A method for beneficiating high-sulfur copper ore

Abstract

The present application provides a beneficiation method for high-sulfur copper ore, and relates to the field of copper ore flotation. The beneficiation method includes: mixing high-sulfur copper ore and water for slurrying to obtain raw ore pulp; raw ore pulp, combined depressant, collector A, and frother are mixed for copper roughing to obtain copper roughing concentrate; copper roughing concentrate and combined depressant are mixed for copper concentrating to obtain copper concentrate; the raw materials of the combined depressant include carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide; collector A includes one or more of Z-200, thiocyanate, thiocarbamate and ethylthiocyanate. The method simplifies the operating steps, improves the utilization rate of copper resources, and the entire process does not require additional acid or alkali to adjust the pH value, and has good economic and environmental benefits.

Description

Technical Field

[0001] The present application relates to the field of copper ore flotation, and in particular to a method for beneficiating high-sulfur copper ore. Background Art

[0002] As an indispensable basic material for modern industry, copper is of great importance. However, in the flotation process of copper sulfide ores, copper and sulfur are difficult to separate effectively due to their similar flotation properties. Especially in some copper ores with high sulfur content, it is a technical problem to effectively separate copper and inhibit the flotation of sulfur, which needs to be solved urgently.

[0003] The traditional lime high-alkali process for high-sulfur copper mines has the following disadvantages: First, the amount of lime used is large and the cost is high. In order to inhibit the flotation of sulfur minerals, a large amount of lime needs to be added to adjust the pH value of the slurry to a high alkaline state, which not only increases the consumption of raw materials, but also significantly increases the production cost; second, it causes environmental pollution. The use of a large amount of lime produces dust pollution during the production process, and the discharge of high-alkalinity wastewater also poses a serious threat to the environment; third, equipment wear and operation difficulty are large. The high-alkalinity slurry environment accelerates the corrosion and wear of the flotation equipment, and causes pipeline blockage, increasing the difficulty of operation; fourth, the sulfur resource recovery rate is low. Due to the addition of a large amount of lime, the pyrite is severely suppressed, resulting in a low subsequent sulfur resource recovery rate; fifth, the environmental protection pressure is high. The high pH value in the tailings increases the difficulty and pressure of environmental protection treatment.

[0004] Therefore, how to efficiently recycle high-sulfur copper ore is a difficult problem that needs to be urgently solved in the current high-sulfur copper ore beneficiation. Summary of the invention

[0005] The purpose of this application is to provide a high-sulfur copper ore dressing method to solve the above problems.

[0006] To achieve the above objectives, the present application provides a high-sulfur copper ore dressing method, comprising:

[0007] Mixing high-sulfur copper ore and water to prepare slurry to obtain raw ore slurry;

[0008] The raw ore pulp, the combined depressant, the collector A and the frother are mixed to perform copper roughing to obtain copper roughing concentrate and copper roughing tailings;

[0009] The copper rougher concentrate and the combined depressant are mixed to perform copper concentration to obtain a copper concentrate;

[0010] The copper roughing tailings, the collector A and the frother are subjected to copper scavenging to obtain copper scavenging tailings;

[0011] The copper scavenging tailings, collector B, and frother are used to perform sulfur roughing to obtain sulfur roughing concentrate;

[0012] The sulfur rougher concentrate is subjected to sulfur concentration to obtain sulfur concentrate;

[0013] The raw materials of the combined inhibitor include carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide;

[0014] The collector A includes one or more of Z-200, propylene thiocyanate, thiocarbamate and ethylthiocyanate;

[0015] The collector B includes one or more of butyl xanthate, Y89, and amyl xanthate.

[0016] Optionally, the mass ratio of the carbonized sodium cyanurate, the sodium thiosulfate, the sodium sulfite and the sodium hydroxide is (1-4):(1-4):(1-4):1.

[0017] Optionally, the foaming agent includes octanol and / or isooctyl alcohol.

[0018] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0019] A. The fineness of the raw ore pulp is -0.074mm, accounting for 55%-85%;

[0020] B. The mass concentration of the raw ore slurry is 30%-45%;

[0021] C. The copper concentration also obtains copper concentration tailings;

[0022] The copper concentrate tailings are returned to the upper level for separation.

[0023] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0024] A. The number of times of copper roughing is greater than or equal to 1 time;

[0025] B. The dosage of the combined depressant in the copper roughing process is 50 g / t to 500 g / t of raw ore;

[0026] C. The amount of the collector A used in the copper roughing process is 30 g / t-150 g / t of raw ore;

[0027] D. The dosage of the frother in the copper roughing process is 5g / t-50g / t of raw ore.

[0028] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0029] A. The copper is concentrated for 3 times or more;

[0030] B. The dosage of the combined depressant in the copper concentration process is 10 g / t to 100 g / t of raw ore.

