentrate comprises a copper mineral inhibitor, a molybdenum mineral collector and a foaming agent in the copper-molybdenum flotation separation process. Wherein the copper mineral inhibitor comprises the following components in parts by weight: 3-7 parts of sodium hydroxide, 3-6 parts of hydrogen peroxide, 15-25 parts of sodium thioglycolate, 2-5 parts of diethylenetriamine pentaacetic acid pentasodium and a proper amount of water; the molybdenum mineral collector comprises the following components in parts by weight: 20-30 parts of kerosene and 5-10 parts of tert-dodecyl mercaptan; the blowing agent is 2-hexanol. The inhibitor and the collector have strong selective adsorption capacity, excellent synergistic effect performance and strong activity of a foaming agent group, and the formed foam is crisp and dense and has good mineralization effect. The copper-molybdenum flotation separation agent system can greatly improve the floatability difference of molybdenum minerals and copper minerals in the complex copper-molybdenum bulk concentrates difficult to separate, effectively reduce the mutual content of copper and molybdenum, has excellent separation indexes, adopts nontoxic and harmless agents, and has little influence on the environment.)

1. A copper-molybdenum bulk concentrate flotation separation reagent system is characterized by comprising a copper mineral inhibitor, a molybdenum mineral collector and a foaming agent:

the copper mineral inhibitor comprises sodium hydroxide, hydrogen peroxide, sodium thioglycolate, diethylene triamine pentaacetic acid pentasodium and water;

the molybdenum mineral collectors comprise kerosene and tertiary dodecyl mercaptan;

the foaming agent is 2-hexanol.

2. the system of claim 1, wherein the copper-molybdenum bulk concentrate flotation separation chemical comprises, in parts by weight: 3-7 parts of sodium hydroxide, 3-6 parts of hydrogen peroxide, 15-25 parts of sodium thioglycolate, 2-5 parts of diethylenetriaminepentaacetic acid pentasodium and 300 parts of water 150-.

3. The copper molybdenum bulk concentrate flotation separation chemical system according to claim 1, wherein the molybdenum mineral collector comprises, in parts by weight: 20-30 parts of kerosene and 5-10 parts of tert-dodecyl mercaptan.

4. The use of the system of any one of claims 1 to 3, wherein the agent is used for flotation separation of copper-molybdenum bulk concentrates, and the copper grade of the copper-molybdenum bulk concentrates does not exceed 5%.

5. the application of the flotation separation chemical system for the copper-molybdenum bulk concentrate according to claim 4 is characterized in that the molybdenum grade of the copper-molybdenum bulk concentrate is 5% -10%, and the copper grade is 1% -3%.

6. The application of the chemical system for flotation separation of copper-molybdenum bulk concentrate according to claim 5 is characterized by comprising the following steps:

(1) grinding the copper-molybdenum bulk concentrate, wherein sodium hydroxide is added in an amount of 150-;

(2) Sequentially adding the copper mineral inhibitor, the molybdenum mineral collector and the foaming agent into the ore pulp obtained by grinding in the step (1) to perform copper-molybdenum separation and rough separation to obtain rough concentrate and rough tailings, wherein the dosage of the copper mineral inhibitor is 2500-;

(3) And (3) sequentially adding the copper mineral inhibitor, the molybdenum mineral collector and the foaming agent into the rough concentrate obtained in the step (2), carrying out molybdenum concentration, wherein the molybdenum concentration is carried out for 4-6 times, each time of molybdenum concentration is carried out to obtain respective concentrated middlings, the last time of molybdenum concentration is carried out to obtain concentrated middlings and molybdenum concentrate, combining the concentrated middlings obtained by at least two times of molybdenum concentration, returning to the copper-molybdenum separation rough concentration operation, combining the concentrated middlings obtained by the rest times of molybdenum concentration, and returning to the first time of molybdenum concentration operation in a concentrated manner.

