Preparation method of low-grade copper sulfide ore froth type collector

Abstract

The application discloses a preparation method of a foaming type collector for low-grade copper sulfide ore. Alkyl dithiophosphate a is dissolved in distilled water or anhydrous ethanol to prepare an alkyl dithiophosphate solution A. Halogen element and sodium hydroxide are added to the alkyl dithiophosphate solution A to prepare an alkyl dithiophosphate halide solution, and the molar ratio of the alkyl dithiophosphate, the halogen element and the sodium hydroxide is 0.8-1.2:0.8-1.2:0.1-0.3. Alkyl dithiophosphate b is dissolved in distilled water or anhydrous ethanol to prepare an alkyl dithiophosphate solution B. The alkyl dithiophosphate solution B is added to the alkyl dithiophosphate halide solution, and the molar ratio of the alkyl dithiophosphate halide and the alkyl dithiophosphate is 1:1-1.1. After the reaction is completed, the solution is left to stand and is separated to obtain the foaming type collector. The method precisely synthesizes a novel dithiophosphate collector through two-step reactions, has high adsorption selectivity, does not need to add a foaming agent, greatly reduces the beneficiation cost, and improves the grade and the recovery rate of the copper concentrate.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing reagents technology, specifically relating to a method for preparing a foaming collector for low-grade copper sulfide ore. Background Technology

[0002] With the large-scale and continuous mining of copper resources, the easily processed rich ores have been almost exhausted. The ores currently available are generally characterized by low grade, fine particle size, complex symbiotic relationships, and increased difficulty in liberation. At the same time, the degree of oxidation of the ores is increasing, the proportion of oxygen-sulfur mixed copper ores is constantly increasing, and the surface properties of the minerals are complex, which significantly increases the difficulty of flotation.

[0003] Currently, the collectors commonly used in industrial beneficiation plants are still mainly traditional reagents such as butyl xanthate, butylammonium black reagent, and Z-200. These reagents have achieved good results for high-grade copper ores with simple dissemination, but when processing current low-grade complex ores, their insufficient selective collection ability is becoming increasingly prominent, making it difficult to meet the concentrate grade, and their collection ability for fine-grained target minerals is weak, resulting in large fluctuations in recovery rate.

[0004] In recent years, domestic and international research on copper collectors has mainly focused on the modification or compounding of xanthates, black ore and sulfur-nitrogen agents. The systematic research on their corresponding ester derivatives is not yet in-depth. In particular, at the level of mechanism of action, related reports are mostly limited to the traditional chelation theory. There is a lack of in-depth exploration of the adsorption behavior of ester collectors in low-grade complex slurry systems, which restricts the development of highly selective collectors.

[0005] Based on this, the present invention aims to provide a method for preparing a foaming collector suitable for low-grade sulfide copper ore and oxygen-sulfur mixed copper ore. While improving selective collection ability, it simplifies the reagent system and reduces the cost of mineral processing reagents, providing a new technical path for efficient, economical and clean flotation recovery of low-grade copper ore resources. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a foaming collector for low-grade copper sulfide ore.

[0007] The objective of this invention is achieved as follows: the preparation method of the foaming collector for low-grade copper sulfide ore includes the following steps: Alkyl dithiophosphate a is dissolved in distilled water or anhydrous ethanol to prepare alkyl dithiophosphate solution A; A alkyl dithiophosphate solution A is prepared by adding a halogen element and sodium hydroxide to the solution A, wherein the molar ratio of alkyl dithiophosphate: halogen element: sodium hydroxide is 0.8~1.2:0.8~1.2:0.1~0.3. Alkyl dithiophosphate b is dissolved in distilled water or anhydrous ethanol to prepare alkyl dithiophosphate solution B. The alkyl dithiophosphates a and b can be the same or different salts. Alkyl dithiophosphate solution B is added to alkyl dithiophosphate halide solution, wherein the molar ratio of alkyl dithiophosphate halide to alkyl dithiophosphate is 1:1~1.1; after the reaction is completed, the resulting liquid is allowed to stand and separated, and the resulting organic phase is the foaming collector for low-grade copper sulfide ore.

