Collecting agent special for copper smelting slag flotation and application method thereof

Abstract

The invention relates to a collecting agent special for copper smelting slag flotation, which is brown yellow oily liquid and is prepared by uniformly stirring the following raw materials in parts by weight at room temperature: 1 part of liquid ammonium dibutyl dithiophosphate, 0.5-1 part of ethyl xanthic acid propionitrile ester and / or butyl xanthic acid propionitrile ester, 0.5-1 part of sulfur nitrogen nitrile ester and 1-1.5 parts of ethylene glycol butyl ether. Meanwhile, the invention further discloses an application method of the collecting agent. A mutually soluble and stable oily liquid product is formed by using multiple collecting agent components at the same time, the cost is low, production, transportation and adding use are easy, and the collecting rate and recovery rate of copper ore and copper smelting slag flotation can be increased.

Description

Technical Field

[0001] The invention relates to the field of mineral processing, and in particular to a collector special for flotation of copper smelting slag and an application method thereof. Background Art

[0002] Copper smelting slag is the slag produced by copper smelting enterprises using pyrometallurgy to extract copper metal. Currently, 80% of the world's copper is produced by pyrometallurgy. According to different slag production equipment, copper smelting slag can be divided into reverberatory slag, converter slag, electric furnace slag, etc. According to different slag cooling methods, it can be divided into water residue slag, natural cooling slag, insulation cooling slag, etc. In addition to a large amount of copper, copper smelting slag also contains a variety of valuable metals such as Fe, Zn, Pb, Co, Ni, and a small amount of precious metals such as Au and Ag. Therefore, effectively recovering the valuable components in copper smelting slag is an important way to achieve resource utilization of copper slag and sustainable development of copper smelting.

[0003] Copper smelting slag is generally enriched and recovered by flotation process. However, due to the difference in smelting process, the ore properties of copper smelting slag vary greatly, and the flotation process and mineral processing reagents used are also different. The 491st issue of the journal Metal Mines disclosed a process for flotation recovery of copper from a slow-cooled copper smelting slag. When the grinding fineness was -0.045mm, accounting for 90%, two roughing selections (one roughing selection directly obtained a high-grade copper concentrate), three cleaning selections, and two scavenging selections were adopted. The amount of collector BK-908 and the amount of frother 2# oil in the first stage of copper sulfide roughing selection was 20g / t, and the amount of collector EP in the second stage of sulfide roughing selection was 40g / t, the amount of lime as a pulp pH adjuster was 500g / t, the amount of sulfiding agent sodium sulfide was 250g / t, and the amount of frother 2# oil was 30g / t. Finally, a copper concentrate with a copper grade of 17.77% and a copper recovery rate of 89.38% was obtained. The journal "Nonferrous Metallurgy Design and Research" Vol. 35 No. 6 disclosed the beneficiation practice of Baiyin furnace copper smelting slag. The beneficiation process adopts a crushing process with a first coarse crushing, semi-autogenous grinding and ball milling closed-circuit grinding and a slow circuit, and a flotation process with two roughing, two scavenging and three fine selections. In the early stage of the trial operation, the reagents used in the slag selection system were Z-200 and 2# oil. Although the flotation index can reach the design index, the high price of Z-200 keeps the reagent cost high. Later, butyl xanthate with a relatively low market price was used as a collector to reduce the beneficiation cost, but the slag selection index still needs to be further improved. Therefore, long-term exploration and continuous research are still needed to improve the metal recovery rate. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a special collector for flotation of copper smelting slag with low cost and good flotation index.

[0005] Another technical problem to be solved by the present invention is to provide an application method of the special collector for flotation of copper smelting slag.

[0006] In order to solve the above problems, the present invention discloses a special collector for flotation of copper smelting slag, characterized in that the collector is a brown-yellow oily liquid, which is prepared by uniformly stirring the following raw materials in parts by weight at room temperature: 1 part of liquid butyl ammonium black medicine, 0.5-1 part of ethyl xanthate propionitrile and / or butyl xanthate propionitrile, 0.5-1 part of thiocyanate, and 1-1.5 parts of ethylene glycol butyl ether.

[0007] The ethyl xanthate propionitrile is prepared by the following method: anhydrous ethanol, carbon disulfide and acrylonitrile are sequentially added into a reaction tank at a molar ratio of 1:1:1, and 2% of the total amount of the materials is added with powdered sodium hydroxide or potassium hydroxide powder, stirring is started, and the reaction is stirred at room temperature for 15 minutes, and then the mixture is put into a packaging barrel and left for more than 5 days.