7. The application of the chemical system for flotation separation of copper-molybdenum bulk concentrate according to claim 6, wherein in the step (3): the dosage of the copper mineral inhibitor is 800-1500 g/ton of bulk concentrate, the dosage of the molybdenum mineral collector is 50-150 g/ton of bulk concentrate, and the dosage of the foaming agent is 20-50 g/ton of bulk concentrate.

8. The application of the copper-molybdenum bulk concentrate flotation separation reagent system according to claim 7, characterized by further comprising molybdenum scavenging, wherein the molybdenum scavenging is performed by sequentially adding a molybdenum mineral collector and a foaming agent to the rougher tailings obtained in the step (2), the scavenging frequency is 1-2 times, and the molybdenum scavenging is performed to obtain copper rougher concentrates and scavenging middlings;

the amount of the molybdenum mineral collecting agent used in each scavenging is 40-100 g/ton of mixed concentrate, the amount of the foaming agent used in each molybdenum scavenging is 50-80 g/ton of mixed concentrate, middlings obtained in each molybdenum scavenging are combined and are returned to the copper-molybdenum separation roughing operation in a centralized manner.

9. The application of the chemical system for flotation and separation of copper-molybdenum bulk concentrate according to claim 8, wherein when the number of times of molybdenum scavenging is two, the usage amount of the molybdenum mineral collector in the first molybdenum scavenging is 80-100 g/ton of bulk concentrate, the usage amount of the frother 2-hexanol is 60-80 g/ton of bulk concentrate, the usage amount of the molybdenum mineral collector in the second molybdenum scavenging is 40-80 g/ton of bulk concentrate, and the usage amount of the frother 2-hexanol is 50-60 g/ton of bulk concentrate.

When the molybdenum concentration times exceed 4 times, the dosage of the copper inhibitor added in each molybdenum concentration for 1-4 times is 1500 g/ton of bulk concentrate, the dosage of the molybdenum mineral collector is 80-150 g/ton of bulk concentrate, the dosage of the foaming agent 2-hexanol is 40-50 g/ton of bulk concentrate, the dosage of the copper inhibitor added in each molybdenum concentration for more than 4 times is 800 g/ton of bulk concentrate, 1000 g/ton of bulk concentrate, 50-80 g/ton of bulk concentrate and 20-40 g/ton of foaming agent 2-hexanol.

Technical Field

The invention belongs to the technical field of copper-molybdenum sulfide ore flotation, and particularly relates to a copper-molybdenum bulk concentrate flotation separation agent system and application thereof.

Background

with the development of high technology, particularly the microelectronic field and military industry, molybdenum will become an important metal material and strategic material, and copper marks the development level of national industry, so that molybdenum and copper are closely related to the development of national economy.

In the ore dressing of molybdenum sulfide ore, the separation of copper and molybdenum from copper-molybdenum bulk concentrate is a difficult problem in the field of mineral processing all the time, and is a great obstacle for restricting the development of copper-molybdenum symbiotic resources, so that the separation becomes a key point for research of ore dressing workers. Molybdenite has good natural floatability, chalcopyrite also has good floatability, molybdenum sulfide ore generally adopts hydrocarbon oil and xanthate to combine and carry out copper molybdenum mixed flotation, and under this condition, a large amount of xanthate collecting agents can be adsorbed on the surface of copper sulfide, various hydrophobic substances are formed, the suppression difficulty is increased, and the copper molybdenum separation effect is poor. Before the inhibitor is added, the hydrophobic substance needs to be resolved, namely, the collector and the hydrophobic substance adsorbed on the surface of the copper sulfide need to be resolved firstly, and then the inhibitor can effectively act on the surface of the copper sulfide to keep the copper sulfide hydrophilic in the flotation separation process, so that the copper sulfide is inhibited. The main molybdenum concentration plants in the world adopt cyanide to inhibit copper minerals to carry out copper-molybdenum separation on copper-molybdenum bulk concentrates, so that a better flotation index is obtained, and although the cyanide has the advantages of strong copper mineral inhibition capacity and small using amount, the cyanide has strong toxicity and is easy to cause serious pollution to the environment, so the application of the cyanide in ore dressing is limited. Researches show that the newly developed green efficient inhibitor needs to have the performances of chemical adsorption, complexing effect and the like, the inhibition capability of the surface hydrophobization chalcopyrite is enhanced, and meanwhile, the selective collecting agent of molybdenum minerals needs to be developed, so that the floatability of the molybdenum minerals in the copper-molybdenum separation process is improved. In addition, copper and molybdenum flotation separation is generally carried out in a strong alkaline ore pulp environment, in the prior art, a foaming agent of the terpineol oil is generally adopted, the terpineol oil is strong in foaming, the flotation foam is high in viscosity and serious in entrainment, and the sorting property is poor. Therefore, the development of a copper mineral inhibitor, a molybdenum mineral collector and a foaming agent which have excellent performance and are environment-friendly is still a main way for realizing the effective separation of copper and molybdenum in the copper-molybdenum bulk concentrate.

