阅读说明：本技术 一种次生硫化铜矿抑制剂及其制备和应用 (Secondary copper sulfide ore inhibitor and preparation and application thereof ) 是由 崔立凤 田树国 孙忠梅 唐浪峰 丛颖 梁治安 周利华 李继福 缪彦 于 2021-08-11 设计创作，主要内容包括：本发明公开了一种次生硫化铜矿抑制剂及其制备和应用,抑制剂的原料按重量百分比包括二氯异氰尿酸钠和三氯异氰尿酸钠中的一种或两种的混合物70％-80％、羧甲基纤维素钠0％-10％、氯化钠20％-30％。本发明开发一种适应性强、绿色环保、对以次生硫化铜矿为主的铜锌多金属矿浮选分离效果好的次生硫化铜矿抑制剂,特别适合黄铁矿含量高、易产酸、重金属盐类难免离子含量高、铜锌矿物嵌布粒度细、铜矿物以次生硫化铜为主的铜锌矿石的铜锌分离；同时也适用于以次生硫化铜矿为主的其它铜多金属矿选矿分离。(The invention discloses a secondary copper sulfide ore inhibitor and preparation and application thereof, wherein the raw materials of the inhibitor comprise 70-80% of one or a mixture of two of sodium dichloroisocyanurate and sodium trichloroisocyanurate, 0-10% of sodium carboxymethylcellulose and 20-30% of sodium chloride by weight percentage. The invention develops the secondary copper sulfide ore inhibitor which has strong adaptability, is green and environment-friendly, has good flotation separation effect on copper-zinc polymetallic ores which mainly contain secondary copper sulfide ores, and is particularly suitable for copper-zinc separation of copper-zinc ores which contain high pyrite content, easily produce acid, have high content of heavy metal salts and unavoidable ions, have fine copper-zinc mineral disseminated particle size and mainly contain secondary copper sulfide; meanwhile, the method is also suitable for mineral separation of other copper polymetallic ores mainly containing secondary copper sulfide ores.)

1. The secondary copper sulfide ore inhibitor is characterized in that the raw materials comprise 70-80 wt% of one or a mixture of two of sodium dichloroisocyanurate and sodium trichloroisocyanurate, 0-10 wt% of sodium carboxymethylcellulose and 20-30 wt% of sodium chloride.

2. A method of producing a secondary copper sulfide ore inhibitor as claimed in claim 1, comprising the steps of:

s1, weighing the raw materials according to the weight percentage, and uniformly mixing the raw materials;

s2, filling the uniformly mixed material obtained in the step S1 into a conical flask, plugging a bottle opening with a bottle plug, putting the conical flask into a constant-temperature vibration table, adjusting the temperature of the constant-temperature vibration table to 15-40 ℃, the rotation speed to 100-.

3. Use of the secondary copper sulfide ore inhibitor of claim 1 in copper-zinc separation of refractory copper-zinc ores.

4. Use according to claim 3, characterized in that it comprises the following steps:

(1) grinding: crushing copper-zinc ores of secondary copper sulfide ores, mixing the crushed copper-zinc ores with water, grinding the ores, adding lime into a grinder during grinding until the fineness of the product is-0.075 mm accounting for 80%, and the pH value of ore pulp is 5.5-7.5;

(2) copper and zinc mixing and roughing operation: adding the ground minerals into a single-groove flotation machine, adding a sulfide collecting agent, namely amyl xanthate, stirring, adding foaming agent, namely pine oil, stirring, and then carrying out copper-zinc mixed roughing operation, wherein the concentrate obtained in the copper-zinc mixed roughing operation is copper-zinc mixed roughing concentrate I, and the tailings obtained in the copper-zinc mixed roughing operation enter copper-zinc mixed roughing operation;

(3) and (2) carrying out copper-zinc mixing and roughing operation: adding a sulfide ore collecting agent amyl xanthate into tailings obtained in the first copper-zinc mixed roughing operation, stirring, adding a foaming agent pinitol oil, stirring, and then performing second copper-zinc mixed roughing operation, wherein the concentrate obtained in the second copper-zinc mixed roughing operation is second copper-zinc mixed roughing concentrate, and the tailings enter third copper-zinc mixed roughing operation;

