Zinc mineral inhibitor, flotation separation method of copper-zinc sulfide minerals and application

Abstract

The invention relates to the technical field of mineral separation, in particular to a zinc mineral inhibitor, a flotation separation method of copper-zinc sulfide minerals and application. The zinc mineral inhibitor comprises modified tamarind polysaccharide gum, and the modified tamarind polysaccharide gum is mainly prepared by performing heat treatment on tamarind polysaccharide gum in an oxygen atmosphere; the heat treatment temperature is 40-220 DEG C; the heat preservation time of the heat treatment is 2-6 hours; the zinc mineral inhibitor is used for flotation of copper-zinc sulfide minerals. The modified tamarind polysaccharide gum is adopted as a zinc mineral inhibitor, efficient flotation separation of chalcopyrite and sphalerite can be achieved, and the flotation agent is small in dosage, biodegradable, environmentally friendly, wide in raw material source, low in cost and simple in preparation method.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a flotation separation method and application of zinc mineral inhibitors and copper-zinc sulfide minerals. Background Art

[0002] Copper and zinc are important nonferrous metal resources for national economy and national defense construction, and are widely used in power transmission, communication, transportation, machinery manufacturing and other fields. Copper-zinc sulfide ore is the main source of copper and zinc metals. With the development of society, the demand for copper and zinc metals continues to increase, which brings challenges to the separation of copper-zinc sulfide ore.

[0003] Chalcopyrite is the most important copper sulfide ore, usually coexisting with other sulfide minerals in the ore, such as sphalerite, pyrite, and galena. These minerals are very similar in physical and chemical properties such as density, magnetism, hydrophobicity, and conductivity, which makes it difficult to extract qualified copper concentrate products before smelting.

[0004] Froth flotation is the main method for separating copper and zinc sulfide ores. Since chalcopyrite has better floatability than sphalerite, the method of suppressing zinc and flotating copper is mostly used to achieve copper and zinc separation. Even so, in actual industrial production, it is necessary to add inhibitors to selectively enhance the hydrophilicity of sphalerite surface, reduce its floatability, and then promote the enrichment of chalcopyrite in concentrate and improve the separation efficiency between the two.

[0005] Common inhibitors for sphalerite include zinc sulfate, lime, sulfite, etc., which are widely used in production practice. However, the above-mentioned agents have problems such as large dosage, difficult degradation, and environmental pollution.

[0006] In addition, Chinese patent CN101693224A discloses a method for separating copper-zinc sulfide minerals. When water-soluble thioglycolate or thioglycolic acid is used as a zinc mineral inhibitor, it exhibits good selectivity, strong inhibitory ability, and is easy to add. However, its preparation process is relatively complicated and costly, which increases the cost of mineral processing operations and hinders the promotion and application of the agent.

[0007] Chinese patent CN109158214B discloses a flotation separation process for sulfide copper-zinc ore, in which zinc sulfate and sodium sulfite are added to the ore pulp as a combined inhibitor, which can not only improve the hydrophilicity of sphalerite but also prevent the adsorption of collectors on the surface of sphalerite, thereby achieving the purpose of copper-zinc separation. However, the agent is not easy to degrade, and long-term and large-scale use will seriously pollute the environment.

[0008] Therefore, there is an urgent need for an efficient, green and environmentally friendly zinc mineral inhibitor and copper-zinc flotation separation method.

[0009] In view of this, the present invention is proposed. Summary of the invention

[0010] The first object of the present invention is to provide a zinc mineral inhibitor, which adopts modified tamarind polysaccharide gum to achieve effective separation of chalcopyrite and sphalerite, and at the same time, it has strong selectivity, small dosage, biodegradability, green environmental protection, low raw material price, and simple preparation method. The existing inhibitors solve the problems of large dosage, difficult degradation, environmental pollution, complicated preparation process and high cost.

[0011] The second purpose of the present invention is to provide a flotation separation method for copper-zinc sulfide minerals. The modified tamarind polysaccharide gum is used as a zinc mineral inhibitor to float the copper-zinc sulfide minerals, so that the efficient separation of chalcopyrite and sphalerite can be achieved. The modified tamarind polysaccharide gum has the advantages of strong selectivity, small dosage, easy acquisition of raw materials and low cost, which can significantly reduce the consumption of reagents, save mineral processing costs, biodegradable, green and environmentally friendly.

[0012] The third object of the present invention is to provide the use of copper concentrate and zinc-containing tailings obtained by the flotation separation method of copper-zinc sulfide minerals in the production of copper products and zinc products.

[0013] In order to achieve the above-mentioned purpose of the present invention, the following technical scheme is specially adopted.