[0031] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0032] A. The number of times of copper sweeping is greater than or equal to 2 times;

[0033] B. The dosage of the collector A in the single copper scavenging process is 5g / t-30g / t of raw ore;

[0034] C. The dosage of the frother in a single copper scavenging process is 1 g / t to 10 g / t of raw ore.

[0035] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0036] A. The number of times of sulfur roughing is greater than or equal to 1 time;

[0037] B. The number of sulfur concentration is greater than or equal to 2 times;

[0038] C. The amount of the collector B used in the sulfur roughing process is 50 g / t to 300 g / t of raw ore;

[0039] D. The dosage of the foaming agent in the sulfur roughing process is 20g / t-100g / t of raw ore.

[0040] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0041] A. The sulfur roughing also produces sulfur roughing tailings;

[0042] The sulfur roughing tailings, the collector B, and the frother are subjected to sulfur scavenging to obtain sulfur scavenging ore;

[0043] The sulfur scavenging and selecting of the minerals is returned to the upper level for selection;

[0044] B. the copper scavenging also obtains copper scavenging ore;

[0045] The copper ore is returned to the upper level for separation.

[0046] Optionally, the beneficiation method of the high-sulfur copper ore satisfies at least one of the following conditions:

[0047] A. The number of sulfur sweeps is greater than or equal to 2 times;

[0048] B. The dosage of the collector B in a single sulfur sweeping process is 10 g / t to 50 g / t of raw ore;

[0049] C. The dosage of the foaming agent in a single sulfur sweeping process is 1 g / t to 10 g / t of raw ore.

[0050] Compared with the prior art, the beneficial effects of this application include:

[0051] The beneficiation method of high-sulfur copper ore provided in the present application realizes effective inhibition of sulfur under nearly neutral pH conditions, promotes effective flotation of copper minerals, and produces qualified copper concentrate by selecting a flotation reagent combination inhibitor, a frother, and a collector A and coordinating the flotation process. Specifically, the combination inhibitor significantly improves the hydrophilicity of the surface of the sulfur mineral by virtue of its unique chemical action mechanism, thereby effectively curbing the floating tendency of the sulfur mineral during the flotation process. The collector A exhibits a high degree of selectivity, and it can be tightly adsorbed on the surface of the copper mineral, significantly enhancing the hydrophobicity of the copper mineral. This characteristic The recovery efficiency of copper minerals is greatly improved. Collector A and frother produce co-adsorption phenomenon at the gas-liquid interface and the mineral surface, which greatly enhances the efficiency of the flotation process. At the same time, since the copper scavenging tailings are at a nearly neutral pH value, there is no need to add additional acid or activator for activation. After adding collector B and frother, sulfur is directly floated to produce high-grade sulfur concentrate, realizing efficient recovery of copper-sulfur ore resources under nearly neutral pH conditions. This method simplifies the operating steps and improves the utilization rate of copper-sulfur resources. The entire process does not require additional acid or alkali to adjust the pH value, and has good economic and environmental benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0053] Figure 1 Schematic diagram of the beneficiation method for high-sulfur copper ore provided in Example 1. DETAILED DESCRIPTION

[0054] As used herein:

[0055] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0056] In these examples, parts and percentages are by mass unless otherwise indicated.

[0057] “And / or” is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0058] The most notable feature of high-sulfur copper ore is its extremely high sulfur content, with the sulfur-to-copper ratio often exceeding 10. This characteristic makes this type of copper ore face many challenges in the process of resource recovery. Specifically, the sulfur element in high-sulfur copper ore is not only abundant, but also mostly exists in the form of complex sulfides, such as pyrite (ferrous disulfide) and marcasite (another isomorphic variant of ferrous disulfide). As a sulfur mineral, marcasite has particularly excellent floatability. Compared with other iron sulfide minerals, marcasite is more difficult to be effectively inhibited during the flotation process. This characteristic greatly increases the difficulty of effectively separating copper and sulfur in high-sulfur copper ore, resulting in low efficiency in the recovery of copper resources.

[0059] Based on this, the present application provides a method for beneficiating high-sulfur copper ore, comprising:

[0060] Mixing high-sulfur copper ore and water to prepare slurry to obtain raw ore slurry;

[0061] The raw ore pulp, the combined depressant, the collector A and the frother are mixed to perform copper roughing to obtain copper roughing concentrate and copper roughing tailings;

[0062] The copper rougher concentrate and the combined depressant are mixed to perform copper concentration to obtain a copper concentrate;

[0063] The copper roughing tailings, the collector A and the frother are subjected to copper scavenging to obtain copper scavenging tailings;

[0064] The copper scavenging tailings, collector B, and frother are used to perform sulfur roughing to obtain sulfur roughing concentrate;

[0065] The sulfur rougher concentrate is subjected to sulfur concentration to obtain sulfur concentrate;

[0066] The raw materials of the combined inhibitor include carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide;