(4) three operations of copper and zinc mixing and roughing: adding a sulfide ore collecting agent amyl xanthate into the tailings obtained by the second copper-zinc mixed roughing operation, stirring, adding a foaming agent pinitol oil, stirring, and then performing third copper-zinc mixed roughing operation, wherein the concentrate obtained by the third copper-zinc mixed roughing operation is a third copper-zinc mixed roughing concentrate, and the tailings obtained by the third copper-zinc mixed roughing operation is a first tailing;

(5) regrinding copper-zinc mixed rough concentrate: combining the copper-zinc mixed rough concentrate I, the copper-zinc mixed rough concentrate II and the copper-zinc mixed rough concentrate III to obtain copper-zinc mixed rough concentrate, finely grinding the copper-zinc mixed rough concentrate, and then performing copper-zinc separation and zinc roughing operation;

(6) separating copper from zinc and roughing zinc: adding finely ground copper-zinc mixed rough concentrate into a single-tank flotation machine, adding lime to adjust the pH value of the ore slurry to 12-12.5, stirring, adding the secondary copper sulfide ore inhibitor, stirring, adding amyl xanthate, stirring, adding a foaming agent terpineol, stirring, performing copper-zinc separation and zinc roughing operation, wherein the concentrate obtained in the copper-zinc separation and zinc roughing operation is zinc rough concentrate, performing zinc concentration operation, and performing copper-zinc separation and zinc scavenging operation on tailings obtained in the copper-zinc separation and zinc roughing operation;

(7) and (3) copper-zinc separation zinc scavenging operation: adding the secondary copper sulfide ore inhibitor into tailings obtained by copper-zinc separation zinc roughing, adding a collecting agent amyl xanthate after stirring, adding a foaming agent terpineol after stirring, performing copper-zinc separation zinc scavenging after stirring, returning concentrate obtained by the copper-zinc separation zinc scavenging to the copper-zinc separation zinc roughing, and allowing the tailings obtained by the copper-zinc separation zinc scavenging to enter the copper roughing;

(8) zinc fine selection, namely an operation: adding the concentrate obtained in the copper-zinc separation and zinc roughing operation into a hanging-groove flotation machine, adding the secondary copper sulfide ore inhibitor, stirring, and then carrying out zinc fine concentration one operation, wherein the concentrate obtained in the zinc fine concentration one operation enters a zinc fine concentration two operation, and the tailings obtained in the zinc fine concentration one operation return to the copper-zinc separation and zinc roughing operation;

(9) and (2) zinc concentration two operations: adding the concentrate obtained in the first zinc concentration operation into a hanging groove flotation machine, adding the secondary copper sulfide ore inhibitor, stirring, and then carrying out second zinc concentration operation, wherein the concentrate obtained in the second zinc concentration operation is the zinc concentrate, and tailings obtained in the second zinc concentration operation are returned to the first zinc concentration operation;

(10) copper roughing operation: adding a collecting agent Z-200 into tailings obtained in the copper-zinc separation and zinc scavenging operation, stirring, and then carrying out copper roughing operation, wherein the concentrate obtained in the copper roughing operation is copper rough concentrate, and then carrying out copper concentration operation, and the tailings obtained in the copper roughing operation are subjected to copper scavenging operation;

(11) copper scavenging one operation: adding a collecting agent Z-200 into tailings obtained in the copper roughing operation, stirring for 2 minutes, and then performing a first copper scavenging operation, returning concentrate obtained in the first copper scavenging operation to the copper roughing operation, and allowing tailings obtained in the first copper scavenging operation to enter a second copper scavenging operation;

(12) and (4) copper scavenging operation: adding a collecting agent Z-200 into tailings obtained in the first copper scavenging operation, stirring, and then performing second copper scavenging operation, returning concentrate obtained in the second copper scavenging operation to the first copper scavenging operation, and allowing tailings obtained in the second copper scavenging operation to enter a third copper scavenging operation;

(13) copper scavenging three operations: adding a collecting agent Z-200 into the tailings obtained by the second copper scavenging operation, stirring to perform third copper scavenging operation, returning the concentrate obtained by the third copper scavenging operation to the second copper scavenging operation, and obtaining tailings which are the second tailings;

(14) copper fine selection operation: and adding the copper rough concentrate into a hanging-groove flotation machine to carry out copper concentration operation, wherein the concentrate obtained in the copper concentration operation is the copper concentrate, and the tailings obtained in the copper concentration operation are returned to the copper rough concentration operation.