[0008] The butyl xanthate propionitrile ester is prepared by the following method: n-butanol, carbon disulfide and acrylonitrile are sequentially added into a reaction tank at a molar ratio of 1:1:1, and 2% of the total amount of the materials is added with powdered sodium hydroxide or potassium hydroxide powder, stirring is started, and the reaction is stirred at room temperature for 15 minutes, and then the mixture is put into a packaging barrel and left for more than 5 days.

[0009] The application method of the special collector for copper smelting slag flotation as described above is characterized in that: the collector is used in combination with butyl xanthate in the fast flotation, roughing and scavenging operations in the copper smelting slag flotation process; the copper smelting slag refers to one or more mixtures of converter slag produced by converter smelting, flash slag produced by flash furnace smelting, and silver slag produced by silver furnace smelting.

[0010] When the copper smelting slag is silver furnace slag, the feed concentration in its flotation process is 40%wt, the grinding fineness is 80%-325 mesh; the fast flotation time is 30s, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector; the roughing time is 6min, the added reagents and the dosage are 240g / t of butyl xanthate and 25g / t of collector; the scavenging time is 2min, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector.

[0011] When the copper smelting slag is flash slag, the feed concentration in its flotation process is 40%wt, the grinding fineness is 87.5%-325 mesh; the fast flotation time is 60s, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector; the roughing time is 5min, the added reagents and the dosage are 240g / t of butyl xanthate and 25g / t of collector; the scavenging time is 2min, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector.

[0012] When the copper smelting slag is converter slag, the feed concentration in its flotation process is 40%wt, the grinding fineness is 85%-325 mesh; the fast flotation time is 4min, the added reagents and the dosage are 180g / t of butyl xanthate and 50g / t of collector; the roughing time is 6min, the added reagents and the dosage are 240g / t of butyl xanthate and 30g / t of collector; the scavenging time is 3min, the added reagents and the dosage are 120g / t of butyl xanthate and 20g / t of collector.

[0013] When the copper smelting slag is a mixed copper slag of silver furnace slag, flash furnace slag and converter slag, the feed concentration in the flotation process is 40%wt, the grinding fineness is 72%-325 mesh; the fast flotation time is 90s, the added reagent and the dosage are 180g / t of butyl xanthate and 30g / t of collector; the roughing time is 5min, the added reagent and the dosage are 80g / t of butyl xanthate and 20g / t of collector; the scavenging I time is 2min, the added reagent and the dosage are 50g / t of butyl xanthate and 10g / t of collector; the scavenging II time is 2min, the added reagent and the dosage are 20g / t of butyl xanthate and 10g / t of collector.

[0014] The mass percentages of silver furnace slag, flash furnace slag and converter slag in the mixed ore-blending copper slag are 21.6%, 62.6% and 15.8% respectively, and the copper grade of the original ore after blending is 2.55%.

[0015] Compared with the prior art, the present invention has the following advantages:

[0016] 1. The reagent of the present invention is compounded in proportion by a plurality of components, wherein: liquid butyl ammonium is a collector and foaming agent with good use effect, and has a special sorting effect on copper, lead, silver and activated zinc sulfide ores, as well as difficult-to-select polymetallic ores, etc. Ethyl xanthate propionitrile and butyl xanthate propionitrile are derivatives of xanthate collectors. Such compounds are non-ionic oily liquids, stable in nature, and can be directly added and used. They have high flotation activity and good selectivity for non-ferrous metal sulfide minerals, and have the advantages of low price, small dosage, less floating sulfur or even no floating, etc. Sulfur nitrogen nitrile is a high-efficiency collector with foaming properties for flotation of non-ferrous metal sulfide ores, and has a good effect on flotation of copper sulfide ores, and the dosage is less than that of xanthate pine oil, which can improve the quality of concentrate and reduce the cost of flotation reagents. Ethylene glycol butyl ether is a multifunctional and multi-purpose organic compound. Its chemical structure has two groups with strong solubility functions: ether bond and hydroxyl group. The former is lipophilic and can dissolve hydrophobic compounds, while the latter is hydrophilic and can dissolve hydrophilic compounds. Therefore, it has strong solubility and excellent emulsification and dispersing properties.

[0017] 2. The ingredients used in the agent of the present invention include collectors with strong affinity for divalent sulfide minerals such as chalcopyrite, collectors with strong affinity for monovalent sulfide minerals such as cuprite, and collectors for oxidizing minerals. By rationally compounding different collectors, the synergistic effect between different collectors is fully utilized.

