A combined inhibitor of sphalerite and its application

Abstract

The present invention discloses a combined inhibitor for sphalerite and its application. The combined inhibitor includes a reducing substance and anthocyanin. As a combined inhibitor for sphalerite, it is used in the flotation separation of chalcopyrite and sphalerite or galena and sphalerite. After the raw ore is crushed and ground, a combined collector and a frother are added to the pulp to carry out copper-zinc or lead-zinc flotation operation. During the copper-zinc or lead-zinc separation operation, the combined inhibitor is added as a sphalerite inhibitor, isoamyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a frother. The foam product is a copper concentrate or a lead concentrate, and the bottom tank product is a zinc concentrate. The combined inhibitor of the present invention has a strong inhibitory effect on sphalerite and can effectively achieve the flotation separation of chalcopyrite and sphalerite or galena and sphalerite. The reducing substance can enhance the inhibitory effect of anthocyanin on sphalerite and reduce the amount of anthocyanin used, thereby improving the separation effect of copper-zinc and lead-zinc sulfide ores while reducing the mineral processing cost.

Description

Technical Field

[0001] The invention relates to a combined inhibitor of sphalerite and application thereof, belonging to the technical field of ore dressing agents. Background Art

[0002] With the development of the world, demand for copper and lead, as important metals, is increasing. Their unique properties make them indispensable materials for modern life, and they are widely used in aerospace, machinery manufacturing, military chemicals, medical devices, and other fields. The primary sources of copper and lead are chalcopyrite and galena, which often coexist with sphalerite. In industrial production, to completely separate sphalerite from other sulfide ores, the flotation principle of "suppressing more and floating less" is often used, selectively suppressing sphalerite and prioritizing chalcopyrite and galena.

[0003] To date, numerous inorganic and organic compounds have been studied and used to separate sphalerite from other sulfide ores. Cyanide and zinc sulfate are the most widely used sphalerite depressants. However, these inorganic depressants suffer from high toxicity and poor inhibitory effectiveness. Organic depressants, due to their widespread availability, environmental friendliness, and excellent selectivity, have found success in copper-zinc and lead-zinc separations. However, as the proportion of low-grade sulfide ores in industrial production increases and the mineral composition becomes more complex, single organic depressants are unable to meet the flotation industry's demand for maximizing the comprehensive utilization of low-grade, complex copper resources. Mineral processing professionals have discovered that combining organic depressants with inorganic compounds can leverage their respective strengths, combining synergistic effects, solvent effects, and other advantages between the different agents to further enhance sphalerite inhibition. Summary of the Invention

[0004] The present invention aims to provide a method for the efficient flotation separation of copper-zinc and lead-zinc minerals under reducing conditions to address the aforementioned problems. The combined depressant of the present invention selectively depresses sphalerite, achieving stable separation of copper-zinc and lead-zinc minerals.

[0005] The combined inhibitor of the present invention includes a reducing substance and anthocyanidin, wherein the reducing substance is sodium sulfide or ferrous sulfate, and the anthocyanidin is one of cranberry extract, peanut skin extract, and grape seed extract. The mass ratio of the reducing substance to the anthocyanidin depends on the reducing strength of the reducing substance. The mass ratio of sodium sulfide with stronger reducing strength to anthocyanidin is 0.5:1, and the mass ratio of ferrous sulfate with weaker reducing strength to anthocyanidin is 2:1.

[0006] The present invention provides an application of a combined depressant in the flotation separation of copper-zinc and lead-zinc sulfide ores, and the specific steps are as follows:

[0007] (1) grinding the primary ore of copper-zinc sulfide ore or lead-zinc sulfide ore and then slurrying to obtain slurry to be flotated;

[0008] (2) adding a combined collector and a frother to the slurry to be floated in step (1) in sequence to perform mixed roughing operation to obtain mixed coarse concentrate and mixed coarse tailings;

[0009] (3) The mixed coarse concentrate obtained in step (2) is subjected to two blank selections to obtain a final mixed concentrate, and the intermediate ores obtained from the two blank selections are sequentially returned to the previous stage to form a closed loop; a combined collector and a frother are sequentially added to the mixed coarse tailings obtained in step (2) to perform mixed scavenging I to obtain mixed scavenging I concentrate and mixed scavenging I tailings, and a combined collector and a frother are sequentially added to the mixed scavenging I tailings to perform mixed scavenging II to obtain mixed tailings, and the mixed scavenging I concentrate and the mixed scavenging II concentrate are sequentially returned to the previous stage to form a closed loop;