Technical Field

The invention relates to the technical field of mineral processing, in particular to preparation and application of a secondary copper sulfide ore inhibitor, which is particularly suitable for mineral separation of copper-zinc ores with high pyrite content and high content of unavoidable ions such as copper, zinc, iron and the like in ore pulp after ore grinding, wherein copper minerals mainly contain secondary copper sulfide, and is also suitable for mineral separation of other copper polymetallic ores mainly containing secondary copper sulfide ores.

Background

The copper-zinc polymetallic sulfide ore is an important production raw material for mineral copper and mineral zinc, and is also an important source raw material for smelting and processing copper-zinc metals. At present, the separation of polymetallic ores is one of the difficult problems in the field of ore dressing, the separation of copper-zinc sulfide ores is one of the difficult problems in the separation of polymetallic sulfide ores, and the main reasons for the difficult separation are as follows: firstly, the embedding granularity of the target mineral is fine, and some minerals are contained in an emulsion drop shape and a leaf shape; secondly, copper-containing ore species are various in nature, and the difference of the floatability of the copper sulfide ores belonging to the same genus is large; thirdly, the soluble heavy metal salt content of the copper-zinc polymetallic sulphide ore containing a considerable amount of secondary copper sulphide ore is relatively high, the sphalerite is easy to activate, and the floatability of the activated sphalerite and the chalcopyrite is close to each other, so that the copper and the zinc are difficult to separate; and fourthly, the copper minerals are mainly secondary copper sulfide ores, the content of the pyrite in the raw ores is extremely high, acid is easily generated during grinding of the raw ores, a large amount of inevitable ions are generated, and the difficulty in separating copper from zinc is caused. In short, the copper-zinc polymetallic sulphide ore has large difference in properties, and the separation process conditions are greatly changed, so that the copper-zinc separation is difficult. Therefore, the domestic and foreign beneficiation scholars do a lot of work on the separation of copper and zinc from the copper-zinc polymetallic sulphide ores.

The copper-zinc separation process is divided into a zinc-inhibiting copper floating process and a copper-inhibiting zinc floating process, and the zinc-inhibiting copper floating process is mainly divided into the following methods: cyanide and its mixture zinc inhibition method, sulfurous acid or sulfite and its mixture zinc inhibition method, sodium sulfide and its mixture zinc inhibition method, carboxymethyl cellulose zinc inhibition method. The copper and zinc floating inhibiting process mainly comprises the following methods: heating floatation method, complex method (copper sulfate and sodium thiosulfate complex) hematite method.

In recent years, the research on the flotation and separation of copper-zinc polymetallic sulphide ores mainly focuses on the aspects of theoretical research, the research on novel beneficiation reagents, the research and development of new separation processes and the like, and a plurality of research results are obtained. However, most research directions are based on a copper-zinc separation process of 'zinc suppression and copper flotation', research and development of high-efficiency zinc inhibitors, high-efficiency copper collectors, new processes and the like are developed, and the separation effect is quite good for primary copper sulfide type copper-zinc polymetallic ores, but research results obtained for copper-zinc polymetallic sulfides mainly comprising secondary copper sulfides, particularly for high-sulfur type copper-zinc polymetallic sulfides mainly comprising secondary copper sulfides are relatively limited. The high mutual metal content of copper and zinc products still seriously affects the subsequent smelting process. Therefore, the development of a beneficiation reagent or a beneficiation method for separating copper and zinc from copper-zinc polymetallic sulphide ores mainly containing secondary copper sulphide ores plays an important role in the development of a copper-zinc polymetallic ore flotation separation technology.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a secondary copper sulfide ore inhibitor and preparation and application thereof, develops the secondary copper sulfide ore inhibitor which has strong adaptability, is green and environment-friendly and has good flotation separation effect on copper-zinc polymetallic ores mainly containing secondary copper sulfide ores, and is particularly suitable for copper-zinc separation of copper-zinc ores which have high pyrite content, are easy to produce acid, have high content of heavy metal salts and high content of unavoidable ions, have fine disseminated granularity of copper-zinc minerals and mainly contain secondary copper sulfide in copper minerals; meanwhile, the method is also suitable for mineral separation of other copper polymetallic ores mainly containing secondary copper sulfide ores.