Disclosure of Invention

the invention aims to provide a copper-molybdenum bulk concentrate flotation separation reagent system and application thereof, and solves the technical problems of low separation efficiency of copper-molybdenum bulk concentrate and poor concentrate product.

The invention provides a copper-molybdenum bulk concentrate flotation separation reagent system, which comprises a copper mineral inhibitor, a molybdenum mineral collector and a foaming agent: the copper mineral inhibitor comprises sodium hydroxide, hydrogen peroxide, sodium thioglycolate, diethylene triamine pentaacetic acid pentasodium and water; the molybdenum mineral collectors comprise kerosene and tertiary dodecyl mercaptan; the foaming agent is 2-hexanol.

Further, the copper mineral inhibitor comprises the following components in parts by weight: 3-7 parts of sodium hydroxide, 3-6 parts of hydrogen peroxide, 15-25 parts of sodium thioglycolate, 2-5 parts of pentasodium diethylenetriaminepentaacetate and 300 parts of water 150-.

Further, the molybdenum mineral collector comprises the following components in parts by weight: 20-30 parts of kerosene and 5-10 parts of tert-dodecyl mercaptan.

Further, the agent is used for flotation separation of copper-molybdenum bulk concentrates, and the copper grade of the copper-molybdenum bulk concentrates is not more than 5%. It should be noted that the copper-molybdenum bulk concentrate of the present invention is typically a rough concentrate obtained by subjecting a low-grade molybdenum sulfide ore raw ore to rough concentration (flotation) or other pre-separation treatment.

further, the molybdenum grade of the copper-molybdenum bulk concentrate is 5% -10%, and the copper grade is 1% -3%.

Further, the invention also provides application of a flotation separation reagent system for copper-molybdenum bulk concentrates, which comprises the following steps:

(1) Grinding the copper-molybdenum bulk concentrate, wherein sodium hydroxide is added in an amount of 150-;

(2) sequentially adding a copper mineral inhibitor, a molybdenum mineral collector and a foaming agent into the ore pulp obtained by grinding in the step (1) to perform copper-molybdenum separation and rough separation to obtain rough concentrate and rough tailings, wherein the using amount of the copper mineral inhibitor is 2500-;

(3) adding the copper mineral inhibitor, the molybdenum mineral collector and the foaming agent into the rough concentrate obtained in the step (2) in sequence, carrying out molybdenum concentration, wherein the molybdenum concentration is carried out for 4-6 times, each time of molybdenum concentration obtains respective concentrated middlings, the last time of molybdenum concentration obtains concentrated middlings and molybdenum concentrate, combining the concentrated middlings obtained by at least two times of molybdenum concentration, returning to the copper-molybdenum separation rough concentration operation, combining the concentrated middlings obtained by the rest times of molybdenum concentration, and returning to the first time of molybdenum concentration operation;

Further, in the step (3): the using amount of the copper mineral inhibitor is 800-1500 g/ton of bulk concentrate, the using amount of the molybdenum mineral collector is 50-150 g/ton of bulk concentrate, and the using amount of the foaming agent is 20-50 g/ton of bulk concentrate;