[0010] (4) adding activated carbon powder to the mixed concentrate obtained in step (3) and grinding the ore again; the product after grinding is dehydrated to obtain overflow and sand settling; the overflow is returned to the grinding operation of step (1) to form a closed loop; the sand settling is subjected to separation operation; a combined inhibitor, a collector and a foaming agent are sequentially added to the sand settling to perform separation roughing operation to obtain a separated roughing concentrate and a separated roughing tailing;

[0011] (5) adding a combined inhibitor, a collector, and a frother to the separated rougher concentrate of step (4) in sequence to perform separation and concentration operation I to obtain separation and concentration I concentrate and separation and concentration I tailings, and performing two blank concentrations on the separation and concentration I concentrate to obtain a final concentrate, and returning the middlings from the two blank concentrations to the previous operation to form a closed loop;

[0012] (6) A combined inhibitor, a collector and a foaming agent are sequentially added to the separation roughing tailings of step (4) to perform separation scavenging I operation to obtain separation scavenging I concentrate and separation scavenging I tailings. The separation scavenging I tailings are subjected to separation scavenging II operation without adding any reagents to obtain final zinc concentrate and separation scavenging II concentrate. The separation scavenging II concentrate is returned to the previous stage to form a closed loop.

[0013] The grinding conditions in step (1) of the present invention are: the fineness of -0.074mm accounts for 64-68%; the grinding conditions in step (4) are: the grinding fineness of -0.074mm accounts for 95-98%.

[0014] In step (2), the combined collector is composed of ethyl xanthate and butyl xanthate, wherein the addition ratio of ethyl xanthate to butyl xanthate is 3:5, and the addition amount of the combined collector is 40-120 g / t; the foaming agent is No. 2 oil, and the addition amount is 10-30 g / t.

[0015] In step (4), the combined inhibitor is a reducing substance and anthocyanin, isoamyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 100-500 g / t, the amount of sodium sulfide as the reducing substance is 50-250 g / t, the amount of ferrous sulfate is 200-1000 g / t, the amount of isoamyl xanthate is 15-25 g / t, and the amount of No. 2 oil is 10-20 g / t.

[0016] The combined collector of step (2) and step (3) of the present invention is configured to be added as a 1% mass concentration aqueous solution. In the mixed flotation, the roughing operation time is 7-8 minutes, the scavenging operation time is 5-6 minutes, and the cleaning operation time is 6-7 minutes.

[0017] In step (4), the combined inhibitor is a reducing substance and anthocyanin, isoamyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 300-400 g / t, the amount of the reducing substance sodium sulfide is 150-200 g / t, the amount of ferrous sulfate is 600-800 g / t, the amount of isoamyl xanthate is 30-50 g / t, the amount of No. 2 oil is 20-25 g / t, and the amount of activated carbon in step (4) is 300-500 g / t.

[0018] In step (5), the combined inhibitor is a reducing substance and anthocyanin, isopentyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 50-100 g / t, the amount of sodium sulfide as the reducing substance is 25-50 g / t, the amount of ferrous sulfate is 100-200 g / t, the amount of isopentyl xanthate is 15-25 g / t, and the amount of No. 2 oil is 10-15 g / t.

[0019] In step (6), the combined inhibitor is a reducing substance and anthocyanin, isoamyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 150-200 g / t, the amount of sodium sulfide as the reducing substance is 75-100 g / t, the amount of ferrous sulfate is 300-400 g / t, the amount of isoamyl xanthate is 20-30 g / t, and the amount of No. 2 oil is 15-20 g / t;

[0020] In the steps (4), (5) and (6) of the present invention, the reducing substance and anthocyanidin are configured as an aqueous solution with a mass concentration of 1-3% and added, and the isopentyl xanthate is configured as an aqueous solution with a mass concentration of 5% and added. During the separation operation, the roughing operation time is 5-6 minutes, the scavenging operation time is 4-5 minutes, and the cleaning operation time is 5-6 minutes.

[0021] No. 2 oil is added according to the weight required for the actual ore volume.