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

the secondary copper sulfide ore inhibitor is prepared with sodium dichloroisocyanurate or sodium trichloroisocyanurate 70-80 wt%, sodium carboxymethylcellulose 0-10 wt% and sodium chloride 20-30 wt%.

The invention also provides a preparation method of the secondary copper sulfide ore inhibitor, which comprises the following steps:

s1, weighing the raw materials according to the weight percentage, and uniformly mixing the raw materials;

s2, filling the uniformly mixed material obtained in the step S1 into a conical flask, plugging a bottle opening with a bottle plug, putting the conical flask into a constant-temperature vibration table, adjusting the temperature of the constant-temperature vibration table to 15-40 ℃, the rotation speed to 100-.

The invention also provides application of the secondary copper sulfide ore inhibitor in copper-zinc separation of refractory copper-zinc ores.

Further, the specific process of the application comprises the following steps:

(1) grinding: crushing copper-zinc ores of secondary copper sulfide ores, mixing the crushed copper-zinc ores with water, grinding the ores, adding lime into a grinder during grinding until the fineness of the product is-0.075 mm accounting for 80%, and the pH value of ore pulp is 5.5-7.5;

(2) copper and zinc mixing and roughing operation: adding the ground minerals into a single-groove flotation machine, adding a sulfide collecting agent, namely amyl xanthate, stirring, adding foaming agent, namely pine oil, stirring, and then carrying out copper-zinc mixed roughing operation, wherein the concentrate obtained in the copper-zinc mixed roughing operation is copper-zinc mixed roughing concentrate I, and the tailings obtained in the copper-zinc mixed roughing operation enter copper-zinc mixed roughing operation;

(3) and (2) carrying out copper-zinc mixing and roughing operation: adding a sulfide ore collecting agent amyl xanthate into tailings obtained in the first copper-zinc mixed roughing operation, stirring, adding a foaming agent pinitol oil, stirring, and then performing second copper-zinc mixed roughing operation, wherein the concentrate obtained in the second copper-zinc mixed roughing operation is second copper-zinc mixed roughing concentrate, and the tailings enter third copper-zinc mixed roughing operation;

(4) three operations of copper and zinc mixing and roughing: adding a sulfide ore collecting agent amyl xanthate into the tailings obtained by the second copper-zinc mixed roughing operation, stirring, adding a foaming agent pinitol oil, stirring, and then performing third copper-zinc mixed roughing operation, wherein the concentrate obtained by the third copper-zinc mixed roughing operation is a third copper-zinc mixed roughing concentrate, and the tailings obtained by the third copper-zinc mixed roughing operation is a first tailing;

(5) regrinding copper-zinc mixed rough concentrate: combining the copper-zinc mixed rough concentrate I, the copper-zinc mixed rough concentrate II and the copper-zinc mixed rough concentrate III to obtain copper-zinc mixed rough concentrate, finely grinding the copper-zinc mixed rough concentrate, and then performing copper-zinc separation and zinc roughing operation;

(6) separating copper from zinc and roughing zinc: adding finely ground copper-zinc mixed rough concentrate into a single-tank flotation machine, adding lime to adjust the pH value of the ore slurry to 12-12.5, stirring, adding the secondary copper sulfide ore inhibitor, stirring, adding amyl xanthate, stirring, adding a foaming agent terpineol, stirring, performing copper-zinc separation and zinc roughing operation, wherein the concentrate obtained in the copper-zinc separation and zinc roughing operation is zinc rough concentrate, performing zinc concentration operation, and performing copper-zinc separation and zinc scavenging operation on tailings obtained in the copper-zinc separation and zinc roughing operation;