[0067] It should be noted that the cyanurate ions in the molecules of carbonized sodium cyanurate react with the metal ions on the surface of pyrite to form insoluble compounds or complexes, thereby inhibiting the flotation of pyrite; sodium thiosulfate and sodium sulfite are used as reducing agents, mainly in the form of H 2 SO 3 , HSO 3 - and SO3 2- These ionic components can adjust the potential of the slurry and put the slurry in a reducing atmosphere. Sodium thiosulfate can desorb the collector adsorbed on the surface of pyrite through desorption, thereby hindering the further adsorption of the collector. After sodium hydroxide is dissolved in the slurry, OH is released. - , adsorbed on the surface of pyrite to form Fe(OH) 2 and Fe(OH) 3 The hydrophilic film is formed, so that pyrite is hydrophilically inhibited. Through the compounding of the above components, the combined inhibitor has the characteristics of good selectivity and strong inhibition ability. A small amount can achieve a good inhibition effect during the roughing process. It can replace the lime inhibitor and overcome the disadvantages of lime as an inhibitor.

[0068] The collector A includes one or more of Z-200, propylene thiocyanate, thiocarbamate and ethylthiocyanate;

[0069] It should be noted that collector A can maintain a high collection efficiency and selectivity for copper under neutral or weakly alkaline conditions, and can selectively adsorb on the surface of copper minerals, while its adsorption capacity for sulfur minerals (such as pyrite and marcasite) is relatively weak, ensuring that copper mineral particles are effectively floated during the flotation process to achieve copper-sulfur separation.

[0070] The collector B includes one or more of butyl xanthate, Y89, and amyl xanthate. It should be noted that the collector B has a strong collecting ability and can strongly adsorb dixanthate on the surface of pyrite, thereby achieving effective separation of pyrite and gangue minerals.

[0071] In some embodiments, the mass ratio of the carbonized sodium cyanurate, the sodium thiosulfate, the sodium sulfite and the sodium hydroxide is (1-4): (1-4): (1-4): 1;

[0072] Optionally, the mass ratio of carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide can be 1:1:1:1, 2:2:1:1, 3:2:1:1, 4:2:3:1, 1:2:1:1, 1:3:1:1, 1:4:1:1, 1:1:2:1, 4:1:3:1, 4:1:4:1, 2:2:2:1, 3:3:3:1, 4:4:4:1 or any value between (1-4):(1-4):(1-4):1.

[0073] It should be noted that when the mass ratio of carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide is (1-4): (1-4): (1-4): 1, the four inhibitors work synergistically at this ratio to effectively inhibit non-target minerals and improve the recovery rate and grade of target minerals. At the same time, the ratio can be adjusted to achieve selective inhibition of different minerals and optimize the flotation process. This ratio setting not only reduces the amount of reagents used and saves costs, but also significantly improves the recovery rate and concentrate grade, improves flotation conditions, and increases production efficiency.

[0074] In some embodiments, the foaming agent comprises octanol and / or isooctyl alcohol.

[0075] It should be noted that the foaming agent can quickly form a large number of tiny bubbles at the gas-liquid interface. These bubbles are evenly distributed and stable, which helps to effectively attach and separate mineral particles.

[0076] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0077] A. The fineness of the raw ore pulp is -0.074mm, accounting for 55%-85%;

[0078] Optionally, the fineness of the copper sulfide ore -0.074 mm can account for 55%, 58%, 64%, 72%, 78%, 82%, 85% or any value between 55% and 85%;

[0079] B. The mass concentration of the raw ore slurry is 30%-45%;

[0080] Optionally, the mass concentration of the raw ore slurry may be 30%, 38%, 42%, 45% or any value between 30% and 45%;

[0081] C. The copper concentration also obtains copper concentration tailings;

[0082] The copper concentrate tailings are returned to the upper level for separation.

[0083] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0084] A. The number of times of copper roughing is greater than or equal to 1 time;

[0085] Optionally, the number of copper roughing selections may be 1 time, 2 times, 4 times, 5 times, 10 times or any value greater than or equal to 1 time.

[0086] B. The dosage of the combined depressant in the copper roughing process is 50 g / t to 500 g / t of raw ore;

[0087] Optionally, the dosage of the combined depressant in the copper roughing process can be 50g / t raw ore, 80g / t raw ore, 120g / t raw ore, 180g / t raw ore, 280g / t raw ore, 320g / t raw ore, 380g / t raw ore, 420g / t raw ore, 480g / t raw ore, 500g / t raw ore or any value between 50g / t raw ore and 500g / t raw ore;

[0088] C. The amount of the collector A used in the copper roughing process is 30 g / t-150 g / t of raw ore;

[0089] Optionally, the amount of collector A used in the copper roughing process can be 30 g / t of raw ore, 40 g / t of raw ore, 80 g / t of raw ore, 120 g / t of raw ore, 150 g / t of raw ore, or any value between 30 g / t of raw ore and 150 g / t of raw ore;

[0090] D. The dosage of the frother in the copper roughing process is 5g / t-50g / t of raw ore.