Further, molybdenum scavenging is also included, molybdenum mineral collecting agents and foaming agents are sequentially added into the roughing tailings obtained in the step (2) for molybdenum scavenging, the scavenging frequency is 1-2, and copper roughing concentrates and middlings of each scavenging are obtained through molybdenum scavenging; the amount of the molybdenum mineral collecting agent used for each molybdenum scavenging is 40-100 g/ton of mixed concentrate, the amount of the foaming agent used for each molybdenum scavenging is 50-80 g/ton of mixed concentrate, middlings obtained by each molybdenum scavenging are combined and return to the copper-molybdenum separation roughing operation in a centralized manner;

Further, when the molybdenum scavenging times are two times, the using amount of the molybdenum mineral collector for the first molybdenum scavenging is 80-100 g/ton of the mixed concentrate, the using amount of the foaming agent 2-hexanol is 60-80 g/ton of the mixed concentrate, the using amount of the molybdenum mineral collector for the second molybdenum scavenging is 40-80 g/ton of the mixed concentrate, and the using amount of the foaming agent 2-hexanol is 50-60 g/ton of the mixed concentrate;

Further, in the step (3), when the molybdenum concentration times exceed 4 times, the dosage of the copper inhibitor added in each molybdenum concentration time is 1000-1500 g/ton of mixed concentrate, the dosage of the molybdenum mineral collector is 80-150 g/ton of mixed concentrate, the dosage of the foaming agent 2-hexanol is 40-50 g/ton of mixed concentrate, the dosage of the copper inhibitor added in each molybdenum concentration time for more than 4 times is 800-1000 g/ton of mixed concentrate, the dosage of the molybdenum mineral collector is 50-80 g/ton of mixed concentrate, and the dosage of the foaming agent 2-hexanol is 20-40 g/ton of mixed concentrate;

In the invention, each time of flotation, fine selection and scavenging are carried out size mixing according to the condition, and the size mixing is carried out according to the conventional technical requirements. The copper mineral inhibitor and the molybdenum mineral collector in the reagent system have strong selective adsorption effect, wherein the copper mineral inhibitor is beneficial to analyzing the hydrophobic group of the collector on the surface of the copper mineral, and generates chemical co-adsorption, oxidation reaction and complexing effect on the surface of the copper mineral, so that the combined inhibition effect is good; the molybdenum mineral collecting agent can selectively act on the surface of molybdenum minerals to form interpenetration cooperative adsorption, the combined collecting capacity is strong, and the collecting effect on micro-fine particle molybdenite is good; the inhibitor has excellent inhibiting effect on copper minerals, does not influence the collecting agent to act on the surface of the molybdenum minerals while inhibiting the copper minerals, and separates copper concentrate and molybdenum concentrate under the synergistic action of the inhibitor and the collecting agent; meanwhile, in the system of the invention, the foaming agent has proper molecular weight and strong radical activity, and the formed foam is crisp and non-sticky, has good mineralization effect and further optimizes the mineral separation property.

the molybdenum mineral collecting agent adopted by the invention is kerosene, tert-dodecyl mercaptan, copper mineral inhibitor sodium hydroxide, hydrogen peroxide, sodium thioglycolate and diethylene triamine pentaacetic acid pentasodium, so that the difference of the floatability of target minerals and non-target minerals in the flotation process can be greatly improved, and the effect is excellent. The using amount of each component and the using amount after combination are limited, for example, the molybdenum mineral collecting agent with a specific parameter range is added in the application process of the copper-molybdenum bulk concentrate flotation separation agent system, so that the excessive collecting agent can be prevented from causing a large amount of floating of slime while enough components are ensured to collect the molybdenum mineral; meanwhile, the copper mineral collecting agent with a specific parameter range is added, so that sufficient components are guaranteed to inhibit the copper minerals, and meanwhile, the floatability reduction of the molybdenum minerals caused by excessive inhibitors is avoided.