(7) and (3) copper-zinc separation zinc scavenging operation: adding the secondary copper sulfide ore inhibitor into tailings obtained by copper-zinc separation zinc roughing, adding a collecting agent amyl xanthate after stirring, adding a foaming agent terpineol after stirring, performing copper-zinc separation zinc scavenging after stirring, returning concentrate obtained by the copper-zinc separation zinc scavenging to the copper-zinc separation zinc roughing, and allowing the tailings obtained by the copper-zinc separation zinc scavenging to enter the copper roughing;

(8) zinc fine selection, namely an operation: adding the concentrate obtained in the copper-zinc separation and zinc roughing operation into a hanging-groove flotation machine, adding the secondary copper sulfide ore inhibitor, stirring, and then carrying out zinc fine concentration one operation, wherein the concentrate obtained in the zinc fine concentration one operation enters a zinc fine concentration two operation, and the tailings obtained in the zinc fine concentration one operation return to the copper-zinc separation and zinc roughing operation;

(9) and (2) zinc concentration two operations: adding the concentrate obtained in the first zinc concentration operation into a hanging groove flotation machine, adding the secondary copper sulfide ore inhibitor, stirring, and then carrying out second zinc concentration operation, wherein the concentrate obtained in the second zinc concentration operation is the zinc concentrate, and tailings obtained in the second zinc concentration operation are returned to the first zinc concentration operation;

(10) copper roughing operation: adding a collecting agent Z-200 into tailings obtained in the copper-zinc separation and zinc scavenging operation, stirring, and then carrying out copper roughing operation, wherein the concentrate obtained in the copper roughing operation is copper rough concentrate, and then carrying out copper concentration operation, and the tailings obtained in the copper roughing operation are subjected to copper scavenging operation;

(11) copper scavenging one operation: adding a collecting agent Z-200 into tailings obtained in the copper roughing operation, stirring for 2 minutes, and then performing a first copper scavenging operation, returning concentrate obtained in the first copper scavenging operation to the copper roughing operation, and allowing tailings obtained in the first copper scavenging operation to enter a second copper scavenging operation;

(12) and (4) copper scavenging operation: adding a collecting agent Z-200 into tailings obtained in the first copper scavenging operation, stirring, and then performing second copper scavenging operation, returning concentrate obtained in the second copper scavenging operation to the first copper scavenging operation, and allowing tailings obtained in the second copper scavenging operation to enter a third copper scavenging operation;

(13) copper scavenging three operations: adding a collecting agent Z-200 into the tailings obtained by the second copper scavenging operation, stirring to perform third copper scavenging operation, returning the concentrate obtained by the third copper scavenging operation to the second copper scavenging operation, and obtaining tailings which are the second tailings;

(14) copper fine selection operation: and adding the copper rough concentrate into a hanging-groove flotation machine to carry out copper concentration operation, wherein the concentrate obtained in the copper concentration operation is the copper concentrate, and the tailings obtained in the copper concentration operation are returned to the copper rough concentration operation.

The invention has the beneficial effects that:

1. the sodium dichloroisocyanurate or sodium trichloroisocyanurate, sodium carboxymethylcellulose, sodium chloride and the like which are used as raw materials of the secondary copper sulfide ore inhibitor are chemical raw materials which are easily purchased in the market, and the raw materials have low price and wide sources and are non-toxic and pollution-free chemical products.

2. The secondary copper sulfide ore inhibitor has simple preparation process, and the product is non-toxic and pollution-free.

3. The secondary copper sulfide ore inhibitor disclosed by the invention is low in dosage of a medicinal agent in the using process and good in effect of inhibiting secondary copper sulfide minerals. Sodium dichloroisocyanurate and/or sodium trichloroisocyanurate and sodium carboxymethyl cellulose react with the surface of mineral to form hydrophilic film on the surface of secondary copper sulfide mineral to inhibit the secondary copper sulfide mineral selectively, and sodium chloride is used in regulating ore pulp and has high selective inhibiting effect and low content of separated product.

Drawings

FIG. 1 is a schematic flow chart of a preparation method of example 5 of the present invention;

FIG. 2 is a process flow diagram of examples 6-9 of the present invention.