[0008] Compared with the prior art, the technical solution described in this invention has the following advantages: 1. The collector molecule prepared by the method described in this invention simultaneously introduces two different or identical alkyl dithiophosphate groups, and the molecule contains multiple S and O electron-donating atoms, which can react with Cu on the surface of copper minerals. 2+ / Cu + It forms a stable multi-component chelate ring, which significantly improves the adsorption strength compared to traditional single-group collectors.

[0009] 2. The preparation method described in this invention can flexibly control the hydrophilicity-hydrophobicity balance of molecules by selecting R groups with different carbon chain lengths, i.e., C1 to C5, so that it can adjust the wetting and covering ability of the mineral surface according to the degree of ore oxidation, thereby adapting to the flotation requirements of copper minerals with different surface characteristics.

[0010] 3. The diester structure in the collector molecule prepared by the method described in this invention endows it with high surface activity. When the double hydrophobic tail chains are oriented at the gas-liquid interface, they can reduce the surface tension of the bubbles, thus eliminating the need for an external frother, simplifying the flotation process, and avoiding competitive adsorption between the frother and the collector in the pulp, further improving selectivity.

[0011] 4. The preparation method described in this invention adopts a segmented temperature control design, which allows the two-step reaction to reach their respective optimal kinetic windows, avoiding the adverse effects of increased byproducts at high temperatures in the one-step method. It also produces no toxic organic byproducts and has greater environmental advantages.

[0012] 5. The preparation method described in this invention maximizes the yield of halogenated intermediates by precisely optimizing the molar ratio of reactants, especially the precise metering of halogen elements. The final product can be obtained with high purity after simple washing and drying. Attached Figure Description

[0013] Figure 1 This is a process flow diagram of the technical solution described in this invention. Detailed Implementation

[0014] The present invention will be further described below, but this is not intended to limit the invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the scope of protection of the present invention.

[0015] The preparation method of the low-grade copper sulfide ore foaming collector of the present invention includes the following steps: Alkyl dithiophosphate a is dissolved in distilled water or anhydrous ethanol to prepare alkyl dithiophosphate solution A; A alkyl dithiophosphate solution A is prepared by adding a halogen element and sodium hydroxide to the alkyl dithiophosphate halide solution, wherein the molar ratio of alkyl dithiophosphate: halogen element: sodium hydroxide is 0.8~1.2:0.8~1.2:0.1~0.3; preferably, the molar ratio is 1:1:0.2.

[0016] Alkyl dithiophosphates undergo substitution reactions with elemental halogens, as shown in the following reaction equation: ( RO )2 PSSMe + X 2→ X ( RO )2 PSSMe + HX In this denominator, R is selected from C1-C5 alkyl groups, such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, and X is one of Cl, Br, and I.

[0017] Alkyl dithiophosphate b is dissolved in distilled water or anhydrous ethanol to prepare alkyl dithiophosphate solution B. The alkyl dithiophosphates a and b can be the same or different salts, preferably the same salt. Alkyl dithiophosphate solution B is added to alkyl dithiophosphate halide solution, wherein the molar ratio of alkyl dithiophosphate halide to alkyl dithiophosphate is 1:1 to 1.1; preferably, the molar ratio is 1:1.04.

[0018] The reaction formulas for alkyl dithiophosphate halides and alkyl dithiophosphates are as follows: X ( RO )2 PSSMe + ( R'O )2 PSSMe → ( R'O )2 PSSS ( RO )2 PSSMe + MeX In this context, R and R′ are selected from C1-C5 alkyl groups, such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, X is one of Cl, Br, and I, and Me is one of Na and K. After the reaction is complete, the resulting liquid is allowed to stand and separated. The organic phase is then purified to obtain a high-purity, low-grade copper sulfide ore foaming collector.

[0019] The alkyl dithiophosphate is selected from any one of methyl dithiophosphate, ethyl dithiophosphate, propyl dithiophosphate, butyl dithiophosphate, isobutyl dithiophosphate, pentyl dithiophosphate, isopentyl dithiophosphate, and neopentyl dithiophosphate.

[0020] The process conditions for dissolving the alkyl dithiophosphate are: temperature 50~80℃, time 30~60min, and stirring speed 250r / min.

[0021] The halogen element is selected from any one of Cl2, Br2, and I2.