[0022] Principle of the Invention: The combined inhibitor comprises sodium sulfide, a reducing agent (ferrous sulfate), and anthocyanins. The invention primarily utilizes the synergistic effect between the reducing agent and anthocyanins to create a combined inhibitor for sphalerite with advantages such as low dosage and strong adaptability to complex ores. Anthocyanins are flavonoids rich in hydroxyl groups, which can adsorb onto metal sites on the surface of sulfide ores, rendering the mineral surface hydrophilic. However, anthocyanins react with oxidizing substances, such as oxygen from the aeration process and inevitably dissolved ions on the mineral surface, reducing their reactivity. However, increasing the anthocyanin dosage to avoid this issue can result in a loss of anthocyanin selectivity. Therefore, adding a reducing agent to the ore slurry for a pre-reduction treatment preserves the anthocyanin activity and also triggers a reduction reaction on the mineral surface, exposing more metal active sites and promoting anthocyanin adsorption on the sphalerite surface. Subsequently, when isopentyl xanthate is used as a collector, chalcopyrite and galena exhibit good floatability, while sphalerite is still strongly suppressed, achieving the desired separation objectives.

[0023] Beneficial effects of the present invention:

[0024] (1) The combined inhibitor provided by the present invention is composed of a reducing substance and anthocyanins. The combined inhibitor has the advantages of good water solubility, wide availability, and biodegradability, avoiding the problems of traditional inorganic inhibitors such as severe toxicity and severe environmental pollution. In addition, the addition of the reducing substance can reduce the amount of anthocyanins used, thereby reducing mineral processing costs.

[0025] (2) The combined inhibitor of the present invention is combined in a certain proportion as a sphalerite inhibitor. Through the synergistic effect between the two agents, it is applied to the flotation separation of copper-zinc sulfide and lead-zinc sulfide, with good separation effect and high concentrate grade, which is of great significance to the efficient recovery and utilization of copper-lead-zinc sulfide ores.

[0026] (3) The reducing substance used in the present invention mainly provides a reducing environment, and is one of sodium sulfide and ferrous sulfate reducing substances. These substances are inexpensive and can reduce the amount of anthocyanins used and the cost of the reagents, while enhancing the separation effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 1 is a process flow chart of an embodiment of the present invention. DETAILED DESCRIPTION

[0028] Example 1: This Example 1 is a flotation separation test study on a copper-zinc sulfide ore in Yunnan. The raw ore contains 0.90-1.00% Cu and 1.60-1.80% Zn. The copper in the ore exists mainly in the form of chalcopyrite, the zinc mainly exists in the form of sphalerite, and the gangue minerals mainly include quartz, dolomite, and feldspar.

[0029] Example 1-1 uses a combined inhibitor reducing substance sodium sulfide and anthocyanin as a sphalerite inhibitor for copper and zinc separation, with a mass ratio of 0.5:1. Figure 1 The specific steps are as follows:

[0030] (1) The copper-zinc sulfide ore is crushed and ground to a fineness of -0.074 mm, accounting for 64%, to obtain a pulp to be flotated;

[0031] (2) adding a copper-zinc mineral combined collector and a frother to the ore pulp to be floated in step (1) in sequence, wherein the combined collector consists of ethyl xanthate and butyl xanthate, wherein the addition ratio of ethyl xanthate to butyl xanthate is 3:5, the dosage is 120 g / t, and the dosage of the frother No. 2 oil is 25 g / t, and performing a copper-zinc mixed roughing operation, the roughing time is 7 minutes, and obtaining a copper-zinc mixed rough concentrate and a copper-zinc mixed rough tailings;

[0032] (3) The copper-zinc mixed coarse concentrate in step (2) is subjected to two blank selections, each selection operation time is 6 minutes, and the final copper-zinc mixed concentrate is obtained, wherein the middlings of copper-zinc mixed selection I and II are respectively returned to the copper-zinc mixed roughing and copper-zinc mixed selection I to form a closed loop, and a combined collector is added to the copper-zinc mixed coarse tailings in an amount of 80g / t and a foaming agent No. 2 oil is 15g / t. After copper-zinc mixed scavenging I, a mixed scavenging I concentrate and a mixed scavenging I tailing are obtained, and then a combined collector is added to the copper-zinc mixed scavenging I tailings in an amount of 40g / t and a foaming agent No. 2 oil is 10g / t. After copper-zinc mixed scavenging II, each scavenging operation time is 5 minutes to obtain a final tailing, and the copper-zinc mixed scavenging I and II concentrates are respectively returned to the copper-zinc mixed roughing and copper-zinc mixed scavenging I to form a closed loop;