[0018] 3. The present invention uses a variety of collector components at the same time to form a mutually soluble and stable oily liquid product, which is not only easy to produce, transport and add for use, but also can improve the capture rate and recovery rate of copper ore and copper smelting slag flotation. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0020] Figure 1 The present invention is a process flow diagram and condition diagram of a flotation method for separating copper concentrate from converter copper smelting slag under optimal grinding fineness conditions.

[0021] Figure 2 The present invention is a process flow diagram and condition diagram of a flotation method for separating copper concentrate from converter copper smelting slag under on-site grinding fineness conditions.

[0022] Figure 3 Schematic diagram of the process flow and conditions for flotation converter smelting copper smelting slag under field conditions.

[0023] Figure 4 The present invention is a process flow diagram and condition diagram of a flotation method for separating copper concentrate from flash furnace smelting copper smelting slag under optimal grinding fineness conditions.

[0024] Figure 5 The present invention is a flotation method for separating copper concentrate from flash furnace smelting copper smelting slag under on-site grinding fineness conditions and a condition schematic diagram.

[0025] Figure 6 Schematic diagram of the process flow and conditions for flotation flash furnace smelting copper smelting slag under field conditions.

[0026] Figure 7 The present invention is a process flow diagram and condition diagram of a flotation method for separating copper concentrate from copper smelting slag from silver furnace smelting under the condition of optimal grinding fineness.

[0027] Figure 8 The present invention is a process flow diagram and condition diagram of a flotation method for separating copper concentrate from copper smelting slag from silver furnace smelting under on-site grinding fineness conditions.

[0028] Fig. 9Schematic diagram of the process flow and conditions for smelting copper smelting slag in a flotation silver furnace under field conditions.

[0029] Fig.10 The present invention is a process flow and condition schematic diagram of a flotation method for separating copper concentrate from mixed ore copper slag in a copper smelting furnace under on-site grinding fineness conditions.

[0030] In the figure, A11 refers to the special collector of the present invention. DETAILED DESCRIPTION

[0031] The invention discloses a special collector for flotation of copper smelting slag. The collector is a brown-yellow oily liquid and is prepared by uniformly stirring the following raw materials in parts by weight (g) at room temperature: 1 part of liquid butyl ammonium black powder, 0.5-1 part of ethyl xanthate propionitrile and / or butyl xanthate propionitrile, 0.5-1 part of thiocyanate and 1-1.5 parts of ethylene glycol butyl ether.

[0032] Wherein: ethyl xanthate propionitrile is prepared by the following method: anhydrous ethanol, carbon disulfide and acrylonitrile are added into a reaction tank in a molar ratio of 1:1:1 in sequence, and 2% of the total amount of the materials is added with powdered sodium hydroxide or potassium hydroxide powder, stirring is started, and the reaction is stirred at room temperature for 15 minutes, and then the mixture is put into a packaging barrel and left for more than 5 days.

[0033] Butyl xanthate propionitrile is prepared by the following method: n-butanol, carbon disulfide and acrylonitrile are added into a reaction tank in a molar ratio of 1:1:1 in sequence, and 2% of the total amount of the materials is added with powdered sodium hydroxide or potassium hydroxide powder, stirring is started, and the reaction is stirred at room temperature for 15 minutes, and then the mixture is put into a packaging barrel and left for more than 5 days.

[0034] Ethyl xanthate propionitrile and butyl xanthate propionitrile are organic synthesis, and no waste water, waste gas, waste liquid or waste residue is discharged.

[0035] The collector obtained by the invention is a mixture of brown-yellow oily organic compounds which is stable in nature and easily soluble in water. It is mainly used as a new collector in combination with a butyl xanthate collector. Without changing the original mineral processing technology and mineral processing equipment, the recovery rate and copper grade of copper concentrate are improved, and efficient separation of copper in copper smelting slag is achieved.

[0036] An application method of a special collector for flotation of copper smelting slag: the collector is used in combination with butyl xanthate in the fast flotation, roughing and scavenging operations in the flotation process of copper smelting slag. Copper smelting slag refers to one or more mixtures of converter slag produced by converter smelting, flash slag produced by flash furnace smelting, and silver slag produced by silver furnace smelting.

[0037] ⑴ When the copper smelting slag is silver furnace slag, its flotation process consists of feeding, grinding, fast flotation, roughing, concentration I, concentration II, and scavenging, and three products of copper concentrate 1, copper concentrate 2 and tailings are obtained respectively. Among them: the feeding concentration is 40%wt, the grinding fineness is 80%-325 mesh; the fast flotation time is 30s, the added reagents and dosage are 120g / t of butyl xanthate and 10g / t of collector; the roughing time is 6min, the added reagents and dosage are 240g / t of butyl xanthate and 25g / t of collector; the scavenging time is 2min, the added reagents and dosage are 120g / t of butyl xanthate and 10g / t of collector.