[0091] Optionally, the dosage of the frother in the copper roughing process can be 5g / t raw ore, 8g / t raw ore, 18g / t raw ore, 28g / t raw ore, 38g / t raw ore, 48g / t raw ore, 50g / t raw ore or any value between 5g / t raw ore and 50g / t raw ore.

[0092] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0093] A. The copper is concentrated for 3 times or more;

[0094] Optionally, the number of copper concentrations may be 3 times, 4 times, 5 times, 10 times, or any value greater than or equal to 3 times;

[0095] B. The dosage of the combined depressant in the copper concentration process is 10 g / t to 100 g / t of raw ore.

[0096] Optionally, the dosage of the combined depressant in the copper concentration process can be 10g / t raw ore, 22g / t raw ore, 32g / t raw ore, 42g / t raw ore, 52g / t raw ore, 62g / t raw ore, 72g / t raw ore, 82g / t raw ore, 92g / t raw ore, 100g / t raw ore or any value between 10g / t raw ore and 100g / t raw ore.

[0097] It should be noted that the dosage of the combined inhibitor is within the range of 10g / t-100g / t of raw ore. When the dosage is too large, the inhibitory ability is too strong, which not only inhibits sulfur minerals, but also inhibits copper, and the copper recovery rate is reduced; when the dosage is too small, the inhibitory ability is insufficient, and it is difficult to effectively inhibit sulfur minerals, resulting in excessive sulfur minerals in the copper concentrate and insufficient copper concentrate grade.

[0098] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0099] A. The number of times of copper sweeping is greater than or equal to 2 times;

[0100] Optionally, the number of copper scanning selections may be 2 times, 3 times, 4 times, 5 times, 10 times, or any value greater than or equal to 2 times;

[0101] B. The dosage of the collector A in the single copper scavenging process is 5g / t-30g / t of raw ore;

[0102] Optionally, the dosage of collector A in a single copper sweeping process can be 5 g / t of raw ore, 8 g / t of raw ore, 18 g / t of raw ore, 28 g / t of raw ore, 30 g / t of raw ore, or any value between 5 g / t of raw ore and 30 g / t of raw ore;

[0103] C. The dosage of the frother in a single copper scavenging process is 1 g / t to 10 g / t of raw ore.

[0104] Optionally, the dosage of the frother in a single copper sweeping process can be 1g / t of raw ore, 2g / t of raw ore, 4g / t of raw ore, 6g / t of raw ore, 8g / t of raw ore, 10g / t of raw ore or any value between 1g / t of raw ore and 10g / t of raw ore.

[0105] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0106] A. The number of times of sulfur roughing is greater than or equal to 1 time;

[0107] Optionally, the number of sulfur roughing operations may be 1, 2, 3, 4, 5, 10, or any value greater than or equal to 1;

[0108] B. The number of sulfur concentration is greater than or equal to 2 times;

[0109] Optionally, the number of sulfur concentrations may be 2, 3, 4, 5, 10, or any value greater than or equal to 2;

[0110] C. The amount of the collector B used in the sulfur roughing process is 50 g / t to 300 g / t of raw ore;

[0111] Optionally, the amount of collector B used in the sulfur roughing process can be 50 g / t of raw ore, 120 g / t of raw ore, 180 g / t of raw ore, 220 g / t of raw ore, 280 g / t of raw ore, 300 g / t of raw ore or any value between 50 g / t of raw ore and 300 g / t of raw ore;

[0112] D. The dosage of the foaming agent in the sulfur roughing process is 20g / t-100g / t of raw ore.

[0113] Optionally, the dosage of the frother in the sulfur roughing process can be 20g / t raw ore, 32g / t raw ore, 42g / t raw ore, 52g / t raw ore, 62g / t raw ore, 72g / t raw ore, 82g / t raw ore, 92g / t raw ore, 100g / t raw ore or any value between 20g / t raw ore and 100g / t raw ore.

[0114] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0115] A. The sulfur roughing also produces sulfur roughing tailings;

[0116] The sulfur roughing tailings, the collector B, and the frother are subjected to sulfur scavenging to obtain sulfur scavenging ore;

[0117] The sulfur scavenging and selecting of the minerals is returned to the upper level for selection;

[0118] B. the copper scavenging also obtains copper scavenging ore;

[0119] The copper ore is returned to the upper level for separation.

[0120] In some embodiments, the beneficiation method of high-sulfur copper ore satisfies at least one of the following conditions:

[0121] A. The number of sulfur sweeps is greater than or equal to 2 times;

[0122] Optionally, the number of sulfur sweeps is 2 times, 3 times, 4 times, 5 times, 10 times, or any value greater than or equal to 2 times;

[0123] B. The dosage of the collector B in a single sulfur sweeping process is 10 g / t to 50 g / t of raw ore;

[0124] Optionally, the dosage of collector B in a single sulfur sweep process can be 10 g / t of raw ore, 22 g / t of raw ore, 32 g / t of raw ore, 42 g / t of raw ore, 50 g / t of raw ore, or any value between 10 g / t of raw ore and 50 g / t of raw ore;

[0125] C. The dosage of the foaming agent in a single sulfur sweeping process is 1 g / t to 10 g / t of raw ore.