[0033] (4) The copper-zinc mixed concentrate product obtained in step (3) is introduced into a ball mill and 500 g / t of activated carbon powder is added at the same time, and ground to a fineness of -0.074 mm accounting for 95%. After dehydration, the overflow is returned to the pre-roughing grinding operation, and the sediment enters the copper-zinc separation operation. 200 g / t of sodium sulfide and 400 g / t of anthocyanin are sequentially added to the sediment as a sphalerite combination inhibitor, 30 g / t of isopentyl xanthate as a collector, and 20 g / t of No. 2 oil as a foaming agent. After a separation and roughing operation, the roughing operation time is 5 minutes to obtain a copper roughing concentrate and a copper roughing tailings.

[0034] (5) Add 50 g / t sodium sulfide and 100 g / t anthocyanin as a sphalerite combination inhibitor, 15 g / t isopentyl xanthate as a collector, and 10 g / t No. 2 oil as a foaming agent to the copper roughing concentrate of step (4), and perform separation and selection I operation to obtain separation and selection I concentrate and separation and selection I tailings. The separation and selection I concentrate is subjected to two blank selections, each selection operation time is 5 minutes, to obtain the final copper concentrate, wherein the tailings of copper selection I, II, and III are returned to the copper roughing, copper selection I, and copper selection II respectively. A closed-loop cycle was formed. 100 g / t sodium sulfide and 200 g / t anthocyanin were added to the copper rougher tailings as a combined zinc blende inhibitor, 20 g / t isopentyl xanthate was used as a collector, and 15 g / t No. 2 oil was used as a foaming agent to carry out separation scavenging I to obtain separation scavenging I concentrate and separation scavenging I tailings. The separation scavenging I tailings were subjected to a blank scavenging operation with each scavenging operation time of 4 minutes to obtain the final zinc concentrate. The copper scavenging I and II concentrates were returned to the copper rougher and copper scavenging I respectively to form a closed-loop cycle. The product indicators are shown in Table 1.

[0035] In Example 1-2, the reducing substances ferrous sulfate and anthocyanin were used as a combined sphalerite depressant for copper and zinc separation, with a mass ratio of 2:1. The amounts of ferrous sulfate and anthocyanin added to the copper and zinc separation process were 800 g / t and 400 g / t, 200 g / t and 100 g / t, and 400 g / t and 200 g / t, respectively, in the roughing, cleaning, and scavenging processes, respectively. Other process conditions remained unchanged, and the product specifications are shown in Table 1.

[0036] Comparative Examples 1-3: Copper-zinc separation was performed using conventional zinc sulfate as a sphalerite inhibitor. The addition amounts of zinc sulfate in the roughing, cleaning I, and scavenging I stages of the copper-zinc separation were 1000 g / t, 400 g / t, and 700 g / t, respectively. Other process conditions remained unchanged. The product specifications are shown in Table 1.

[0037] Comparative Examples 1-4: A single anthocyanin was used as a sphalerite inhibitor for copper-zinc separation. The anthocyanin addition amounts in the roughing, cleaning I, and scavenging I stages of the copper-zinc separation were 500 g / t, 200 g / t, and 300 g / t, respectively. Other process conditions remained unchanged. The product indicators are shown in Table 1.

[0038] Table 1 Flotation separation results of Example 1

[0039]

[0040]

[0041] It can be seen from Table 1 that under the condition of the lowest dosage of reagents, the grade of copper concentrate and the recovery rate of copper increased by 2.73 percentage points and 4.74 percentage points compared with the zinc sulfate inhibitor for single anthocyanin, and the grade of zinc in the copper concentrate decreased by 3.52 percentage points; while the grade of copper concentrate and the recovery rate of copper increased compared with the single anthocyanin inhibitor for combined inhibitors. The grade and recovery rate of copper concentrate for combined inhibitors sodium sulfide and anthocyanin increased by 4.07 percentage points and 5.74 percentage points, respectively. The grade and recovery rate of copper concentrate for combined inhibitors ferrous sulfate and anthocyanin increased by 4.3 percentage points and 4.11 percentage points, respectively. Moreover, the grade of zinc in the copper concentrate also decreased, which decreased by 3.18 percentage points for combined inhibitors sodium sulfide and anthocyanin, and by 3.08 percentage points for combined inhibitors ferrous sulfate and anthocyanin. This indicates that the addition of reducing substances can enhance the inhibition of anthocyanin on sphalerite and improve the recovery rate of copper.