[0014] The present invention first provides a zinc mineral inhibitor, comprising modified tamarind polysaccharide gum; wherein the modified tamarind polysaccharide gum is mainly prepared by subjecting tamarind polysaccharide gum to heat treatment under an oxygen atmosphere; the heat treatment temperature is 40-220°C; the heat treatment insulation time is 2-6h; the zinc mineral inhibitor is used for flotation of copper-zinc sulfide minerals.

[0015] Furthermore, when the zinc mineral inhibitor is used to float the copper-zinc sulfide ore, the dosage of the zinc mineral inhibitor is 80-300 g / t.

[0016] The present invention further provides a flotation separation method for copper-zinc sulfide minerals, comprising the following steps: grinding the copper-zinc sulfide minerals and mixing them with water to obtain flotation pulp; adding the zinc mineral inhibitor to the flotation pulp, and adding a collector and a frother thereto to perform flotation.

[0017] Furthermore, the grinding is performed to a particle size of less than 0.074 mm, which accounts for 75% to 90% by mass.

[0018] Furthermore, the concentration of the flotation pulp is 27% to 35%.

[0019] Furthermore, the total dosage of the zinc mineral inhibitor is 80-300 g / t.

[0020] Furthermore, the collector includes at least one of Z-200, ethylthiocyanate and butyl xanthate.

[0021] Furthermore, the total amount of the collector is 50-150 g / t.

[0022] Furthermore, the foaming agent includes at least one of terpineol and 2# oil.

[0023] Furthermore, the total amount of the foaming agent is 25-100 g / t.

[0024] Furthermore, the flotation includes roughing selection, scavenging selection, first cleaning selection and second cleaning selection.

[0025] The present invention also provides the use of the copper concentrate and zinc-containing tailings obtained by the flotation separation method of the copper-zinc sulfide minerals in the production of copper products and zinc products.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows.

[0027] (1) The zinc mineral inhibitor provided by the present invention adopts modified tamarind polysaccharide gum, can achieve effective separation of chalcopyrite and sphalerite, has a strong inhibitory effect, and is used in a small amount, can significantly reduce the cost of mineral processing, is biodegradable, green and environmentally friendly, and has low raw material prices and a simple preparation method.

[0028] (2) The zinc mineral inhibitor provided by the present invention, on the one hand, the hydroxyl groups in the molecular structure of the modified tamarind polysaccharide gum can enhance the hydrophilicity of the sphalerite surface; on the other hand, the molecular structure of the modified tamarind polysaccharide gum contains a large number of aldehyde groups, which have strong reducing properties and will be hydrolyzed in the solution to obtain carboxyl groups, which can react with Cu in the ore pulp. 2+ Chelation of metal ions such as Cu 2+ Activation of sphalerite; at the same time, the carboxyl group is a strong solid-affinity group, which can be strongly adsorbed on the surface of sphalerite, significantly enhancing the hydrophilicity of sphalerite, thereby achieving efficient flotation separation between chalcopyrite and sphalerite.

[0029] (3) The zinc mineral inhibitor provided by the present invention uses modified tamarind polysaccharide gum as raw material, which has the advantages of wide source, low cost, biodegradability, green environmental protection, etc., and the preparation method of modified tamarind polysaccharide gum is simple, the process is short, and it is suitable for mass production.

[0030] (4) The flotation separation method of copper-zinc sulfide minerals provided by the present invention adopts modified tamarind polysaccharide gum as a zinc mineral inhibitor to flotate copper-zinc sulfide minerals, which can achieve efficient separation of chalcopyrite and sphalerite, and has a strong inhibitory effect. In addition, the modified tamarind polysaccharide gum has the advantages of small dosage, easy acquisition of raw materials and low raw material cost, which can significantly reduce the consumption of reagents, save mineral processing costs, and is biodegradable and environmentally friendly. DETAILED DESCRIPTION

[0031] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be appreciated by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work, all belong to the scope of protection of the present invention. If specific conditions are not indicated in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0032] If there is no special explanation, in the present invention, "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "the first", "the second", "the third", "the fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0033] If there is no special explanation, the "include" and "comprising" mentioned in the present invention represent open-ended or closed-ended expressions. For example, the "include" and "comprising" may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0034] If there is no special explanation, in the present invention, "one or more" or "at least one" refers to any one, any two or more of the listed items. Among them, "several" refers to any two or more of the listed items.

[0035] In a first aspect, the present invention provides a zinc mineral inhibitor, comprising modified tamarind polysaccharide gum; wherein the modified tamarind polysaccharide gum is mainly prepared by heat-treating tamarind polysaccharide gum under an oxygen atmosphere.

[0036] Wherein, the temperature of the heat treatment is 40~220℃, including but not limited to any point value of 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 120℃, 130℃, 150℃, 160℃, 180℃, 200℃, 220℃ or the range value between any two of them.

[0037] The heat treatment holding time is 2 to 6 hours, including but not limited to any one of 2 hours, 3 hours, 4 hours, 5 hours, and 6 hours, or a range between any two of them.