Detailed Description

The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.

Example 1

The embodiment provides a secondary copper sulfide ore inhibitor, which comprises 70% of a mixture of sodium dichloroisocyanurate and sodium trichloroisocyanurate, 10% of sodium carboxymethylcellulose and 20% of sodium chloride by weight; wherein the mass ratio of the sodium dichloroisocyanurate to the sodium trichloroisocyanurate is 1: 1.

Example 2

The embodiment provides a secondary copper sulfide ore inhibitor, which comprises 80% of sodium dichloroisocyanurate, 0% of sodium carboxymethylcellulose and 20% of sodium chloride by weight.

Example 3

The embodiment provides a secondary copper sulfide ore inhibitor, which comprises 70% of sodium trichloroisocyanurate, 0% of sodium carboxymethylcellulose and 30% of sodium chloride by weight.

Example 4

The embodiment provides a secondary copper sulfide ore inhibitor, which comprises, by weight, 70% of sodium dichloroisocyanurate, 5% of sodium carboxymethylcellulose and 25% of sodium chloride.

Example 5

The embodiment also provides a preparation method of the secondary copper sulfide ore inhibitor in the embodiment 1-4, which is shown in figure 1 and comprises the following steps:

s1, weighing the raw materials according to the weight percentage, placing the raw materials on a square soft rubber pad, and uniformly mixing the raw materials by adopting a rolling and uniformly mixing method;

the rolling and mixing method includes holding opposite corners of a square soft rubber pad with two hands, drawing the opposite corners of the rubber pad as close as possible to form a certain angle, lifting the opposite corners of the rubber pad with the two hands to move back and forth to roll materials on the rubber pad, changing the other opposite corner after the materials are rolled for 6-9 times to repeat material rolling motion for 6-9 times, and performing reciprocating exchange and rolling for 8-10 times to mix the materials.

S2, filling the uniformly mixed material obtained in the step S1 into a conical flask, plugging a bottle opening with a bottle plug, putting the conical flask into a constant-temperature vibration table, adjusting the temperature of the constant-temperature vibration table to 15-40 ℃, the rotation speed to 100-.

In FIG. 1, a is one or two of sodium dichloroisocyanurate and sodium trichloroisocyanurate, b is sodium carboxymethylcellulose, c is sodium chloride, and E is TC 1912.

Example 6

The refractory copper-zinc multi-metal sulfide ore contains copper minerals mainly including chalcocite and copper blue, a small amount of blue chalcocite, and a very small amount of bornite, chalcopyrite and enargite; the zinc mineral is mainly sphalerite, the impurity mineral is mainly pyrite, the content of the pyrite is high, the content of the pyrite mineral accounts for 65-80% of the ore, and the pyrite mineral contains a small amount of quartz and aluminosilicate minerals.

The copper-zinc separation process test for inhibiting copper and floating zinc is carried out on the raw ores of different mining sections of the mining area by adopting the secondary copper sulfide ore inhibitor described in the embodiment 1-4, wherein the raw ores contain 1.79% of copper and 2.53% of zinc.