[0126] Optionally, the dosage of the frother in a single sulfur sweeping process can be 1g / t of raw ore, 3g / t of raw ore, 5g / t of raw ore, 7g / t of raw ore, 9g / t of raw ore, 10g / t of raw ore or any value between 1g / t of raw ore and 10g / t of raw ore.

[0127] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0128] Example 1

[0129] The present embodiment provides a beneficiation method for a high-sulfur copper ore, wherein a flotation operation is performed on a high-sulfur copper ore (Cu content is 0.78%, S content is 10.51%), and the ore is treated by copper flotation + sulfur flotation process after grinding. The copper flotation adopts a one-roughing, two-sweeping and three-fine flotation process, wherein the intermediate ore obtained by copper concentration I and copper scavenging I is returned to copper roughing, the intermediate ore obtained by copper concentration II and copper concentration III is returned to the previous concentration operation in turn, and the intermediate ore obtained by copper scavenging II is returned to copper scavenging I; the sulfur flotation adopts a one-roughing, two-sweeping and two-fine flotation process, wherein the intermediate ore obtained by sulfur concentration I and sulfur scavenging I is returned to sulfur roughing, the intermediate ore obtained by sulfur concentration II is returned to sulfur concentration I in turn, and the intermediate ore obtained by sulfur scavenging II is returned to sulfur scavenging I. The process steps of the flotation method are as follows: Figure 1 As shown, the specific steps are as follows:

[0130] S1: Grind the high-sulfur copper ore to a fineness of -0.074 mm accounting for 65%, and prepare a raw ore slurry with a mass concentration of 35%;

[0131] S2: adding 200 g / t of combined depressant, 80 g / t of collector A (Z-200), and 30 g / t of foaming agent isooctyl alcohol to the raw ore pulp, and performing a copper roughing to obtain a copper roughing concentrate and a copper roughing tailings;

[0132] S3: The copper rough concentrate is added with a combined depressant for three concentration operations. The combined depressant is added with 60g / t of raw ore, 30g / t of raw ore and 10g / t of raw ore in Concentration I, Concentration II and Concentration III respectively. The intermediate ore obtained from Concentration I, Concentration II and Concentration III is returned to the previous operation for selection. After the concentrating is completed, the copper concentrate is obtained;

[0133] S4: Collector A and frother are added to the copper roughing tailings to carry out copper scavenging twice. The dosage of collector A (Z-200) in copper scavenging I and copper scavenging II is 20g / t of raw ore and 10g / t of raw ore respectively, and the dosage of frother isooctanol is 5g / t of raw ore and 3g / t of raw ore respectively, to obtain copper scavenging middlings I, copper scavenging tailings and copper scavenging middlings II, and the middlings obtained after copper scavenging are sequentially returned to the previous operation for separation;

[0134] S5: The copper scavenging tailings are added with collector B butyl xanthate 200g / t original ore and foaming agent isooctyl alcohol 60g / t original ore, and a sulfur roughing is carried out to obtain sulfur roughing concentrate and sulfur roughing tailings;

[0135] S6: The sulfur rougher concentrate undergoes two blank concentration operations, and sulfur concentrate is obtained after sulfur concentration is completed;

[0136] S7: The sulfur roughing tailings are added with collector B butyl xanthate and frother isooctanol for two sulfur scavenging operations. The dosage of collector B butyl xanthate in sulfur scavenging I and sulfur scavenging II is 60g / t of raw ore and 30g / t of raw ore respectively, and the dosage of frother isooctanol is 10g / t of raw ore and 6g / t of raw ore respectively. The sulfur scavenging ore I and sulfur scavenging ore II obtained after sulfur scavenging are sequentially returned to the previous operation for separation;

[0137] The combined inhibitor is a mixture of carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide in a mass ratio of 2:2:4:1.

[0138] Example 2

[0139] This embodiment provides a beneficiation method for high-sulfur copper ore, and flotation operation is performed on a high-sulfur copper ore (Cu content is 0.71%, S content is 9.39%), and the specific steps are as follows:

[0140] S1: Grind the high-sulfur copper ore to a fineness of -0.074 mm accounting for 70%, and prepare a raw ore slurry with a mass concentration of 38%;

[0141] S2: adding 200 g / t of combined inhibitor, 80 g / t of collector A sulphuric acid propylene ester, and 30 g / t of foaming agent isooctyl alcohol to the raw ore pulp, and performing a copper roughing to obtain a copper roughing concentrate and a copper roughing tailings;