[0042] Example 2: This Example 2 conducted a flotation separation test on a lead-zinc sulfide ore in Yunnan. The raw ore contained 3.05-3.15% Pb and 4.40-4.50% Zn. The lead in the ore existed primarily as galena, the zinc primarily as sphalerite, and the gangue minerals primarily included quartz and dolomite.

[0043] Example 2-1 uses a combined inhibitor reducing substance sodium sulfide and anthocyanin as a galena inhibitor for lead and zinc separation, with a mass ratio of 1:2. Figure 1 The specific steps are as follows:

[0044] (1) Grinding the primary ore to a fineness of -0.074 mm (68%) by crushing and grinding to obtain slurry to be flotated;

[0045] (2) adding 120 g / t of lead-zinc mineral combined collector and 25 g / t of No. 2 foaming agent to the slurry to be floated, and performing lead-zinc mixed roughing for 8 minutes to obtain lead-zinc mixed rough concentrate and lead-zinc mixed rough tailings;

[0046] (3) The lead-zinc mixed coarse concentrate in step (2) is blank-selected twice, and each selection operation time is 7 minutes to obtain a final lead-zinc mixed concentrate, wherein the concentrates of lead-zinc mixed selection I and II are respectively returned to the lead-zinc mixed roughing and lead-zinc mixed selection I to form a closed loop, and a combined collector is added to the lead-zinc mixed coarse tailings in an amount of 80g / t and a foaming agent No. 2 oil is 15g / t, and the lead-zinc mixed scavenging I is subjected to lead-zinc mixed scavenging I to obtain lead-zinc mixed scavenging I concentrate and lead-zinc mixed scavenging I tailings; and a combined collector is added to the lead-zinc mixed scavenging I tailings in an amount of 40g / t and a foaming agent No. 2 oil is 10g / t, and the lead-zinc mixed scavenging II is subjected to lead-zinc mixed scavenging II, and each scavenging operation time is 6 minutes to obtain a final tailing, and the lead-zinc mixed scavenging I and II concentrates are respectively returned to the lead-zinc mixed roughing and lead-zinc mixed scavenging I to form a closed loop;

[0047] (4) The lead-zinc mixed concentrate product is introduced into a ball mill and 500 g / t of activated carbon powder is added. It is ground to a fineness of -0.074 mm, accounting for 98%. After dehydration, the overflow is returned to the pre-roughing grinding operation, and the sand is sent to the lead-zinc separation operation. The lead-zinc separation flotation operation is carried out, and 150 g / t of sodium sulfide and 300 g / t of anthocyanin are added as sphalerite combined inhibitors, 50 g / t of isopentyl xanthate is used as a collector, and 25 g / t of No. 2 oil is used as a frother. After a roughing operation, the roughing operation time is 6 minutes to obtain a lead roughing concentrate and a lead roughing tailing.

[0048] (6) 25 g / t sodium sulfide and 50 g / t anthocyanin were added to the lead roughing concentrate in step (5) as a sphalerite combination inhibitor, 25 g / t isopentyl xanthate was used as a collector, and 15 g / t No. 2 oil was used as a foaming agent to perform lead concentration I; the lead concentration I concentrate was subjected to two blank concentrations, each concentration operation time was 6 minutes, and the final lead concentrate was obtained, wherein the concentrates of lead concentration I, II, and III were respectively returned to the lead roughing, lead concentration I, and lead concentration II to form a closed system. The lead roughing tailings were subjected to a closed-circuit cycle, with 75 g / t sodium sulfide and 150 g / t anthocyanin added as a combined zinc blend inhibitor, 30 g / t isopentyl xanthate as a collector, and 20 g / t No. 2 oil as a frother, to carry out lead scavenging I. The lead scavenging I tailings were subjected to a blank scavenging, with each scavenging operation lasting 5 minutes to obtain the final zinc concentrate. The lead scavenging I and II concentrates were returned to the lead roughing and lead scavenging I, respectively, to form a closed-circuit cycle. The product indicators are shown in Table 2.