As shown in figure 2, raw ore is crushed to 2mm and mixed with water according to the weight ratio of 1:1 for grinding, 3500g of lime is added into a grinding machine per ton of dry weight of the raw ore during grinding, the grinding is carried out until the fineness of the product is-0.075 mm accounting for 80%, and the pH value of ore pulp is 6.8. Adding the ground minerals into a single-groove flotation machine, adding a sulfide mineral collecting agent amyl xanthate with the dosage of 30g/t of dry weight of the raw ore, stirring for 2 minutes, adding a foaming agent pinitol oil with the dosage of 10g/t of dry weight of the raw ore, stirring for 1 minute, and then carrying out copper-zinc mixed roughing, wherein the concentrate (foam product) is the copper-zinc mixed roughing concentrate I, and the tailings enter the copper-zinc mixed roughing II. Adding a sulfide ore collecting agent amyl xanthate into the first copper-zinc mixed rough concentration tailings, wherein the dosage of the amyl xanthate is 20g/t of the dry weight of the raw ore, adding a foaming agent pinitol oil after stirring for 2 minutes, wherein the dosage of the pinitol oil is 5g/t of the dry weight of the raw ore, stirring for 1 minute, performing second copper-zinc mixed rough concentration, wherein the concentrate (foam product) is a second copper-zinc mixed rough concentrate, and the tailings enter a third copper-zinc mixed rough concentration. Adding a sulfide ore collecting agent amyl xanthate into the tailings of the second copper-zinc mixed rough concentration, wherein the dosage of the amyl xanthate is 10g/t of the dry weight of the raw ore, adding a foaming agent pinitol oil after stirring for 2 minutes, the dosage of the pinitol oil is 3g/t of the dry weight of the raw ore, and after stirring for 1 minute, carrying out third copper-zinc mixed rough concentration, wherein the concentrate (foam product) is the third copper-zinc mixed rough concentrate, and the tailings are the first tailings. And combining the copper-zinc mixed rough concentrate I, the copper-zinc mixed rough concentrate II and the copper-zinc mixed rough concentrate III to obtain copper-zinc mixed rough concentrate, finely grinding by using an Aisha grinding machine until the product fineness is-0.030 mm and the content accounts for 80%, and performing copper-zinc separation by using a copper-restraining and zinc-floating process. Adding finely ground copper-zinc mixed rough concentrate into a single-tank flotation machine, adding 5000g/t of lime of raw ore dry weight to adjust the pH value of ore pulp, adjusting the pH value of the ore pulp to 12.26, stirring for 3 minutes, adding the inhibitor TC1912 described in example 1 in an amount of 1200g/t of the raw ore dry weight, stirring for 3 minutes, adding pentylxanthate in an amount of 5g/t of the raw ore dry weight, stirring for 2 minutes, adding the foaming agent terpineol oil in an amount of 10g/t of the raw ore dry weight, stirring for 1 minute, performing copper-zinc separation and rough separation, wherein the concentrate (foam product) is zinc rough concentrate, performing zinc fine separation and tailings are subjected to copper-zinc separation and zinc scavenging. Adding the inhibitor TC1912 described in example 1 into tailings obtained through copper-zinc separation zinc roughing, wherein the using amount is 500g/t of the dry weight of raw ore, stirring for three minutes, adding the collecting agent amyl xanthate, the using amount of the amyl xanthate is 5g/t of the dry weight of the raw ore, stirring for 2 minutes, adding the foaming agent terpineol, the using amount of the foaming agent terpineol is 5g/t of the dry weight of the raw ore, stirring for 1 minute, performing copper-zinc separation zinc scavenging, returning concentrate (foam product) to the copper-zinc separation zinc roughing operation, and enabling the tailings to enter the copper roughing operation. Adding the zinc rough concentrate into a hanging-groove flotation machine, adding the inhibitor TC1912 described in example 1 with the dosage of 350g/t dry weight of raw ore, stirring for three minutes, performing zinc concentration first operation, feeding the concentrate (foam product) into zinc concentration second operation, and returning tailings to copper-zinc separation zinc rough concentration operation. Adding the concentrate obtained in the first zinc concentration operation into a hanging-groove flotation machine, adding the inhibitor TC1912 prepared in the example 1, wherein the dosage is 200g/t of the dry weight of the raw ore, stirring for three minutes, and then carrying out the second zinc concentration operation, wherein the concentrate (foam product) is the zinc concentrate, and the tailings are returned to the first zinc concentration operation. Adding a collecting agent Z-200 into tailings obtained by copper-zinc separation and zinc scavenging, wherein the using amount of the collecting agent Z-200 is 50g/t of the dry weight of raw ore, stirring for 2 minutes, and then carrying out copper roughing operation, wherein the concentrate (foam product) is copper rough concentrate and enters copper concentration operation, and the tailings enter copper scavenging operation. Adding a collecting agent Z-200 into tailings obtained in the copper roughing operation, wherein the using amount of the collecting agent Z-200 is 20g/t of the dry weight of raw ores, stirring for 2 minutes, then carrying out first copper scavenging operation, returning concentrate (foam product) to the copper roughing operation, and enabling the tailings to enter second copper scavenging operation. Adding a collecting agent Z-200 into the tailings obtained in the first copper scavenging operation, wherein the using amount of the collecting agent Z-200 is 10g/t of the dry weight of the raw ore, stirring for 2 minutes, then carrying out second copper scavenging operation, returning the concentrate (foam product) to the first copper scavenging operation, and enabling the tailings to enter third copper scavenging operation. Adding a collecting agent Z-200 into the tailings obtained in the second copper scavenging operation, wherein the using amount of the collecting agent Z-200 is 5g/t of the dry weight of the raw ore, stirring for 2 minutes, then carrying out the third copper scavenging operation, and returning the concentrate (foam product) to the second copper scavenging operation, wherein the tailings are the second tailings. And adding the copper rough concentrate into a hanging-groove flotation machine for copper concentration, wherein the concentrate (foam product) is the copper concentrate, and the tailings are returned to the copper rough concentration operation.