[0038] ⑵ When the copper smelting slag is flash slag, its flotation process consists of feeding, grinding, fast flotation, roughing, concentration I, concentration II, and scavenging, and three products of copper concentrate 1, copper concentrate 2 and tailings are obtained respectively. Among them: the feeding concentration is 40%wt, the grinding fineness is 87.5%-325 mesh; the fast flotation time is 60s, the added reagents and dosage are butyl xanthate 120g / t, and the collector is 10g / t; the roughing time is 5min, the added reagents and dosage are butyl xanthate 240g / t, and the collector is 25g / t; the scavenging time is 2min, and the added reagents and dosage are butyl xanthate 120g / t, and the collector is 10g / t.

[0039] ⑶ When the copper smelting slag is converter slag, its flotation process consists of feeding, grinding, fast flotation, roughing, concentration I, concentration II, and scavenging, and three products of copper concentrate 1, copper concentrate 2 and tailings are obtained respectively. Among them: the feeding concentration is 40%wt, the grinding fineness is 85%-325 mesh; the fast flotation time is 4min, the added reagents and dosage are 180g / t of butyl xanthate and 50g / t of collector; the roughing time is 6min, the added reagents and dosage are 240g / t of butyl xanthate and 30g / t of collector; the scavenging time is 3min, the added reagents and dosage are 120g / t of butyl xanthate and 20g / t of collector.

[0040] (4) When the copper smelting slag is a mixed copper slag of silver furnace slag, flash furnace slag and converter slag, the mass percentages of silver furnace slag, flash furnace slag and converter slag in the mixed copper slag are 21.6%, 62.6% and 15.8% respectively, and the copper grade of the original ore after blending is 2.55%. The flotation process consists of feeding, grinding, fast flotation, roughing, concentration I, concentration II, scavenging I and scavenging II. Among them: the feed concentration is 40%wt, the grinding fineness is 72%-325 mesh; the fast flotation time is 90s, the added reagents and the dosage are 180g / t of butyl xanthate and 30g / t of collector; the roughing time is 5min, the added reagents and the dosage are 80g / t of butyl xanthate and 20g / t of collector; the scavenging I time is 2min, the added reagents and the dosage are 50g / t of butyl xanthate and 10g / t of collector; the scavenging II time is 2min, the added reagents and the dosage are 20g / t of butyl xanthate and 10g / t of collector.

[0041] The special collector used in the following Examples 1-2 is prepared by stirring 1 g of liquid butyl ammonium black medicine, 0.5 g of ethyl xanthate propionitrile, 0.5 g of thiocyanate nitrile, and 1 g of ethylene glycol butyl ether at room temperature.

[0042] Example 1 A flotation method for separating copper concentrate from converter copper smelting slag under optimal grinding fineness conditions.

[0043] Through the mineral processing condition test and open circuit test, it was determined that the feed concentration was 40%wt, the best grinding fineness was 85%-325 mesh, and the new reagent solution was "butyl xanthate + special collector". Based on the condition test and open circuit test, a closed circuit test was carried out under the conditions of feed concentration of 40%wt and best grinding fineness of 85%-325 mesh. The test process and conditions are shown in Figure 1 , the test results are shown in Table 1.

[0044] Table 1 Closed circuit test results of the flotation method of the present invention under the conditions of optimal grinding fineness (unit: %)

[0045]

[0046] It can be seen from the results of the closed-circuit test that the process of flotation recovery of copper from converter slag has met the index requirements. In the closed-circuit process, the grade of copper concentrate 1 is 33.25%, and the recovery rate is 92.27%; the grade of copper concentrate 2 is 10.07%, and the recovery rate is 2.52%; the copper grade of the total copper concentrate is 31.33%, and the copper recovery rate is 94.79%, and the copper grade of the tailings is 0.287%.

[0047] Example 2 A flotation method for separating copper concentrate from converter copper smelting slag under on-site grinding fineness conditions.

[0048] Through the ore dressing condition test and open circuit test, it was determined that the feed concentration was 40%wt, the on-site grinding fineness was 72%-325 mesh, and the new reagent solution was "butyl xanthate + special collector". Based on the condition test and open circuit test, a closed circuit test was carried out under the conditions of feed concentration of 40%wt and on-site grinding fineness of 72%-325 mesh. The test process and conditions are shown in Figure 2 , the test results are shown in Table 2.