[0049] Example 2-2 used the reducing substances ferrous sulfate and anthocyanin as a combined sphalerite depressant for copper and zinc separation, with a mass ratio of 2:1. The amounts of ferrous sulfate and anthocyanin added in the roughing, cleaning I, and scavenging I stages of the copper and zinc separation were 600 g / t and 300 g / t, 100 g / t and 50 g / t, and 300 g / t and 150 g / t, respectively. Other process conditions remained unchanged, and the product specifications are shown in Table 2.

[0050] Comparative Example 2-3: Lead-zinc separation was performed using conventional inhibitor zinc sulfate as a sphalerite inhibitor, wherein the addition amounts of zinc sulfate in the roughing, cleaning I, and scavenging I stages of the lead-zinc separation were 1000 g / t, 400 g / t, and 700 g / t, respectively. Other process conditions remained unchanged, and the product indicators were shown in Table 2.

[0051] Comparative Example 2-4: Copper-lead separation was performed using a single anthocyanin as a sphalerite inhibitor. The anthocyanin addition amounts in the roughing, cleaning I, and scavenging I stages of the lead-zinc separation were 400 g / t, 100 g / t, and 200 g / t, respectively. Other process conditions remained unchanged. The product indicators are shown in Table 2.

[0052] Table 2 Flotation separation results of Example 2

[0053]

[0054] It can be seen from Table 1 that under the lowest dosage conditions, the grade and lead recovery rate of lead concentrate with single anthocyanin increased by 3.66 percentage points and 2.47 percentage points respectively compared with zinc sulfate inhibitor, and the grade of zinc in lead concentrate decreased by 1.23 percentage points, indicating that the inhibition effect of single anthocyanin on sphalerite was not as good as zinc sulfate; the grade and lead recovery rate of lead concentrate with combined inhibitors increased compared with single anthocyanin inhibitor, the grade and lead recovery rate of lead concentrate with combined inhibitors sodium sulfide and anthocyanin increased by 2.65 percentage points and 0.77 percentage points respectively, and the grade and lead recovery rate of lead concentrate with combined inhibitors ferrous sulfate and anthocyanin increased by 3.71 percentage points and 0.18 percentage points respectively, and the grade of zinc in lead concentrate also decreased, the grade of combined inhibitors sodium sulfide and anthocyanin decreased by 2.13 percentage points, and the grade of combined inhibitors ferrous sulfate and anthocyanin decreased by 2.15 percentage points, indicating that the addition of reducing substances can enhance the inhibition of anthocyanin on sphalerite and improve the recovery rate of lead.

[0055] Example 3: This Example 3 conducted a flotation separation test on a copper-zinc sulfide ore in Inner Mongolia Autonomous Region. The ore contained 2.90-3.00% Cu and 1.7-1.8% Zn. The lead in the ore existed primarily as galena, the zinc primarily as sphalerite, and the gangue minerals primarily included quartz, pyroxene, garnet, and feldspar.

[0056] Example 3-1 uses a combined inhibitor reducing substance sodium sulfide and anthocyanin as a sphalerite inhibitor for copper and zinc separation, with a mass ratio of 0.5:1. Figure 1 The specific steps are as follows:

[0057] (1) The copper-zinc sulfide ore is crushed and ground to a fineness of -0.074 mm accounting for 66% to obtain a pulp to be flotated;

[0058] (2) adding a copper-zinc mineral combined collector and a frother to the ore pulp to be floated in step (1) in sequence, wherein the combined collector consists of ethyl xanthate and butyl xanthate, wherein the addition ratio of ethyl xanthate to butyl xanthate is 3:5, the dosage is 120 g / t, and the dosage of the frother No. 2 oil is 25 g / t, and performing a copper-zinc mixed roughing operation, the roughing time is 7 minutes, and obtaining a copper-zinc mixed rough concentrate and a copper-zinc mixed rough tailings;

[0059] (3) The copper-zinc mixed coarse concentrate in step (2) is subjected to two blank selections, each selection operation time is 6 minutes, and the final copper-zinc mixed concentrate is obtained, wherein the middlings of copper-zinc mixed selection I and II are respectively returned to the copper-zinc mixed roughing and copper-zinc mixed selection I to form a closed loop, and a combined collector is added to the copper-zinc mixed coarse tailings in an amount of 80g / t and a foaming agent No. 2 oil is 15g / t. After copper-zinc mixed scavenging I, a mixed scavenging I concentrate and a mixed scavenging I tailing are obtained, and then a combined collector is added to the copper-zinc mixed scavenging I tailings in an amount of 40g / t and a foaming agent No. 2 oil is 10g / t. After copper-zinc mixed scavenging II, each scavenging operation time is 5 minutes to obtain a final tailing, and the copper-zinc mixed scavenging I and II concentrates are respectively returned to the copper-zinc mixed roughing and copper-zinc mixed scavenging I to form a closed loop;