[0038] The zinc mineral depressant is used for flotation of copper-zinc sulfide minerals. That is, the zinc mineral depressant is used to flotation of copper-zinc sulfide minerals.

[0039] The present invention uses modified tamarind polysaccharide gum as a zinc mineral inhibitor. On the one hand, the hydroxyl group (-OH) in its molecular structure can enhance the hydrophilicity of the sphalerite surface; on the other hand, the molecular structure contains a large number of aldehyde groups (-CHO), which have strong reducing properties and will hydrolyze in the solution to obtain carboxyl groups (-COOH). The carboxyl groups can react with Cu in the slurry. 2+ Chelation of metal ions to avoid Cu 2+ Activation of sphalerite; at the same time, carboxyl is a strong solid-affinity group, which can be strongly adsorbed on the surface of sphalerite, significantly enhancing the hydrophilicity of sphalerite, thereby achieving efficient flotation separation between chalcopyrite and sphalerite, providing a strong theoretical support for the flotation separation of copper-zinc sulfide ores.

[0040] Among them, after the tamarind polysaccharide gum is subjected to heat treatment and oxidation modification, the hydroxyl groups in the tamarind polysaccharide gum are partially converted into aldehyde groups, and the bound water between molecules is removed, resulting in a significant decrease in the molecular weight of the tamarind polysaccharide gum. After further reaction, part of the aldehyde groups in the tamarind polysaccharide gum are oxidized and converted into carboxyl groups, the molecular chain will break, and the molecular weight will be further reduced. The oxidatively modified tamarind polysaccharide gum can be selectively adsorbed on the surface of sphalerite, hindering the further adsorption of the collector on the surface of sphalerite, and improving the hydrophilicity of the sphalerite surface, thereby achieving effective separation of chalcopyrite and sphalerite.

[0041] In addition, modified tamarind polysaccharide gum is a modified macromolecular agent of plant origin, which has the advantages of good selectivity, small dosage, strong inhibitory effect, wide source, low cost and biodegradability.

[0042] Compared with the traditional sphalerite inorganic inhibitor or combined inhibitor, the preparation method of the zinc mineral inhibitor proposed in the present invention is simple, and the raw materials are easy to obtain, green and environmentally friendly, low in price, and can be naturally degraded.

[0043] The zinc mineral inhibitor provided by the present invention has good use effect, strong selectivity and small dosage, and can significantly reduce the consumption of reagents and save the ore dressing cost while efficiently inhibiting sphalerite.

[0044] In some specific embodiments, the heat treatment may be performed using any heating equipment commonly used in the art, such as a tube furnace, but is not limited thereto.

[0045] In some specific embodiments, when the zinc mineral inhibitor is used to float the copper-zinc sulfide mineral, the dosage of the zinc mineral inhibitor is 80-300 g / t, including but not limited to any one of 80 g / t, 90 g / t, 100 g / t, 110 g / t, 120 g / t, 130 g / t, 140 g / t, 150 g / t, 160 g / t, 170 g / t, 180 g / t, 190 g / t, 200 g / t, 250 g / t, and 280 g / t or any range between two thereof. That is, the mass of the modified tamarind polysaccharide gum added to each ton of the copper-zinc sulfide mineral is 80-300 g.

[0046] The present invention uses modified tamarind polysaccharide gum as a zinc mineral inhibitor. On the one hand, the hydroxyl group (-OH) in its molecular structure can enhance the hydrophilicity of the sphalerite surface; on the other hand, the molecular structure contains a large number of aldehyde groups (-CHO), which have strong reducing properties and will hydrolyze in the solution to obtain carboxyl groups (-COOH). The carboxyl groups can react with Cu in the slurry. 2+ Chelation of metal ions such as Cu 2+ Activation of sphalerite; at the same time, carboxyl is a strong affinity group, which can strongly adsorb on the surface of sphalerite, significantly enhancing the hydrophilicity of sphalerite, thereby achieving efficient flotation separation between chalcopyrite and sphalerite, providing a strong theoretical support for the flotation separation of copper-zinc sulfide ores. In addition, modified tamarind polysaccharide gum has the advantages of good selectivity, low dosage, strong inhibition effect, wide source of raw materials, low cost, biodegradability, and green environmental protection.

[0047] In some specific embodiments, the flotation method comprises froth flotation.

[0048] In a second aspect, the present invention provides a flotation separation method for copper-zinc sulfide minerals, including froth flotation, specifically comprising the following steps: the copper-zinc sulfide minerals are coarsely crushed and ground, and then mixed with water to obtain a flotation pulp. The above-mentioned zinc mineral inhibitor is added to the flotation pulp, and a collector and a frother are added thereto to perform flotation to obtain a copper concentrate and a zinc-containing tailing. Among them, the zinc mineral inhibitor is a modified tamarind polysaccharide gum, and the modified tamarind polysaccharide gum is mainly prepared by heat treatment of tamarind polysaccharide gum under an oxygen atmosphere, and the heat treatment temperature is 40~220℃; the heat treatment insulation time is 2~6h.