[0049] Table 2 Closed circuit test results of the flotation method of the present invention under on-site grinding fineness conditions (unit: %)

[0050]

[0051] From the results of the closed-circuit test, it can be seen that when the converter slag is ground to a fineness of -325 mesh 72%, the selected concentration C=40%, and the dosage of butyl xanthate reaches the optimal conditions, the new reagent scheme is adopted, the fast-floating copper concentrate 1 grade is 31.45%, and the recovery rate is 91.34%; the copper concentrate 2 grade is 8.20%, and the recovery rate is 2.06%; the total copper concentrate copper grade is 29.60%, the copper recovery rate is 93.40%, and the tailings copper grade is 0.367%.

[0052] Example 3 Comparative example under field conditions.

[0053] The on-site conditions of the converter copper smelting slag beneficiation system are: the feed concentration is 40%wt, the on-site grinding fineness is 72%-325 mesh, and the beneficiation reagent scheme is "butyl xanthate + 2# oil". On the basis of the conditional test and open circuit test, the on-site conditional closed circuit test is carried out. The test process and conditions are shown in Figure 3 , the test results are shown in Table 3.

[0054] Table 3 Closed circuit test results under field conditions (unit: %)

[0055]

[0056] The results of the closed-circuit test of converter slag show that under the conditions of grinding fineness -325 mesh accounting for 72%, selected concentration C=40%, and butyl xanthate dosage reaching the optimal level, the copper grade of quick-float concentrate 1 is 31.10%, and the copper recovery rate is 90.84%; the copper grade of selected concentrate 2 is 8.80%, and the copper recovery rate is 1.91%; the copper grade of the comprehensive copper concentrate is 29.57%, the copper recovery rate is 92.75%, and the copper content of the tailings is 0.40%.

[0057] Comparative Examples 1 to 3 show that, under respective suitable fineness conditions, when the special collector of the present invention is used in comparison with the reagent system of the on-site 2# oil, under the conditions of the best fineness (85%-325 mesh) of the converter slag test laboratory, the closed-circuit copper concentrate with a copper grade of 31.33%, a copper recovery rate of 94.79%, and a tailings copper grade of 0.287% is obtained, which is 1.73 percentage points higher than the on-site fineness (72%-325 mesh) to obtain the total concentrate copper grade, 1.39 percentage points higher copper recovery rate, and 0.08 percentage points lower copper content in the tailings.

[0058] The special collector used in the following Examples 4 to 5 is prepared by stirring 1 g of liquid butyl ammonium black medicine, 1 g of ethyl xanthate propionitrile and butyl xanthate propionitrile (1:1), 1 g of thiocyanate, and 1.5 g of ethylene glycol butyl ether at room temperature.

[0059] Example 4 A flotation method for separating copper concentrate from flash furnace smelting copper smelting slag under optimal grinding fineness conditions.

[0060] Through the mineral processing condition test and open circuit test, it was determined that the feed concentration was 40%wt, the best grinding fineness was 85%-325 mesh, and the new reagent solution was "butyl xanthate + special collector". Based on the condition test and open circuit test, a closed circuit test was carried out under the conditions of feed concentration of 40%wt and best grinding fineness of 85%-325 mesh. The test process and conditions are shown in Figure 4 , the test results are shown in Table 4.

[0061] Table 4 Closed circuit test results of the flotation method of the present invention under the conditions of optimal grinding fineness (unit: %)

[0062]

[0063] From the closed-circuit test results, it can be seen that the grade of copper concentrate 1 is 23.13%, and the recovery rate is 73.55%; the grade of copper concentrate 2 is 10.87%, and the recovery rate is 17.28%; the copper grade of the total copper concentrate is 19.04%, the copper recovery rate is 90.83%, and the copper grade of the tailings is 0.238%.

[0064] Example 5 is an example of a flotation method for separating copper concentrate from flash furnace smelting copper smelting slag under on-site grinding fineness conditions.

[0065] Through the ore dressing condition test and open circuit test, it was determined that the feed concentration was 40%wt, the on-site grinding fineness was 72%-325 mesh, and the new reagent solution was "butyl xanthate + special collector". Based on the condition test and open circuit test, a closed circuit test was carried out under the conditions of feed concentration of 40%wt and on-site grinding fineness of 72%-325 mesh. The test process and conditions are shown in Figure 5 , the test results are shown in Table 5.

[0066] Table 5 Closed circuit test results of the flotation method of the present invention under on-site grinding fineness conditions (unit: %)

[0067]

[0068] The results of closed-circuit tests under on-site fineness conditions show that, under the conditions of ore fineness of 72%-325 mesh, selected concentration C=40%, and optimal dosage of butyl xanthate, the new reagent scheme is adopted, the copper grade of quick-float concentrate 1 is 22.51%, and the copper recovery rate is 71.75%; the copper grade of selected concentrate 2 is 11.52%, and the copper recovery rate is 18.35%; the copper grade of total copper concentrate is 18.85%, the copper recovery rate is 90.10%, and the copper content of tailings is 0.257%.