[0060] (4) The copper-zinc mixed concentrate product obtained in step (3) is introduced into a ball mill and 500 g / t of activated carbon powder is added at the same time, and ground to a fineness of -0.074 mm accounting for 97%. After dehydration, the overflow is returned to the pre-roughing grinding operation, and the sediment enters the copper-zinc separation operation. 175 g / t of sodium sulfide and 350 g / t of anthocyanin are sequentially added to the sediment as a sphalerite combination inhibitor, 40 g / t of isopentyl xanthate as a collector, and 22 g / t of No. 2 oil as a foaming agent. After a separation and roughing operation, the roughing operation time is 5 minutes to obtain a copper roughing concentrate and a copper roughing tailings.

[0061] (5) Add 40 g / t sodium sulfide and 80 g / t anthocyanin as a sphalerite combination inhibitor, 20 g / t isopentyl xanthate as a collector, and 12 g / t No. 2 oil as a foaming agent to the copper roughing concentrate of step (4), and perform separation and selection I operation to obtain separation and selection I concentrate and separation and selection I tailings. The separation and selection I concentrate is subjected to two blank selections, each selection operation time is 5 minutes, to obtain the final copper concentrate, wherein the tailings of copper selection I, II, and III are returned to the copper roughing, copper selection I, and copper selection II respectively. The copper rougher tailings were added with 90 g / t sodium sulfide and 180 g / t anthocyanin as a combined zinc blend inhibitor, 25 g / t isopentyl xanthate as a collector, and 17 g / t No. 2 oil as a foaming agent to form a closed loop. Separation scavenging I was carried out to obtain separation scavenging I concentrate and separation scavenging I tailings. The separation scavenging I tailings were subjected to a blank scavenging operation with each scavenging operation time of 4 minutes to obtain the final zinc concentrate. The copper scavenging I and II concentrates were returned to the copper rougher and copper scavenging I respectively to form a closed loop. The product indicators are shown in Table 3.

[0062] Example 3-2 used the reducing substances ferrous sulfate and anthocyanin as a combined sphalerite depressant for copper and zinc separation, with a mass ratio of 2:1. The amounts of ferrous sulfate and anthocyanin added in the roughing, cleaning I, and scavenging I processes for copper and zinc separation were 700 g / t and 350 g / t, 160 g / t and 80 g / t, and 360 g / t and 180 g / t, respectively. Other process conditions remained unchanged, and the product specifications are shown in Table 3.

[0063] Table 3 Flotation separation results of Example 3

[0064]

[0065] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any modifications of various equivalent forms based on the technical essence of the present invention made by those skilled in the art shall fall within the scope defined by the claims attached to this application.

Claims

1. A combined inhibitor of sphalerite, characterized in that: The combined inhibitor includes a reducing substance and anthocyanins, wherein the reducing substance is sodium sulfide or ferrous sulfate, and the anthocyanins are one of cranberry extract, peanut skin extract, and grape seed extract. The mass ratio of the reducing substance to the anthocyanins depends on the reducing strength of the reducing substance; the mass ratio of sodium sulfide with stronger reducing properties to anthocyanins is 0.5:1, and the mass ratio of ferrous sulfate with weaker reducing properties to anthocyanins is 2:

1.

2. The combined inhibitor of sphalerite according to claim 1, characterized in that: The combined depressant is used for flotation separation of chalcopyrite and sphalerite or galena and sphalerite.