[0049] The flotation separation method of copper-zinc sulfide minerals provided by the present invention adopts modified tamarind polysaccharide gum as a zinc mineral inhibitor to flotate copper-zinc sulfide minerals, and can achieve efficient separation of chalcopyrite and sphalerite. In addition, the modified tamarind polysaccharide gum has the advantages of strong selectivity, small dosage, easy acquisition of raw materials and low cost, can significantly reduce the consumption of reagents, save mineral processing costs, is biodegradable, and is green and environmentally friendly.

[0050] In addition, the above flotation separation method has the advantages of simple operation, short process and high separation efficiency.

[0051] In some specific embodiments, in order to achieve effective monomer dissociation of the target mineral and the gangue mineral and improve the flotation separation efficiency, the ore is ground to a mass percentage in which the particle size of the mineral is less than 0.074 mm, accounting for 75% to 90%, including but not limited to any one of 75%, 78%, 80%, 82%, 85%, 88%, and 90%, or a range between any two of the values.

[0052] In some specific implementations, due to differences in ore properties, flotation machine models and process flows, in order to achieve a good flotation effect and avoid the adverse effects of too low or too high slurry concentration on the flotation process, the concentration of the flotation slurry is controlled to be 27% to 35%, for example, 28%, 29%, 30%, 32% or 33%.

[0053] In some specific embodiments, the total dosage of the zinc mineral inhibitor is 80-300 g / t, including but not limited to any point value of 80 g / t, 90 g / t, 100 g / t, 110 g / t, 120 g / t, 130 g / t, 140 g / t, 150 g / t, 160 g / t, 170 g / t, 180 g / t, 190 g / t, 200 g / t, 230 g / t, 250 g / t, 290 g / t or any range value between two of them, that is, the mass of the modified tamarind polysaccharide gum added per ton of copper-zinc sulfide mineral is 80-300 g. The total dosage refers to the sum of the dosages in each stage (roughing, scavenging and cleaning) of the flotation process.

[0054] In some specific embodiments, the collector includes at least one of Z-200 (ethylthiocarbamate), ethylthiocarbamate and butyl xanthate. The collector can effectively capture copper minerals, but has a weaker ability to capture other gangue minerals, which is conducive to the enrichment and separation of copper minerals.

[0055] In some specific embodiments, the total amount of the collector is 50-150 g / t, including but not limited to any point value of 50 g / t, 60 g / t, 70 g / t, 80 g / t, 90 g / t, 100 g / t, 110 g / t, 120 g / t, 130 g / t, 140 g / t, 150 g / t or any range value between two of them, that is, the mass of the collector added per ton of copper-zinc sulfide ore is 50-150 g. The total amount refers to the sum of the amounts used in each stage of the flotation process (roughing, scavenging and cleaning).

[0056] In some specific embodiments, the foaming agent includes at least one of terpineol and 2# oil.

[0057] In some specific embodiments, the total amount of the frother is 25-100 g / t, including but not limited to any point value of 25 g / t, 30 g / t, 40 g / t, 50 g / t, 60 g / t, 70 g / t, 80 g / t, 90 g / t, 100 g / t or any range value between two of them, that is, the mass of the frother added per ton of copper-zinc sulfide ore is 25-100 g. The total amount refers to the sum of the amounts used in each stage of the flotation process (roughing, scavenging and cleaning).

[0058] In some specific embodiments, the flotation comprises roughing, scavenging, first cleaning and second cleaning.

[0059] In some specific embodiments, during the roughing process, the zinc mineral inhibitor, the collector and the foaming agent are added in sequence; during the scavenging process, the collector and the foaming agent are added; during the first concentrating process, the zinc mineral inhibitor is added; and during the second concentrating process, the zinc mineral inhibitor is added.

[0060] In some specific embodiments, the mass of the zinc mineral inhibitor added during the roughing is 3 to 4 times the mass of the zinc mineral inhibitor added during the first concentrating, and the mass of the zinc mineral inhibitor added during the roughing is 7 to 8 times the mass of the zinc mineral inhibitor added during the second concentrating.

[0061] In a third aspect, the present invention provides the use of the copper concentrate and zinc-containing tailings obtained by the flotation separation method of the copper-zinc sulfide minerals in the production of copper products and zinc products.

