阅读说明：本技术 一种浮选铅锌硫化矿的组合锌捕收剂及其应用 (Combined zinc collector for flotation of lead-zinc sulfide ore and application thereof ) 是由 焦芬 覃文庆 杨聪仁 韩俊伟 魏茜 胡陈强 崔艳芳 张政权 徐乐 于 2020-07-13 设计创作，主要内容包括：本发明公开了一种浮选铅锌硫化矿的组合锌捕收剂及其应用,按照重量份数,活性成分包括有丁铵黑药10-30份、乙硫氮30-50份、2-氨基苯硫酚30-50份。本发明一种闪锌矿浮选的高效组合捕收剂,所述组合捕收剂由丁铵黑药、乙硫氮、2-氨基苯硫酚组成,易获取,价格低,药剂用量少,无污染。丁铵黑药捕收能力弱,但具有起泡性；硫氮捕收能力强,对铅、锌硫化矿均具有一定的捕收能力；2-氨基苯硫酚捕收能力强,相比于常规捕收剂丁黄药,2-氨基苯硫酚对铁闪锌矿即便在不用铜离子活化的情况下浮选效果仍然较好,而对硫化铅矿浮选效果较差。但是,2-氨基苯硫酚是弱酸性化合物,在pH较低时不能充分和硫化锌矿作用。因此本发明组合捕收剂各组分能够相互补充。(The invention discloses a combined zinc collector for flotation of lead-zinc sulfide ores and application thereof, wherein active ingredients comprise, by weight, 10-30 parts of ammonium nitrate-ammonium black chemicals, 30-50 parts of ethion nitrogen and 30-50 parts of 2-amino thiophenol. The high-efficiency combined collector for zinc blende flotation is composed of ammonium butyrate black powder, ethionamide and 2-aminothiophenol, and is easy to obtain, low in price, low in medicament dosage and free of pollution. The ammonium butyrate black powder is weak in collecting capacity, but has foamability; the sulfur and nitrogen collecting capacity is strong, and the sulfur and nitrogen collecting agent has certain collecting capacity on lead and zinc sulfide ores; the 2-amino thiophenol has strong collecting capability, and compared with a conventional collecting agent butyl xanthate, the 2-amino thiophenol still has good flotation effect on the sphalerite even under the condition of not using copper ions for activation, and has poor flotation effect on lead sulfide ore. However, 2-aminothiophenol is a weakly acidic compound and does not sufficiently act on zinc sulfide ore at a low pH. Therefore, the components of the combined collector can complement each other.)

1. The combined zinc collector for flotation of lead-zinc sulfide ore is characterized in that active ingredients comprise, by weight, 10-30 parts of ammonium nitrate-ammonium black powder, 30-50 parts of ethion nitrogen and 30-50 parts of 2-amino thiophenol.

2. The combined zinc collector for the flotation of lead-zinc sulphide ore according to claim 1, characterized in that the combined zinc collector is prepared into an aqueous solution to be added into ore pulp, and the three active ingredients are mixed to prepare the aqueous solution with the mass concentration of 0.5-10%.

3. A method of flotation of lead zinc sulphide ores in combination with a zinc trap according to claim 1 or 2, comprising the steps of:

1) crushing and grinding raw ores, and adding water to adjust the raw ores into ore pulp;

2) adding an inhibitor, a zinc inhibitor, a lead collecting agent and a foaming agent into the ore pulp obtained in the step 1), and then performing lead flotation to obtain lead concentrate and lead tailings;

3) adding an inhibitor, a zinc activator, a combined zinc collector and a foaming agent into the lead tailings, and then performing zinc flotation to obtain zinc concentrate.

4. The method for flotation of lead-zinc sulphide ore by using the combined zinc collector as claimed in claim 3, wherein in the step 1), the ore is ground to a fineness of 70-85% in a-0.074 mm fraction, water is added for size mixing, and the concentration of ore pulp is 20-35%.