[0142] S3: The copper rough concentrate is added with a combined depressant for three concentration operations. The combined depressant is added with 60g / t of raw ore, 30g / t of raw ore and 10g / t of raw ore in Concentration I, Concentration II and Concentration III respectively. The intermediate ore obtained from Concentration I, Concentration II and Concentration III is returned to the previous operation for selection. After the concentrating is completed, the copper concentrate is obtained;

[0143] S4: The copper roughing tailings are added with collector A and frother to carry out copper scavenging twice. In the copper scavenging I and copper scavenging II, the dosage of collector A thiocyanate is 20g / t of raw ore and 10g / t of raw ore respectively, and the dosage of frother isooctanol is 5g / t of raw ore and 3g / t of raw ore respectively, to obtain copper scavenging middlings I, copper scavenging tailings and copper scavenging middlings II, and the middlings obtained after copper scavenging are sequentially returned to the previous operation for separation;

[0144] S5: The copper scavenging tailings are added with collector B amyl xanthate 200g / t of original ore and foaming agent isooctyl alcohol 60g / t of original ore, and a sulfur roughing is carried out to obtain a sulfur roughing concentrate and a sulfur roughing tailings;

[0145] S6: The sulfur rougher concentrate undergoes two blank concentration operations, and sulfur concentrate is obtained after sulfur concentration is completed;

[0146] S7: Collector B and frother are added to the sulfur roughing tailings for two sulfur scavenging operations. The dosage of collector B amyl xanthate is 60 g / t of raw ore and 30 g / t of raw ore in sulfur scavenging I and sulfur scavenging II, respectively. The dosage of frother isooctanol is 10 g / t of raw ore and 6 g / t of raw ore, respectively. The sulfur scavenging ore I and sulfur scavenging ore II obtained after sulfur scavenging are sequentially returned to the previous operation for separation.

[0147] The combined inhibitor is a mixture of carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide in a mass ratio of 2:3:4:1.

[0148] Example 3

[0149] This embodiment provides a beneficiation method for high-sulfur copper ore, and flotation operation is performed on a high-sulfur copper ore (Cu content is 0.82%, S content is 12.42%), and the specific steps are as follows:

[0150] S1: Grind the high-sulfur copper ore to a fineness of -0.074 mm accounting for 65%, and prepare a raw ore slurry with a mass concentration of 40%;

[0151] S2: adding 200 g / t of combined depressant, 80 g / t of collector A (Z-200), and 25 g / t of foaming agent isooctyl alcohol to the raw ore pulp, and performing a copper roughing separation to obtain a copper roughing concentrate and a copper roughing tailings;

[0152] S3: The copper rough concentrate is added with a combined depressant for three concentration operations. The combined depressant is added with 60g / t of raw ore, 40g / t of raw ore and 20g / t of raw ore in Concentration I, Concentration II and Concentration III respectively. The intermediate ore obtained from Concentration I, Concentration II and Concentration III is returned to the previous operation for selection. After the concentrating is completed, the copper concentrate is obtained;

[0153] S4: Collector A and frother are added to the copper roughing tailings to carry out copper scavenging twice. The dosage of collector A (Z-200) in copper scavenging I and copper scavenging II is 15g / t of raw ore and 8g / t of raw ore respectively, and the dosage of frother isooctyl alcohol is 4g / t of raw ore and 2g / t of raw ore respectively, to obtain copper scavenging middlings I, copper scavenging tailings and copper scavenging middlings II, and the middlings obtained after copper scavenging are sequentially returned to the previous operation for separation;

[0154] S5: The copper scavenging tailings are added with collector B butyl xanthate 250g / t original ore and foaming agent isooctyl alcohol 70g / t original ore, and a sulfur roughing is carried out to obtain sulfur roughing concentrate and sulfur roughing tailings;

[0155] S6: The sulfur rougher concentrate undergoes two blank concentration operations, and sulfur concentrate is obtained after sulfur concentration is completed;

[0156] S7: The sulfur roughing tailings are added with collector B butyl xanthate and frother isooctanol for two sulfur scavenging operations. The dosage of collector B butyl xanthate in sulfur scavenging I and sulfur scavenging II is 60g / t of raw ore and 40g / t of raw ore respectively, and the dosage of frother isooctanol is 12g / t of raw ore and 8g / t of raw ore respectively. The sulfur scavenging ore I and sulfur scavenging ore II obtained after sulfur scavenging are sequentially returned to the previous operation for separation;

[0157] The combined inhibitor is a mixture of carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide in a mass ratio of 3:2:3:1.