[0062] The flotation separation method of copper-zinc sulfide minerals provided by the present invention can realize the efficient separation of chalcopyrite and sphalerite, and adopts modified tamarind polysaccharide gum as a zinc mineral inhibitor. The modified tamarind polysaccharide gum has the advantages of strong selectivity, small dosage, easy acquisition of raw materials and low cost, can significantly reduce the consumption of reagents, save mineral processing costs, is biodegradable, green and environmentally friendly, and has broad application prospects.

[0063] Among them, the copper concentrate obtained by the flotation separation method of copper-zinc sulfide minerals can be used to produce copper products, namely copper-containing parts, components, products, etc.

[0064] Among them, the zinc-containing tailings obtained by the flotation separation method of copper-zinc sulfide minerals can be used to produce zinc products, namely zinc-containing parts, components, products, etc.

[0065] The embodiments of the present invention will be described in detail below in conjunction with the examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. If no specific conditions are specified in the examples, the conditions are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be obtained commercially.

[0066] Example 1 The zinc mineral inhibitor provided in this embodiment is modified tamarind polysaccharide gum, and its preparation method is as follows: tamarind polysaccharide gum is placed in a tubular furnace and heat-treated at 50° C. for 6 hours in an oxygen atmosphere.

[0067] Example 2 The zinc mineral inhibitor provided in this embodiment is modified tamarind polysaccharide gum, and the preparation method thereof is as follows: tamarind polysaccharide gum is placed in a tubular furnace and heat-treated at 100° C. for 4 hours in an oxygen atmosphere.

[0068] Example 3 The zinc mineral inhibitor provided in this embodiment is modified tamarind polysaccharide gum, and its preparation method is as follows: tamarind polysaccharide gum is placed in a tubular furnace and heat-treated at 200° C. for 2 hours in an oxygen atmosphere.

[0069] Example 4 This embodiment provides an application of a zinc mineral inhibitor in the flotation of copper-zinc sulfide minerals. The zinc mineral inhibitor prepared in Example 1 is used to flotate copper-zinc sulfide minerals, and a pure mineral mixed flotation test is performed. The specific steps are: 1 g of chalcopyrite with a particle size of 0.038 mm to 0.074 mm and 1 g of sphalerite with a particle size of 0.038 mm to 0.074 mm are weighed respectively, and a proper amount of deionized water is added thereto and stirred evenly, and then the mixture is poured into the flotation tank of a hanging tank flotation machine, and the speed of the flotation machine is adjusted to 1. 690r / min, adjust the slurry pH to 7, add 100g / t of modified tamarind polysaccharide gum (i.e., add 100g of modified tamarind polysaccharide gum per ton of mineral) and stir for 3min, then add 100g / t of collector butyl xanthate and 50g / t of foaming agent pine oil (i.e., add 100g of collector and 50g of foaming agent per ton of mineral) and stir for 2min, carry out aeration flotation, filter, dry and weigh the obtained foam product and tailings respectively, and the yield and recovery results are shown in Table 1.

[0070] Table 1 Yield and recovery results

[0071] Example 5 The present embodiment provides an application of a zinc mineral inhibitor in the flotation of copper-zinc sulfide minerals. The zinc mineral inhibitor prepared in Example 2 is used to flotate copper-zinc sulfide minerals, and a pure mineral mixed flotation test is performed. The specific steps are: 1 g of chalcopyrite with a particle size of 0.038 mm to 0.074 mm and 1 g of sphalerite with a particle size of 0.038 mm to 0.074 mm are weighed respectively, mixed, and an appropriate amount of deionized water is added thereto and stirred evenly, and then poured into the flotation tank of a hanging tank flotation machine, the speed of the flotation machine is adjusted to 1690 r / min, the pH of the slurry is adjusted to 8, 120 g / t of modified tamarind polysaccharide gum is added thereto, and stirred for 3 min, then 100 g / t of a collector butyl xanthate and 50 g / t of a foaming agent pine oil are added and stirred for 2 min, and aeration flotation is performed, and the obtained foam product and tailings are filtered, dried, and weighed respectively. The yield and recovery rate results are shown in Table 2.

[0072] Table 2 Yield and recovery results

[0073] Example 6 The present embodiment provides an application of a zinc mineral inhibitor in the flotation of copper-zinc sulfide minerals. The zinc mineral inhibitor prepared in Example 3 is used to flotate copper-zinc sulfide minerals, and a pure mineral mixed flotation test is performed. The specific steps are: 1 g of chalcopyrite with a particle size of 0.038 mm to 0.074 mm and 1 g of sphalerite with a particle size of 0.038 mm to 0.074 mm are weighed respectively, mixed, and an appropriate amount of deionized water is added thereto and stirred evenly, and then poured into the flotation tank of a hanging tank flotation machine, the speed of the flotation machine is adjusted to 1690 r / min, the pH of the pulp is adjusted to 9, 140 g / t of modified tamarind polysaccharide gum is added thereto, and stirred for 3 min, then 100 g / t of a collector butyl xanthate and 50 g / t of a foaming agent pine oil are added and stirred for 2 min, and aeration flotation is performed, and the obtained foam product and tailings are filtered, dried, and weighed respectively. The yield and recovery rate results are shown in Table 3.