5. The method for flotation of lead-zinc sulfide ore by using the combined zinc collector according to claim 3, wherein the lead flotation in the step 2) is two-coarse two-scavenging three-fine, the inhibitor is lime, the zinc inhibitor is zinc sulfate and sodium carbonate, the lead collector is ethidium nitrate and ammonium-butyl black powder; the foaming agent is terpineol.

6. The method for flotation of lead-zinc sulphide ore by using the combined zinc collector as claimed in claim 5, wherein the chemical system for lead flotation is as follows:

firstly, coarse: lime with the concentration of 5000-; zinc inhibitor zinc sulfate 2000-; 30-60g/t of lead collecting agent ethidium and 10-40g/t of ammonium butyl black medicine; the foaming agent terpineol is 20-50 g/t.

Secondly, coarse: 20-40g/t of lead collecting agent ethidium and 10-20g/t of ammonium butyl black medicine;

and (6) scanning: 5-15g/t of lead collecting agent ethidium and 1-10g/t of ammonium butyl black medicine;

secondly, sweeping: 2-15g/t of lead collecting agent ethidium and 1-10g/t of ammonium butyl black medicine;

firstly, refining: 300-800g/t of inhibitor lime, 600g/t of zinc sulfate as zinc inhibitor and 300g/t of sodium carbonate as 100 inhibitor;

II, refining: 400/t of inhibitor lime 200, 300g/t of zinc inhibitor zinc sulfate 100 and 50-150g/t of sodium carbonate;

three essences: no medicament is added.

7. The method for flotation of lead-zinc sulphide ore with the combined zinc collector of claim 3, wherein in the step 3), the zinc flotation is coarse dicumyl chloride, the inhibitor is lime, the zinc activator is copper sulfate, and the foaming agent is terpineol.

8. The method for flotation of lead-zinc sulphide ore by using the combined zinc collector as claimed in claim 7, wherein the roughing medicament system is as follows: 1000-2000g/t of inhibitor lime, 300-1000g/t of zinc activator copper sulfate, 60-180g/t of combined zinc collecting agent and 20-60g/t of foaming agent terpineol.

9. The method for flotation of lead-zinc sulphide ores by combining zinc collectors according to claim 7, wherein the scavenging chemical regime is: one sweep of adding the combined zinc collecting agent is 10-50g/t, and the second sweep of adding the zinc collecting agent is 5-25 g/t.

10. The method for flotation of lead-zinc sulphide ore by using the combined zinc collector as claimed in claim 3, wherein the concentration system comprises the following components: 500g/t of lime serving as an inhibitor is added in the first step, and 300g/t of lime serving as an inhibitor is added in the second step.

Technical Field

The invention belongs to the technical field of lead-zinc sulfide ore flotation, and particularly relates to a combined zinc collector for flotation of lead-zinc sulfide ore and application thereof.

Background

Zinc is a silvery white metal with light blue, is often combined with copper, tin, lead and the like into brass or aluminum, magnesium, copper and the like into die-casting alloy, and is applied to a plurality of fields of metallurgy, chemical industry, machinery, electricity, military affairs and the like; another important use of zinc is galvanization, which is used for galvanic corrosion protection. Zinc compounds are useful in the textile industry and in the manufacture of paints, dyes, pigments, and the like.

The sphalerite is one of the most important sources of zinc metal, about 90 percent of zinc yield source sphalerite has a chemical formula that ZnS sphalerite often has Fe element mixed in a similar homoimage form in the geological ore formation process of an ore deposit, and the sphalerite is called as wurtzite with the iron content of more than 6 percent. The floatability of sphalerite generally depends on the content of Fe as an impurity, and it is generally considered that the more Fe is contained, the larger the lattice parameter thereof is, so that the hydration of sphalerite is enhanced and the natural floatability thereof is reduced.