[0158] Comparative Example 1

[0159] The difference between this comparative example and Example 1 is that in this comparative example, the combined depressant in Example 1 is replaced with lime, the amount of lime used in the copper roughing process is 3000 g / t of raw ore, and the conventional lime high alkali copper flotation method is used for treatment, and the specific steps are as follows:

[0160] S1: Grind the high-sulfur copper ore to a fineness of -0.074 mm accounting for 65%, and prepare a raw ore slurry with a mass concentration of 35%;

[0161] S2: adding 3000 g / t lime, 80 g / t collector A (Z-200), and 30 g / t foaming agent isooctyl alcohol to the raw ore pulp, and performing a copper roughing to obtain a copper roughing concentrate and a copper roughing tailings;

[0162] S3: The copper rough concentrate is added with a combined depressant for three concentration operations. Lime 600g / t of raw ore, 300g / t of raw ore and 100g / t of raw ore are added to concentration I, concentration II and concentration III respectively. The intermediate ore obtained from concentration I, concentration II and concentration III is returned to the previous operation for selection. After the concentration is completed, copper concentrate is obtained;

[0163] S4: Collector A and frother are added to the copper roughing tailings to carry out copper scavenging twice. The dosage of collector A (Z-200) in copper scavenging I and copper scavenging II is 20g / t of raw ore and 10g / t of raw ore respectively, and the dosage of frother isooctanol is 5g / t of raw ore and 3g / t of raw ore respectively, to obtain copper scavenging middlings I, copper scavenging tailings and copper scavenging middlings II, and the middlings obtained after copper scavenging are sequentially returned to the previous operation for separation;

[0164] S5: The copper scavenging tailings are added with collector B butyl xanthate 200g / t original ore and foaming agent isooctyl alcohol 60g / t original ore, and a sulfur roughing is carried out to obtain sulfur roughing concentrate and sulfur roughing tailings;

[0165] S6: The sulfur rougher concentrate undergoes two blank concentration operations, and sulfur concentrate is obtained after sulfur concentration is completed;

[0166] S7: Collector B butyl xanthate and frother isooctanol are added to the sulfur roughing tailings for two sulfur scavengings. The dosage of collector B butyl xanthate in sulfur scavenging I and sulfur scavenging II is 60g / t of original ore and 30g / t of original ore respectively, and the dosage of frother isooctanol is 10g / t of original ore and 6g / t of original ore respectively. The sulfur scavenging ore I and sulfur scavenging ore II obtained after sulfur scavenging are returned to the previous operation in sequence for separation.

[0167] Comparative Example 2

[0168] The difference between this comparative example and comparative example 1 is that 1500 g / t of sulfuric acid is added to the copper scavenging tailings before sulfur roughing.

[0169] Comparative Example 3

[0170] The difference between this comparative example and Example 1 is that the combined inhibitor does not contain carbonized sodium cyanurate.

[0171] Comparative Example 4

[0172] The difference between this comparative example and Example 1 is that the combined inhibitor does not contain sodium thiosulfate.

[0173] Comparative Example 5

[0174] The difference between this comparative example and Example 1 is that the combined inhibitor does not contain sodium sulfite.

[0175] Comparative Example 6

[0176] The difference between this comparative example and Example 1 is that the combined inhibitor does not contain sodium hydroxide.

[0177] Comparative Example 7

[0178] The difference between this comparative example and Example 1 is that the collector A is ethyl xanthate.

[0179] Comparative Example 8

[0180] The difference between this comparative example and Example 1 is that the collector B is butylammonium black medicine.

[0181] Comparative Example 9

[0182] The difference between this comparative example and Example 1 is that collector B is used for copper flotation, and collector A is used for sulfur flotation.

[0183] The products prepared in the above examples and comparative examples were tested for content, and the specific results are shown in Table 1.

[0184] Table 1 Product content detection

[0185]

[0186] It can be seen from the data in Table 1 that the beneficiation method for high-sulfur copper ore provided in the present application is used to treat copper-sulfur ore. By selecting a flotation reagent combination inhibitor, a frother, and a collector A and coordinating the flotation process, effective suppression of sulfur under nearly neutral pH conditions is achieved, and effective flotation of copper minerals is promoted to produce qualified copper concentrate. At the same time, since the copper scavenging tailings have a neutral pH value, there is no need to add acid or activator for activation. After adding collector B and a frother, sulfur is directly floated to produce high-grade sulfur concentrate, and efficient recovery of copper-sulfur ore resources under nearly neutral pH conditions is achieved. The method simplifies the operating steps, improves the utilization rate of copper-sulfur resources, and the entire process does not require additional acid or alkali to adjust the pH value, which has good economic and environmental benefits.

[0187] It can be seen from Examples 1-3 that the copper grade in the copper concentrate is ≥23.17%, the copper recovery rate is ≥89.78%, the sulfur grade in the sulfur concentrate is ≥48.77%, and the sulfur recovery rate is ≥82.68%.

[0188] By comparing Example 1 with Comparative Examples 1-6, it can be seen that compared with conventional lime inhibitors, the inhibitor using a combination of carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide has improved the copper recovery rate in the copper concentrate obtained by flotation, and improved the sulfur recovery rate in the sulfur concentrate. When one of the components is removed or replaced by other agents, the copper grade or copper recovery rate in the copper concentrate decreases, and the sulfur grade or sulfur recovery rate in the sulfur concentrate decreases.