[0074] Table 3 Yield and recovery results

[0075] Example 7 The flotation separation method of copper-zinc sulfide minerals provided in this embodiment uses a polymetallic sulfide ore in Inner Mongolia as an ore sample, wherein the copper (element) grade in the original ore sample is 0.44%, the zinc (element) grade is 0.65%, the main components are chalcopyrite, sphalerite, pyrite and pyrrhotite, and a small amount of bismuthinite and arsenopyrite, and the modified tamarind polysaccharide gum prepared in Example 3 is used as a zinc mineral inhibitor, and a flotation closed-circuit process of one coarse, two fines and one sweep is adopted, comprising the following steps: (1) The raw ore sample is placed in a ball mill for grinding to obtain a grinding product with a grinding fineness of -0.074 mm accounting for 90% (i.e., 90% of the particle size is less than 0.074 mm by mass percentage). The grinding product is transferred to a flotation tank and water is added to adjust the pulp concentration to 30%.

[0076] (2) A single-tank flotation machine was used for flotation. 110 g / t of modified tamarind polysaccharide gum (i.e., 110 g of modified tamarind polysaccharide gum was added to each ton of raw ore), 80 g / t of collector Z-200 and 40 g / t of frother pine oil (i.e., 80 g of collector and 40 g of frother were added to each ton of raw ore) were added to the pulp in sequence. Each agent was allowed to act for 2 min after being added, and then roughing was carried out for 5 min.

[0077] Then, scavenging is carried out, and 20g / t of collector Z-200 and 5g / t of frother pine oil are added to the slurry (i.e., 20g of collector and 5g of frother are added to each ton of raw ore), stirred for 2min, and then floated for 5min.

[0078] Then, concentration I (i.e., the first concentration) is carried out, 30 g / t of modified tamarind polysaccharide gum is added to the slurry (i.e., 30 g of modified tamarind polysaccharide gum is added to each ton of raw ore), stirred for 3 minutes, and then floated for 5 minutes.

[0079] Finally, concentration II (i.e., the second concentration) is carried out, 15 g / t of modified tamarind polysaccharide gum is added to the slurry (i.e., 15 g of modified tamarind polysaccharide gum is added to each ton of original ore), and flotation is performed for 4 minutes to obtain copper concentrate and zinc-containing tailings.

[0080] The yield, grade and recovery results of this example are shown in Table 4.

[0081] Table 4 Yield, grade and recovery results

[0082] Example 8 The flotation separation method of copper-zinc sulfide minerals provided in this embodiment uses a medium-sized porphyry copper mine in Sichuan as an ore sample, wherein the main components are pyrrhotite, followed by chalcopyrite and sphalerite, wherein the copper (element) and zinc (element) grades are 2.18% and 1.32%, respectively, and the ore also contains a small amount and trace amount of chalcocite, hematite, limonite, calcite, quartz, etc., and the modified tamarind polysaccharide gum prepared in Example 2 is used as a zinc mineral inhibitor, and a flotation closed-circuit process of one coarse, two fines and one sweep is adopted, comprising the following steps: (1) The raw ore sample is placed in a ball mill for grinding to obtain a grinding product with a grinding fineness of -0.074 mm accounting for 85% (i.e., 85% of the particle size is less than 0.074 mm in terms of mass percentage). The grinding product is transferred to a flotation cell and water is added to adjust the pulp concentration to 30%.

[0083] (2) A single-tank flotation machine was used for flotation. 150 g / t of modified tamarind polysaccharide gum, 120 g / t of collector butyl xanthate and 40 g / t of frother 2# oil were added to the pulp in sequence. Each agent was allowed to act for 2 min after addition, and then roughing was carried out for 5 min.

[0084] After that, scavenging is carried out, 30g / t of collector butyl xanthate and 5g / t of frother 2# oil are added to the pulp, stirred for 2min and then floated for 5min.

[0085] Then, concentration I (i.e., the first concentration) was carried out, 40 g / t of modified tamarind polysaccharide gum was added to the pulp, stirred for 3 minutes, and then floated for 5 minutes.

[0086] Finally, concentration II (i.e., the second concentration) is carried out, 20 g / t of modified tamarind polysaccharide gum is added to the slurry, and flotation is performed for 4 minutes to obtain copper concentrate and zinc-containing tailings.

[0087] The yield, grade and recovery results of this example are shown in Table 5.