High-sulfur lead-zinc ore is a common lead-zinc ore deposit type and is widely distributed in China, and the ore is typically characterized in that: (1) the S content in the ore is high, the S grade can reach 30% usually, and the main iron sulfide minerals are pyrite and pyrrhotite; (2) the grade of zinc is high, lead and zinc in the ore can usually reach 10 percent, and the grade of zinc is far higher than that of lead; (3) the floatability difference of the minerals is large, and the efficient separation is difficult; (4) mineral embedding relationship is complex, high-efficiency dissociation is difficult, for example, valuable minerals such as galena, sphalerite and the like in the ores are often embedded in pyrite or gangue ores in the form of micro-fine particle inclusion or dip-dyeing, and sufficient monomer dissociation is difficult; (5) the associated valuable components in the ore are rich, and the comprehensive utilization value is high.

The main principle of lead-zinc sulfide ore separation is lead flotation and zinc suppression, and zinc blende is usually floated from lead-dressing tailings, so that a zinc collector with strong collecting capacity and high selectivity is selected, and is very important particularly in the high-sulfur lead-zinc ore separation process. At present, the common sphalerite collecting agent mainly comprises xanthate, black xanthate and sulfur and nitrogen, and the xanthate has strong collecting capability but poor selectivity; the black powder has weak collecting capacity, small using amount and foamability; strong sulfur and nitrogen collecting capacity, good selectivity and less medicament consumption. However, in the actual flotation of high-sulfur lead-zinc ores, the sulfur content is high, a large amount of lime needs to be added, the pH value of ore pulp is high, a zinc-selecting foam layer is thin, foams are small and fine, the impurity content of zinc concentrate is high, and in order to improve the grade of the zinc concentrate and improve the recovery rate, a collecting agent with higher selectivity and collecting property on the zinc sulfide ores needs to be researched.

Disclosure of Invention

The invention aims to provide a combined zinc collector for floating lead-zinc sulfide ores, which has good selectivity and strong collecting property, and application thereof.

The combined zinc collector for the flotation lead-zinc sulfide ore comprises, by weight, 10-30 parts of ammonium buthylate, 30-50 parts of ethion and 30-50 parts of 2-aminothiophenol.

The combined zinc collector is added by preparing an aqueous solution from the active ingredients, and the three active ingredients are mixed to prepare an aqueous solution with the mass concentration of 0.5-10%.

The method for flotation of lead-zinc sulphide ore by using the combined zinc collector comprises the following steps:

1) crushing and grinding raw ores, and adding water to adjust the raw ores into ore pulp;

2) adding an inhibitor, a zinc inhibitor, a lead collecting agent and a foaming agent into the ore pulp obtained in the step 1), and then performing lead flotation to obtain lead concentrate and lead tailings;

3) adding an inhibitor, a zinc activator, a combined zinc collector and a foaming agent into the lead tailings, and then performing zinc flotation to obtain zinc concentrate.

In the step 1), grinding the ore to the fineness of 70-85% of the-0.074 mm size fraction, and adding water for size mixing, wherein the concentration of the ore pulp is 20-35%.

In the step 2), lead flotation is performed by two-coarse two-scavenging three-fine, the inhibitor is inhibited to obtain lime, the zinc inhibitor is zinc sulfate and sodium carbonate, and the lead collecting agent is ethidium nitrate and ammonium nitrate black powder; the foaming agent is terpineol.

The lead flotation reagent system comprises:

firstly, coarse: lime with the concentration of 5000-; zinc inhibitor zinc sulfate 2000-; 30-60g/t of lead collecting agent ethidium and 10-40g/t of ammonium butyl black medicine; the foaming agent terpineol is 20-50 g/t.

Secondly, coarse: 20-40g/t of lead collecting agent ethidium and 10-20g/t of ammonium butyl black medicine;

and (6) scanning: 5-15g/t of lead collecting agent ethidium and 1-10g/t of ammonium butyl black medicine;

secondly, sweeping: 2-15g/t of lead collecting agent ethidium and 1-10g/t of ammonium butyl black medicine;

firstly, refining: 300-800g/t of inhibitor lime, 600g/t of zinc sulfate as zinc inhibitor and 300g/t of sodium carbonate as 100 inhibitor;

II, refining: 400/t of inhibitor lime 200, 300g/t of zinc inhibitor zinc sulfate 100 and 50-150g/t of sodium carbonate;

three essences: no medicament is added.