3. Use of the combined inhibitor for sphalerite according to claim 1 or 2 in the flotation separation of chalcopyrite and sphalerite or galena and sphalerite, characterized in that: The specific steps are as follows: (1) Grinding the primary ore of copper-zinc sulfide ore or lead-zinc sulfide ore and then slurrying to obtain slurry to be flotated; (2) adding a combined collector and a frother to the slurry to be floated in step (1) in sequence to perform mixed roughing operation to obtain mixed coarse concentrate and mixed coarse tailings; (3) The mixed coarse concentrate obtained in step (2) is subjected to two blank selections to obtain a final mixed concentrate, and the intermediate ores obtained from the two blank selections are returned to the previous stage in sequence to form a closed loop; a combined collector and a frother are sequentially added to the mixed coarse tailings obtained in step (2) to perform mixed scavenging I to obtain mixed scavenging I concentrate and mixed scavenging I tailings, and a combined collector and a frother are sequentially added to the mixed scavenging I tailings to perform mixed scavenging II to obtain mixed tailings, and the mixed scavenging I concentrate and the mixed scavenging II concentrate are sequentially returned to the previous stage to form a closed loop; (4) adding activated carbon powder to the mixed concentrate obtained in step (3) and grinding the ore again; the product after grinding is dehydrated to obtain overflow and sedimentation; the overflow is returned to the grinding operation of step (1) to form a closed loop; the sedimentation is separated; a combined inhibitor, a collector and a foaming agent are sequentially added to the sedimentation to perform a separation roughing operation to obtain a separated roughing concentrate and a separated roughing tailing; (5) adding a combined depressant, a collector and a frother to the separated rougher concentrate of step (4) in sequence to perform separation and concentration operation I, thereby obtaining separation and concentration I concentrate and separation and concentration I tailings, and performing two blank concentrations on the separation and concentration I concentrate to obtain a final concentrate, and returning the middlings from the two blank concentrations to the previous operation to form a closed loop; (6) A combined inhibitor, a collector and a foaming agent are sequentially added to the separation roughing tailings of step (4) to perform separation scavenging I operation to obtain separation scavenging I concentrate and separation scavenging I tailings. The separation scavenging I tailings are subjected to separation scavenging II operation without adding any reagents to obtain final zinc concentrate and separation scavenging II concentrate. The separation scavenging II concentrate is returned to the previous stage to form a closed loop.

4. Use of the combined inhibitor for sphalerite according to claim 3 in the flotation separation of chalcopyrite and sphalerite or galena and sphalerite, characterized in that: Step (1) grinding the ore to a particle fineness of -0.074 mm accounts for 64% to 68%; step (4) grinding the ore to a particle fineness of -0.074 mm accounts for 95% to 98%.

5. Use of the combined inhibitor for sphalerite according to claim 3 in the flotation separation of chalcopyrite and sphalerite or galena and sphalerite, characterized in that: In step (2), the combined collector is composed of ethyl xanthate and butyl xanthate, wherein the addition ratio of ethyl xanthate to butyl xanthate is 3:5, and the addition amount of the combined collector is 40-120 g / t; the foaming agent is No. 2 oil, and the addition amount is 10-25 g / t.

6. Use of the combined inhibitor for sphalerite according to claim 3 in the flotation separation of chalcopyrite and sphalerite or galena and sphalerite, characterized in that: In step (4), the combined inhibitor is a reducing substance and anthocyanin, isopentyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 300-400 g / t, the amount of the reducing substance sodium sulfide is 150-200 g / t, the amount of ferrous sulfate is 600-800 g / t, the amount of isopentyl xanthate is 30-50 g / t, the amount of No. 2 oil is 20-25 g / t, and the amount of activated carbon in step (4) is 300-500 g / t.

7. Use of the combined inhibitor for sphalerite according to claim 4 in the flotation separation of chalcopyrite and sphalerite or galena and sphalerite, characterized in that: In step (5), the combined inhibitor is a reducing substance and anthocyanin, isoamyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 50-100 g / t, the amount of sodium sulfide as a reducing substance is 25-50 g / t, the amount of ferrous sulfate is 100-200 g / t, the amount of isoamyl xanthate is 15-25 g / t, and the amount of No. 2 oil is 10-15 g / t; in step (6), the combined inhibitor is a reducing substance and anthocyanin, isoamyl xanthate is used as a chalcopyrite or galena collector, and No. 2 oil is used as a foaming agent, wherein the amount of anthocyanin is 150-200 g / t, the amount of sodium sulfide as a reducing substance is 75-100 g / t, and the amount of sodium sulfide as a reducing substance is 100-100 g / t. g / t, the dosage of ferrous sulfate is 300~400g / t, the dosage of isopentyl xanthate is 20~30g / t, and the dosage of No. 2 oil is 15~20g / t.

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