[0088] Table 5 Yield, grade and recovery results

[0089] Example 9 The flotation separation method of copper-zinc sulfide minerals provided in this embodiment uses a polymetallic sulfide ore in Yunnan as an ore sample. The copper (element) and zinc (element) grades in the original ore sample are 0.90% and 1.62%, respectively, in the form of chalcopyrite and sphalerite, respectively. The gangue minerals mainly include quartz, pyrite, feldspar and dolomite, etc. The modified tamarind polysaccharide gum prepared in Example 1 is used as a zinc mineral inhibitor. A one-rough, two-fine and one-sweep flotation closed-circuit process is adopted, comprising the following steps: (1) The raw ore sample is placed in a ball mill for grinding to obtain a grinding product with a grinding fineness of -0.074 mm accounting for 80% (i.e., 80% of the particles with a mass percentage of less than 0.074 mm). The grinding product is transferred to a flotation tank and water is added to adjust the pulp concentration to 30%.

[0090] (2) A single-tank flotation machine was used for flotation. 200 g / t of modified tamarind polysaccharide gum, 100 g / t of collector ethylthiocarb and 40 g / t of frother pine were added to the pulp in sequence. Each agent was allowed to act for 2 min after addition, and then roughing was carried out for 5 min.

[0091] After that, scavenging is carried out, 25g / t of collector ethylthiocarb and 5g / t of frother pine alcohol are added to the pulp, stirred for 2min and then floated for 5min.

[0092] Then, concentration I (i.e., the first concentration) was carried out, 50 g / t of modified tamarind polysaccharide gum was added to the pulp, stirred for 3 minutes, and then floated for 5 minutes.

[0093] Finally, concentration II (i.e., the second concentration) is carried out, 25 g / t of modified tamarind polysaccharide gum is added to the slurry, and flotation is performed for 4 minutes to obtain copper concentrate and zinc-containing tailings.

[0094] The yield, grade and recovery results of this example are shown in Table 6.

[0095] Table 6 Yield, grade and recovery results

[0096] Example 10 The flotation separation method of copper-zinc sulfide minerals provided in this embodiment is basically the same as that in Example 7, except that 60 g / t of modified tamarind polysaccharide gum is added in roughing, 13 g / t of modified tamarind polysaccharide gum is added in fine selection I, and 7 g / t of modified tamarind polysaccharide gum is added in fine selection II, that is, the total amount of modified tamarind polysaccharide gum is 80 g / t. The yield, grade and recovery rate of this embodiment are shown in Table 7 (the grade of copper element in the original ore has a slight error).

[0097] Table 7 Yield, grade and recovery results

[0098] Comparative Example 1 The flotation separation method of copper-zinc sulfide minerals provided in this comparative example is basically the same as that in Example 7, except that zinc sulfate is used as a zinc mineral inhibitor, and the modified tamarind polysaccharide gum is replaced with zinc sulfate during flotation, wherein the amount of zinc sulfate used in roughing is 1000 g / t, the amount of zinc sulfate used in fine separation I is 300 g / t, and the amount of zinc sulfate used in fine separation II is 150 g / t. The yield, grade and recovery rate of this comparative example are shown in Table 8.

[0099] Table 8 Yield, grade and recovery results

[0100] By comparing Example 7 with Comparative Example 1, it can be seen that the copper grade in the copper concentrate obtained by using the traditional zinc sulfate inhibitor is only 21.32%, and the recovery rate is only 84.79%. Compared with Example 7 using modified tamarind polysaccharide gum, the inhibitory effect of Comparative Example 1 on zinc is poor. In addition, the amount of zinc mineral inhibitor used in Comparative Example 1 is significantly higher than that in Example 7.

[0101] Comparative Example 2 The zinc mineral inhibitor provided in this comparative example is modified tamarind polysaccharide gum, and its preparation method is as follows: tamarind polysaccharide gum is placed in a tubular furnace and heat-treated at 400° C. for 2 h in an oxygen atmosphere.

[0102] The flotation separation method of copper-zinc sulfide minerals provided in this comparative example is basically the same as that in Example 7, except that the modified tamarind polysaccharide gum prepared in this comparative example is used as a zinc mineral depressant for flotation. The yield, grade and recovery rate of this comparative example are shown in Table 9 (the grade of copper element in the original ore has a slight error).

[0103] Table 9 Yield, grade and recovery results

[0104] By comparing Example 7 and Comparative Example 2, it can be seen that the copper grade and recovery rate in the copper concentrate obtained by using the modified tamarind polysaccharide gum prepared in Comparative Example 2 are lower than those in Example 7, that is, the inhibitory effect of Comparative Example 2 on zinc is worse than that of Example 7. This is because the heat treatment temperature of Comparative Example 2 is relatively high, resulting in a large number of breaks in the molecular chains in the tamarind polysaccharide gum, and some polysaccharides in the molecules are carbonized by heat, which significantly reduces the effective components that exert the inhibitory effect, thereby significantly weakening the inhibitory effect on sphalerite.