[0189] By comparing Example 1 with Comparative Examples 7-9, it can be seen that compared with conventional collectors, collector A using Z-200, propylene thiocyanate, thiocarbamate and ethylthiocyanate can improve the copper recovery rate in the copper concentrate obtained by flotation, and improve the sulfur recovery rate in the sulfur concentrate. Collector B using ethyl xanthate, butyl ammonium black medicine or collector A can achieve similar copper recovery rates in the copper concentrate obtained by flotation, but the sulfur grade or sulfur recovery rate in the sulfur concentrate decreases.

[0190] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

[0191] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A method for beneficiating lime-free high-sulfur copper ore, characterized in that: include: Mixing high-sulfur copper ore and water to prepare slurry to obtain raw ore slurry; The raw ore pulp, the combined depressant, the collector A and the frother are mixed to perform copper roughing to obtain copper roughing concentrate and copper roughing tailings; The copper rougher concentrate and the combined depressant are mixed to perform copper concentration to obtain a copper concentrate; The copper roughing tailings, the collector A and the frother are subjected to copper scavenging to obtain copper scavenging tailings; The copper scavenging tailings, collector B and the frother are used to perform sulfur roughing to obtain a sulfur roughing concentrate; The sulfur rougher concentrate is subjected to sulfur concentration to obtain sulfur concentrate; The raw materials of the combined inhibitor include carbonized sodium cyanurate, sodium thiosulfate, sodium sulfite and sodium hydroxide; The collector A includes one or more of Z-200, propylene thiocyanate, thiocarbamate and ethylthiocyanate; The collector B includes one or more of butyl xanthate, Y89 and amyl xanthate; The mass ratio of the carbonized sodium cyanurate, the sodium thiosulfate, the sodium sulfite and the sodium hydroxide is (1-4): (1-4): (1-4): 1; The amount of the combined depressant used in the copper roughing process is 50 g / t-500 g / t of raw ore; The dosage of the combined depressant in the copper concentration process is 10 g / t to 100 g / t of raw ore; The above-mentioned mineral processing method does not need to add additional acid or alkali to adjust the pH value and is carried out under the condition of nearly neutral pH value.

2. The method for beneficiating lime-free high-sulfur copper ore according to claim 1, characterized in that: The foaming agent includes octanol and / or isooctyl alcohol.

3. The beneficiation method of lime-free high-sulfur copper ore according to claim 1, characterized in that: At least one of the following conditions is met: A. The fineness of the raw ore pulp is -0.074mm, accounting for 55%-85%; B. The mass concentration of the raw ore slurry is 30%-45%; C. The copper concentration also obtains copper concentration tailings; The copper concentrate tailings are returned to the upper level for separation.

4. The beneficiation method of lime-free high-sulfur copper ore according to claim 1, characterized in that: At least one of the following conditions is met: A. The number of times of copper roughing is greater than or equal to 1 time; B. The amount of the collector A used in the copper roughing process is 30 g / t-150 g / t of raw ore; C. The dosage of the foaming agent in the copper roughing process is 5g / t-50g / t of raw ore.

5. The method for beneficiating lime-free high-sulfur copper ore according to claim 1, characterized in that: The copper is concentrated for more than 3 times.

6. The method for beneficiating lime-free high-sulfur copper ore according to claim 1, characterized in that: At least one of the following conditions is met: A. The number of times of copper sweeping is greater than or equal to 2 times; B. The dosage of the collector A in the single copper scavenging process is 5g / t-30g / t of raw ore; C. The dosage of the frother in a single copper scavenging process is 1 g / t to 10 g / t of raw ore.

7. The beneficiation method of lime-free high-sulfur copper ore according to claim 1, characterized in that: At least one of the following conditions is met: A. The number of times of sulfur roughing is greater than or equal to 1 time; B. The number of sulfur concentration is greater than or equal to 2 times; C. The amount of the collector B used in the sulfur roughing process is 50 g / t to 300 g / t of raw ore; D. The dosage of the foaming agent in the sulfur roughing process is 20g / t-100g / t of raw ore.

8. The beneficiation method of lime-free high-sulfur copper ore according to any one of claims 1 to 7, characterized in that: At least one of the following conditions is met: A. The sulfur roughing also produces sulfur roughing tailings; The sulfur roughing tailings, the collector B and the frother are subjected to sulfur scavenging to obtain sulfur scavenging ore; The sulfur scavenging and selecting of the minerals is returned to the upper level for selection; B. the copper scavenging also obtains copper scavenging ore; The copper ore is returned to the upper level for separation.

9. The method for beneficiating lime-free high-sulfur copper ore according to claim 8, characterized in that: At least one of the following conditions is met: A. The number of sulfur sweeps is greater than or equal to 2 times; B. The dosage of the collector B in a single sulfur sweeping process is 10 g / t to 50 g / t of raw ore; C. The dosage of the foaming agent in a single sulfur sweeping process is 1 g / t to 10 g / t of raw ore.

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