[0069] Example 6 Comparative example under field conditions.

[0070] The on-site conditions of the flash furnace copper smelting slag beneficiation system are: the feed concentration is 40%wt, the on-site grinding fineness is 72%-325 mesh, and the beneficiation reagent scheme is "butyl xanthate + 2# oil". On the basis of the conditional test and open circuit test, the on-site conditional closed circuit test is carried out. The test process and conditions are shown in Figure 6 , the test results are shown in Table 6.

[0071] Table 6 Closed circuit test results under field conditions (unit: %)

[0072]

[0073] The results of the flash slag closed-circuit test show that under the conditions of grinding fineness 72%-325 mesh, selection concentration C=40%, and optimal dosage of butyl xanthate, the copper grade of quick-float concentrate 1 is 23.42%, the copper recovery rate is 71.27%, the copper grade of concentrated concentrate 2 is 12.78%, the copper recovery rate is 18.03%, the copper grade of total copper concentrate is 20.05%, the copper recovery rate is 89.30%, and the copper content of tailings is 0.276%.

[0074] Comparative Examples 4 to 6 show that, under respective suitable fineness conditions, the flash furnace copper smelting slag adopts the special collector of the present invention compared with the reagent system of the on-site 2# oil: under the conditions of the flash furnace slag laboratory optimal fineness (87.5%-325 mesh), the closed circuit obtains a total copper concentrate with a copper grade of 19.04%, a copper recovery rate of 90.83%, and a tailings copper grade of 0.238%, which are 0.19 percentage points higher than the total concentrate copper grade obtained at the on-site fineness (72%-325 mesh), 0.73 percentage points higher in copper recovery rate, and 0.019 percentage points lower in copper content in the tailings.

[0075] The special collector used in the following Examples 7 to 8 is prepared by stirring 1 g of liquid butyl ammonium black medicine, 0.8 g of ethyl xanthate propionitrile, 0.8 g of thiocyanate, and 1.2 g of ethylene glycol butyl ether at room temperature.

[0076] Example 7 A flotation method for separating copper concentrate from copper smelting slag from a silver furnace under optimal grinding fineness conditions.

[0077] Through the ore dressing condition test and open circuit test, it is determined that the feed concentration of the present invention is 40%wt, the best grinding fineness is 85%-325 mesh, and the new reagent scheme is "butyl xanthate + special collector". On the basis of the condition test and open circuit test, a closed circuit test under field conditions is carried out. The test process and conditions are shown in Figure 7 , the test results are shown in Table 7.

[0078] Table 7 Closed circuit test results of the flotation method of the present invention under the optimal grinding fineness conditions (unit: %)

[0079]

[0080] The results of the closed-circuit test show that the flotation process for recovering copper from silver slag has met the index requirements. In the closed-circuit process, the grade of copper concentrate 1 is 22.30%, and the recovery rate is 60.85%; the grade of copper concentrate 2 is 8.25%, and the recovery rate is 18.97%; the copper grade of the total copper concentrate is 15.88%, and the copper recovery rate is 79.82%, and the copper grade of the tailings is 0.290%.

[0081] Example 8 A flotation method for separating copper concentrate from copper smelting slag from a silver furnace under on-site grinding fineness conditions.

[0082] Through the mineral processing condition test and open circuit test, it is determined that the feed concentration of the present invention is 40%wt, the on-site grinding fineness is 72%-325 mesh, and the new reagent scheme is "butyl xanthate + special collector". Based on the condition test and open circuit test, a closed circuit test is carried out under the conditions of 40%wt feed concentration and 72%-325 mesh on-site grinding fineness. The test process and conditions are shown in Figure 8 , the test results are shown in Table 8.

[0083] Table 8 Closed circuit test results of the flotation method of the present invention under on-site grinding fineness conditions (unit: %)

[0084]

[0085] The results of the closed-circuit test under on-site fineness conditions show that, under the conditions of ore fineness of -325 mesh, 72% selected concentration C=40%, and the optimal dosage of butyl xanthate, the new reagent scheme is adopted, the copper grade of quick flotation concentrate 1 is 23.49%, and the copper recovery rate is 59.28%; the copper grade of selected concentrate 2 is 7.85%, and the copper recovery rate is 19.22%; the copper grade of total copper concentrate is 15.79%, the copper recovery rate is 78.50%, and the copper content of tailings is 0.309%.

[0086] Example 9 Comparative example under field conditions.