In the step 3), zinc flotation is carried out on the first coarse second scavenging three refined products, the inhibitor is lime, the zinc activator is copper sulfate, and the foaming agent is terpineol;

the roughly selected medicament system comprises: 1000-2000g/t of inhibitor lime, 300-1000g/t of zinc activator copper sulfate, 60-180g/t of combined zinc collecting agent and 20-60g/t of foaming agent terpineol. The scavenging medicament system comprises: one sweep of adding the combined zinc collecting agent is 10-50g/t, and the second sweep of adding the zinc collecting agent is 5-25 g/t.

The selected medicament system is as follows: 500g/t of lime serving as an inhibitor is added in the first step, and 300g/t of lime serving as an inhibitor is added in the second step.

The above-mentioned chemicals except inhibitor lime are all formulated into aqueous solution and added into ore pulp, the addition quantity of them is calculated according to the addition quantity of solid, for example, 60-180g/t of combined zinc-collecting agent is the addition quantity of added solid combined zinc-collecting agent, but not the addition quantity after formulating into solution, the inhibitor lime mainly plays the role of inhibiting pyrite.

The principle of the invention is as follows:

after the lead tailings are fully acted by an activator copper sulfate, zinc ions on the surface of zinc sulfide ore are released, zinc hydroxylation is generated under the action of water in ore pulp, then ethidium nitrate, ammonium butyrate niger and 2-amino thiophenol molecules respectively act with the zinc hydroxylation to generate chemical adsorption to generate collecting agent metal salt, a hydrophobic membrane is formed on the surface of the ore, and the hydrophobic membrane floats upwards through bubbles. The low-concentration 2-aminothiophenol can obtain better recovery rate, can replace part of ethidium and ammonium nitrate, can reduce the dosage of the medicament, and can ensure that the 2-aminothiophenol can be mixed more uniformly, improve the synergistic effect of the medicament and ensure that the medicament can act with minerals more quickly. The 2-amino thiophenol has higher affinity to the surface of ZnS, can quickly generate exothermic adsorption reaction, has strong collecting capability, higher mineral floating speed, reduced flotation time and increased zinc recovery rate.

The invention has the beneficial effects that:

(1) the high-efficiency combined collector for zinc blende flotation is composed of ammonium butyrate black powder, ethionamide and 2-aminothiophenol, and is easy to obtain, low in price, low in medicament dosage and free of pollution.

(2) The ammonium butyrate black powder is weak in collecting capacity, but has foamability; the sulfur and nitrogen collecting capacity is strong, and the sulfur and nitrogen collecting agent has certain collecting capacity on lead and zinc sulfide ores; the 2-amino thiophenol has strong collecting capability, and compared with a conventional collecting agent butyl xanthate, the 2-amino thiophenol still has good flotation effect on the sphalerite even under the condition of not using copper ions for activation, and has poor flotation effect on lead sulfide ore. However, 2-aminothiophenol is a weakly acidic compound and does not sufficiently act on zinc sulfide ore at a low pH. Therefore, the components of the combined collector can complement each other, and the effect that 1+1 is more than 2 is achieved.

(3) The invention has simple field application, only needs to adjust the medicament proportion, does not need to change the field process flow, has simple operation and stable index.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

According to the invention, the lead collecting agents are ethidium nitrogen and butyl ammonium black, the combined zinc collecting agents are butyl ammonium black, ethidium nitrogen and 2-aminothiophenol, the difference of the components of the two agents is similar, and a zinc inhibitor is added in the lead flotation process to prevent the ethidium nitrogen and the butyl ammonium black from collecting zinc, so that the grade of lead concentrate is improved. During zinc flotation, a zinc activating agent is added to fully act with a collecting agent to generate chemical adsorption, 2-amino thiophenol is added into the collecting agent to promote the collection of zinc, the floating speed of zinc is accelerated, and the recovery rate of zinc is improved.