[0105] Comparative Example 3 The zinc mineral inhibitor provided in this comparative example is tamarind polysaccharide gum, that is, it is not subjected to heat treatment modification.

[0106] The flotation separation method of copper-zinc sulfide minerals provided in this comparative example is basically the same as that in Example 7, except that the unmodified tamarind polysaccharide gum described above in this comparative example is used as a zinc mineral depressant for flotation. The yield, grade and recovery rate of this comparative example are shown in Table 10 (the grade of zinc element in the original ore has a slight error).

[0107] Table 10 Yield, grade and recovery results

[0108] By comparing Example 7 with Comparative Example 3, it can be seen that the copper grade and recovery rate in the copper concentrate obtained by using the unmodified tamarind polysaccharide gum of Comparative Example 3 are significantly lower than those of Example 7, that is, the selective inhibition of zinc in Comparative Example 3 is significantly worse than that in Example 7. This is because the tamarind polysaccharide gum of Comparative Example 3 has not been oxidatively modified. Although the hydroxyl groups in the unmodified tamarind polysaccharide gum molecules can be adsorbed on the surface of sphalerite through acid-base interaction and hydrogen bonding, inhibiting the floatability of sphalerite, the selectivity of the hydroxyl groups is relatively poor, and they will also interact with the surface of chalcopyrite, inhibiting the flotation of chalcopyrite to a certain extent. At the same time, the molecular weight of the unmodified tamarind polysaccharide gum is relatively large, which will play a certain role as a flocculant, causing fine particles of chalcopyrite and sphalerite to flocculate, exacerbating the difficulty of flotation separation of chalcopyrite and sphalerite.

[0109] In summary, the conventional zinc mineral inhibitors such as zinc sulfate have poor inhibitory effect, and the dosage is large, which seriously pollutes the environment. The modified tamarind polysaccharide gum provided by the present invention has a strong inhibitory effect as a zinc mineral inhibitor, can achieve efficient flotation separation of chalcopyrite and sphalerite, and has a small dosage, low cost, biodegradability, environmental friendliness, meets actual production needs, and can be widely used in the separation and flotation of copper-zinc sulfide ores.

[0110] Although the present invention has been illustrated and described with specific embodiments, it should be appreciated that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Those skilled in the art should understand that the technical solutions described in the above embodiments may be modified, or some or all of the technical features thereof may be replaced by equivalents without departing from the spirit and scope of the present invention. However, these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention. Therefore, this means that all such replacements and modifications within the scope of the present invention are included in the appended claims.

Claims

1. A zinc mineral inhibitor, characterized in that including modified tamarind polysaccharide gum; The modified tamarind polysaccharide gum is mainly prepared by heat-treating tamarind polysaccharide gum in an oxygen atmosphere; The temperature of the heat treatment is 40-220°C; The heat treatment holding time is 2 to 6 hours; The zinc mineral depressant is used for flotation of copper-zinc sulfide minerals.

2. The zinc mineral inhibitor according to claim 1, characterized in that: When the zinc mineral inhibitor is used to float the copper-zinc sulfide ore, the dosage of the zinc mineral inhibitor is 80-300 g / t.

3. A flotation separation method for copper-zinc sulfide minerals, characterized in that: The steps include: After grinding, copper-zinc sulfide minerals are mixed with water to obtain flotation pulp; The zinc mineral depressant as claimed in claim 1 is added to the flotation pulp, and a collector and a frother are added thereto to carry out flotation.

4. The flotation separation method of copper-zinc sulfide minerals according to claim 3, characterized in that: The grinding process is performed to obtain a particle size of 75% to 90% by mass less than 0.074 mm.

5. The flotation separation method of copper-zinc sulfide minerals according to claim 3, characterized in that: The concentration of the flotation pulp is 27% to 35%.

6. The flotation separation method of copper-zinc sulfide minerals according to claim 3, characterized in that: The total dosage of the zinc mineral inhibitor is 80-300 g / t.

7. The flotation separation method of copper-zinc sulfide minerals according to claim 3, characterized in that: At least one of the following conditions is met: (1) The collector includes at least one of Z-200, ethylthiocyanate and butyl xanthate; (2) The total amount of the collector is 50-150 g / t.

8. The flotation separation method of copper-zinc sulfide minerals according to claim 3, characterized in that: At least one of the following conditions is met: (1) The foaming agent includes at least one of terpineol and 2# oil; (2) The total amount of the foaming agent is 25-100 g / t.

9. The flotation separation method of copper-zinc sulfide minerals according to claim 3, characterized in that: The flotation includes roughing, scavenging, primary cleaning and secondary cleaning.

10. Use of the copper concentrate and zinc-containing tailings obtained by the flotation separation method of copper-zinc sulfide minerals according to any one of claims 3 to 9 in the production of copper products and zinc products.

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