[0087] The on-site conditions of the Baiyin furnace copper smelting slag beneficiation system are: the feed concentration is 40%wt, the on-site grinding fineness is 72%-325 mesh, and the beneficiation reagent scheme is "butyl xanthate + 2# oil". On the basis of the conditional test and open circuit test, a closed circuit test under on-site conditions was carried out. The test process and conditions are shown in Fig. 9 , the test results are shown in Table 9.

[0088] Table 9 Closed circuit test results under field conditions (unit: %)

[0089]

[0090] The results of the closed-circuit test show that under the conditions of grinding fineness -325 mesh 72%, selected concentration C=40%, and optimal dosage of butyl xanthate, the copper grade of quick-float concentrate 1 is 21.47%, and the copper recovery rate is 55.40%; the copper grade of selected concentrate 2 is 9.74%, and the copper recovery rate is 22.30%; the copper grade of the total copper concentrate is 15.96%, the copper recovery rate is 77.70%, and the copper content of the tailings is 0.320%.

[0091] Comparative Examples 7 to 9, under respective suitable fineness conditions, the special collector of the present invention is used as compared with the reagent system of the on-site 2# oil: under the conditions of the optimal fineness (80%-325 mesh) of the silver slag laboratory, the closed circuit obtains a total copper concentrate with a copper grade of 15.88%, a copper recovery rate of 79.82%, and a tailings copper grade of 0.290%, which is 0.09 percentage points higher than the total concentrate copper grade obtained at the on-site fineness (72%-325 mesh), 1.32 percentage points higher than the on-site fineness, and the copper recovery rate is reduced by 0.019 percentage points.

[0092] The special collector used in the following Example 10 is prepared by stirring 1 g of liquid butyl ammonium black medicine, 1 g of butyl xanthate propionitrile, 0.6 g of thiocyanate, and 1.4 g of ethylene glycol butyl ether at room temperature.

[0093] Example 10 A flotation method for separating copper concentrate from mixed ore blending copper slag in a copper smelting furnace under on-site grinding fineness conditions.

[0094] On the basis of the field condition test of single copper smelting slag, the field conditions of ore fineness 72%-325 mesh and selection concentration C=40% were maintained, and the flotation test of three types of copper smelting slags, namely silver furnace slag, flash furnace slag and converter slag, was carried out. The proportion of ore blending was: 62.6% flash furnace slag, 21.6% silver furnace slag and 15.8% converter slag. The copper grade of the original ore after blending was 2.55%. Through the ore dressing condition test and open circuit test, the new reagent scheme was determined to be "butyl xanthate + special collector". The closed circuit test process and conditions are shown in Fig.10 , the test results are shown in Table 10.

[0095] Table 10 Closed circuit test results of the flotation method of the present invention under on-site grinding fineness conditions (unit: %)

[0096]

[0097] The closed-circuit test results of the mixed slag of the three slags under the new reagent system showed that under the conditions of ore fineness -325 mesh 72% and selected concentration C=40%, the copper grade of quick flotation concentrate 1 was 23.46%, and the copper recovery rate was 77.03%; the copper grade of selected concentrate 2 was 11.82%, and the copper recovery rate was 13.25%; the copper grade of the comprehensive copper concentrate was 20.50%, the copper recovery rate was 90.28%, and the copper content of the tailings was 0.279%.

[0098] Example 11 Comparative example under field conditions.

[0099] On the basis of the field condition test of single copper smelting slag, the field conditions of ore fineness 72%-325 mesh and selected concentration C=40% were maintained, and the flotation test of three copper smelting slags, namely silver furnace slag, flash furnace slag and converter slag, was carried out. The proportion of ore blending was: 62.6% flash furnace slag, 21.6% silver furnace slag and 15.8% converter slag. The copper grade of the original ore after blending was 2.55%. The test results are shown in Table 11.

[0100] Table 11 Closed circuit test results under field conditions (unit: %)

[0101]

[0102] The closed-circuit test results of the mixed slag of the three slags show that, under the conditions of grinding fineness -325 mesh 72% and selected concentration C=40%, the copper grade of quick flotation concentrate 1 is 23.39%, and the copper recovery rate is 76.68%; the copper grade of selected concentrate 2 is 11.67%, and the copper recovery rate is 13.06%; the copper grade of the comprehensive copper concentrate is 20.41%, the copper recovery rate is 89.74%, and the copper content of the tailings is 0.295%.