According to the invention, sodium hydroxide is added during grinding of the copper-molybdenum bulk concentrate, the sodium hydroxide has the function of adjusting the pH value of ore pulp to provide a proper acid-base environment for flotation of the ore pulp, and the sodium hydroxide is strong alkali and has the function of dissolving active particles or an activation film on the surface of the copper mineral, which easily act with a collecting agent, so that the hydrophobicity of the copper mineral is broken, and then the molybdenum mineral collecting agent and a copper mineral inhibitor are added to carry out molybdenum concentrate to enrich the molybdenum mineral.

The molybdenum mineral collecting agent adopts the combination of kerosene and tertiary dodecyl mercaptan, the combined collecting mechanism of the kerosene and the tertiary dodecyl mercaptan is mainly a co-adsorption mechanism, and specifically is a laminated adsorption mechanism, namely, the kerosene and the molybdenite with high activity are firstly acted, so that the molybdenite changes the original surface wettability or chemical adsorption characteristic of minerals and then is subjected to secondary laminated adsorption with the tertiary dodecyl mercaptan, the hydrophobicity of the molybdenum mineral is further increased, the two medicaments generate a 'synergistic effect', and the tertiary dodecyl mercaptan has strong defoaming performance, is easy to form a molybdenum mineral hydrophobic thin layer and is very favorable for collecting the fine-particle molybdenum mineral.

The copper mineral inhibitor has the advantages that a novel combined inhibitor, namely hydrogen peroxide, sodium thioglycolate and diethylene triamine pentaacetic acid pentasodium are adopted as copper mineral inhibitors in the copper-molybdenum separation process, the copper mineral inhibitors are not good in inhibition effect of a single inhibitor on copper minerals, the copper mineral inhibitors commonly achieve the effect of jointly inhibiting the copper minerals by utilizing the mutual combination of various agents in the practical production of the copper-molybdenum minerals, the hydrogen peroxide is a strong oxidizing agent and can oxidize biflavones on the surfaces of the copper minerals into xanthate ions so as to separate the xanthate ions from the surfaces of the minerals, the copper mineral inhibitors have strong action capacity and remarkable effect, the sodium thioglycolate is an effective copper mineral inhibitor and excellent in selective inhibition effect, a molecular structure of the sodium thioglycolate has various polar groups, wherein an-S ^- group has reducibility and mineral affinity and can perform chemical adsorption with the minerals, the sodium thioglycolate and the COO-group can form a hydrophilic film with the minerals so as to form a hydrophilic film between the copper minerals and the agents, the hydrophilicity of the copper minerals is increased, the chances of impurities entering the molybdenum concentrates are reduced, the minerals, the pentaacetic acid pentasodium pentaacetic acid pentasodium is a complexing agent which can quickly and can be used for quickly removing the copper minerals, the copper minerals are not used as a water-molybdenum mineral inhibitors, the copper mineral inhibitors can be used for effectively and the copper minerals, the copper mineral inhibitors can be used for effectively and the copper minerals, the copper.

The invention has the beneficial effects that:

According to the flotation separation agent system of the copper-molybdenum bulk concentrate, the copper mineral inhibitor and the molybdenum mineral collector act synergistically, the inhibitor does not influence the adsorption of the collector on the surface of a molybdenum mineral while inhibiting the copper mineral, and the foaming agent 2-hexanol is used in a matched manner, so that the floatability difference between the molybdenum mineral and the copper mineral in the complex copper-molybdenum bulk concentrate difficult to separate can be greatly improved, the separation precision is improved, the mutual content of copper and molybdenum is effectively reduced, the copper-molybdenum separation index is excellent, and the adopted agent is non-toxic and harmless and has little influence on the environment;

the method provided by the invention performs flotation separation on copper-molybdenum bulk concentrates in different producing areas, adopts unique modes of deep molybdenum concentration, batch concentrated return of middlings and the like, enhances the flotation separation efficiency, effectively improves the grade and recovery rate of molybdenum minerals, obtains the molybdenum concentrate with low copper content, and has excellent indexes and strong reagent adaptability.

Detailed Description

the technical effects of the present invention will be specifically described below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art without departing from the spirit and scope of the invention.