In FIG. 2, d is raw ore, e is lime, f is amyl xanthate, g is pine oil, h is TC1912, and i is Z-200. A is first tailings, B is zinc concentrate, C is second tailings, and D is copper concentrate.

Example 7

The raw ore used in this example contained 1.77% copper and 2.56% zinc, and the copper concentrate contained 36.58% copper and 4.52% zinc, and the copper recovery rate was 84.94%, and the zinc concentrate contained 1.51% copper and 53.08% zinc, and the zinc recovery rate was 81.81%. The flotation process was the same as in example 6, but in this example the depressant TC1912 described in example 2 was used.

Example 8

The raw ore used in this example contained 1.79% copper and 2.63% zinc, and the copper concentrate contained 35.97% copper and 4.63% zinc with a copper recovery of 84.99% and the zinc concentrate contained 1.49% copper and 53.07% zinc with a zinc recovery of 81.60%. The flotation process was the same as in example 6, but in this example the depressant TC1912 described in example 3 was used

Example 9

The raw ore used in this example contained 1.77% copper and 2.59% zinc, and copper concentrate contained 36.12% copper and 4.54% zinc with a copper recovery of 86.14% and zinc concentrate contained 1.43% copper and 53.38% zinc with a zinc recovery of 82.46%. The flotation process was the same as in example 3, but in this example the depressant TC1912 described in example 4 was used.

Comparative example 1

The raw ore used in comparative example 1 contained 1.75% copper and 2.08% zinc.

The comparative example adopts the traditional zinc-inhibiting copper-floating process, adopts the zinc sulfate sodium sulfite system to inhibit zinc and float copper under the traditional high-alkali condition, has high medicament consumption, poor flotation separation effect, high mutual content of concentrate products and low copper-zinc recovery rate, and the experimental indexes of the comparative example are shown in table 1.

TABLE 1 comparative example Experimental indices

Comparative example 2

The raw ore used in this comparative example contained 1.86% copper and 2.64% zinc.

The comparative example adopts the same copper-inhibiting and zinc-floating process flow as that of the examples 6 to 9, and is different from the prior art that D8 is adopted to replace the inhibitor TC1912 to be used as the copper-zinc separation copper inhibitor, so that the flotation separation effect is poor, the copper content in the zinc concentrate is high, the zinc grade of the zinc concentrate is low, and the copper recovery rate of the copper concentrate is low, and the experimental indexes of the comparative example are shown in the table 2.

TABLE 2

The specific process experimental indexes of example 6, example 7, example 8 and example 9 are shown in table 3.

TABLE 3

As can be seen from tables 1, 2 and 3, compared with examples 6-9, in comparative examples 1 and 2, the secondary copper sulfide ore inhibitor TC1912 is used as a copper-zinc separation copper mineral inhibitor, copper and zinc floating is inhibited, copper and zinc minerals can be effectively separated, the recovery rate of copper-zinc concentrate is improved, and the mutual content of concentrate products is reduced. Meanwhile, the raw ores of different ore points are adopted to carry out the copper-zinc separation test of the composite inhibitor TC1912, so that the beneficiation index is stable, the separation effect is good, and the application prospect is good.

Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.