[0103] Comparative Examples 10 to 11 show that according to the three copper smelting slag capacity blending (flash slag 62.6%, silver slag 21.6%, converter slag 15.8%), under the conditions of grinding fineness -325 mesh 72% and selected concentration C=40%, the total concentrate copper grade obtained by blending the ore increased by 0.09 percentage points, the copper recovery rate increased by 0.54 percentage points, and the copper content of the tailings decreased by 0.016 percentage points compared with the reagent system of the on-site 2# oil by using the special collector of the present invention.

Claims

1. A collector for flotation of copper smelting slag, characterized by: The collector is a brown-yellow oily liquid, and is prepared by uniformly stirring the following raw materials in parts by weight at room temperature: 1 part of liquid butyl ammonium black medicine, 0.5-1 part of ethyl xanthate propionitrile and / or butyl xanthate propionitrile, 0.5-1 part of thiocyanate, and 1-1.5 parts of ethylene glycol butyl ether.

2. A collector for flotation of copper smelting slag as claimed in claim 1, characterized in that: The ethyl xanthate propionitrile is prepared by the following method: anhydrous ethanol, carbon disulfide, and acrylonitrile are sequentially added into a reaction tank at a molar ratio of 1:1:1, and 2% of the total amount of the materials is added with powdered sodium hydroxide or potassium hydroxide powder, stirring is started, and the reaction is stirred at room temperature for 15 minutes, and then the mixture is put into a packaging barrel and left for more than 5 days.

3. A collector for flotation of copper smelting slag according to claim 1, characterized in that: The butyl xanthate propionitrile ester is prepared by the following method: n-butanol, carbon disulfide, and acrylonitrile are sequentially added into a reaction tank at a molar ratio of 1:1:1, and 2% of the total amount of the materials is added with powdered sodium hydroxide or potassium hydroxide powder, stirring is started, and the reaction is stirred at room temperature for 15 minutes, and then the mixture is put into a packaging barrel and left for more than 5 days.

4. The method for applying a collector for flotation of copper smelting slag according to any one of claims 1 to 3, characterized in that: The collector is used in combination with butyl xanthate in the fast flotation, roughing and scavenging operations in the flotation process of copper smelting slag; the copper smelting slag refers to one or more mixtures of converter slag produced by converter smelting, flash slag produced by flash furnace smelting, and silver slag produced by silver furnace smelting.

5. The method for applying a collector for flotation of copper smelting slag according to claim 4, characterized in that: When the copper smelting slag is silver furnace slag, the feed concentration in its flotation process is 40%wt, the grinding fineness is 80%-325 mesh; the fast flotation time is 30s, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector; the roughing time is 6min, the added reagents and the dosage are 240g / t of butyl xanthate and 25g / t of collector; the scavenging time is 2min, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector.

6. The method for applying a collector for flotation of copper smelting slag according to claim 4, characterized in that: When the copper smelting slag is flash slag, the feed concentration in its flotation process is 40%wt, the grinding fineness is 87.5%-325 mesh; the fast flotation time is 60s, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector; the roughing time is 5min, the added reagents and the dosage are 240g / t of butyl xanthate and 25g / t of collector; the scavenging time is 2min, the added reagents and the dosage are 120g / t of butyl xanthate and 10g / t of collector.

7. The method for using a collector for flotation of copper smelting slag according to claim 4, characterized in that: When the copper smelting slag is converter slag, the feed concentration in the flotation process is 40%wt, the grinding fineness is 85%-325 mesh; the fast flotation time is 4min, the added reagents and the dosage are 180g / t of butyl xanthate and 50g / t of collector; the roughing time is 6min, the added reagents and the dosage are 240g / t of butyl xanthate and 30g / t of collector; the scavenging time is 3min, the added reagents and the dosage are 120g / t of butyl xanthate and 20g / t of collector.

8. The method for using a collector for flotation of copper smelting slag according to claim 4, characterized in that: When the copper smelting slag is a mixed copper slag of silver furnace slag, flash furnace slag and converter slag, the feed concentration in the flotation process is 40%wt, the grinding fineness is 72%-325 mesh; the fast flotation time is 90s, the added reagent and dosage are 180g / t of butyl xanthate and 30g / t of collector; the roughing time is 5min, the added reagent and dosage are 80g / t of butyl xanthate and 20g / t of collector; the scavenging time I is 2min, the added reagent and dosage are 50g / t of butyl xanthate and 10g / t of collector; The sweeping time of II is 2min, and the added reagents and dosage are 20g / t of butyl xanthate and 10g / t of collector.

9. The method for applying a collector for flotation of copper smelting slag according to claim 8, characterized in that: The mass percentages of silver furnace slag, flash furnace slag and converter slag in the mixed ore-blending copper slag are 21.6%, 62.6% and 15.8% respectively, and the copper grade of the original ore after blending is 2.55%.

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