[0022] The reaction conditions between the alkyl dithiophosphate and the halogen element are a temperature of 120~180℃ and a time of 120~200min.

[0023] The reaction conditions for the alkyl dithiophosphate and the alkyl dithiophosphate halide are a temperature of 25~50℃ and a time of 120~200min.

[0024] The settling time for separation is 5-6 hours.

[0025] The purification process specifically includes organic phase washing, drying, and filtration.

[0026] The cleaning refers to rinsing with distilled water at least 3 times.

[0027] The drying temperature is 50~80℃ and the drying time is 12~14h.

[0028] Example 1

[0029] Place 528.32g of sodium dibutyldithiophosphate into a 1000ml beaker, add 300ml of distilled water, and heat in a water bath for 40min at a stirring speed of 250r / min and a temperature of 60℃ to dissolve and prepare a sodium dibutyldithiophosphate solution.

[0030] After dividing the solution into two equal parts, 160g of elemental bromine was added dropwise to one part at a rate of 2 drops / second, and then 39.99g of sodium hydroxide was added dropwise to the solution at a rate of 2 drops / second. The reaction was carried out for 200 minutes under the conditions of stirring speed of 250r / min and reaction temperature of 120℃ to obtain a solution of dibutyl dithiophosphate bromide.

[0031] Another portion of sodium dibutyldithiophosphate solution was added to the dibutyldithiophosphate bromide solution, and the reaction was carried out for 150 min at a stirring speed of 250 r / min and a reaction temperature of 50 °C.

[0032] The obtained liquid was transferred to a separatory funnel and allowed to stand for 5 hours for separation. The organic phase was then taken, washed three times with distilled water, filtered, and dried at 50°C for 13 hours. After filtration, the organic phase was obtained as a foaming collector for the target low-grade copper sulfide ore with a purity of 59.11% and a yield of 67.02%.

[0033] Example 2

[0034] Place 416.24g of sodium diethyldithiophosphate in a 1000ml beaker, add 300ml of distilled water, and heat in a water bath for 35min at a stirring speed of 250r / min and a temperature of 55℃ to dissolve and prepare a sodium diethyldithiophosphate solution.

[0035] After dividing the solution into two equal parts, 160g of elemental bromine was added dropwise to one part at a rate of 2 drops / second, followed by 39.99g of sodium hydroxide at a rate of 2 drops / second. The reaction was carried out for 170 minutes at a stirring speed of 250r / min and a reaction temperature of 130℃ to obtain a solution of diethyldithiophosphate bromide.

[0036] Another portion of sodium diethyldithiophosphate solution was added to the diethyldithiophosphate bromide solution, and the reaction was carried out for 180 min at a stirring speed of 250 r / min and a reaction temperature of 35℃.

[0037] The obtained liquid was transferred to a separatory funnel and allowed to stand for 6 hours for separation. The organic phase was then taken, washed three times with distilled water, filtered, and dried at 60°C for 12 hours. After filtration, the target low-grade copper sulfide ore foaming collector was obtained with a purity of 56.48% and a yield of 65.55%.

[0038] Example 3

[0039] —Application Examples A copper mine has a raw ore copper grade of 0.45%. After grinding to a particle size of -0.074 mm (70%), a process flow of one roughing operation, two cleaning operations, and one scavenging operation is adopted. In the laboratory, after treating the copper ore with the collector prepared in Example 1, the copper recovery rate reached 82.56%, and the copper concentrate grade reached 23.33%. At the beneficiation site, after sulfiding the slurry with sodium sulfide and then treating the copper ore with the collector prepared in Example 1, the copper recovery rate was 83.27%, and the copper concentrate grade was 21.69%, without the need for frothers.

Claims

1. A method for preparing a foaming collector for low-grade copper sulfide ore, characterized in that, The process includes the following steps: Alkyl dithiophosphate a is dissolved in distilled water or anhydrous ethanol to prepare alkyl dithiophosphate solution A; A alkyl dithiophosphate solution A is prepared by adding a halogen element and sodium hydroxide to the solution A, wherein the molar ratio of alkyl dithiophosphate: halogen element: sodium hydroxide is 0.8~1.2:0.8~1.2:0.1~0.

3. Alkyl dithiophosphate b is dissolved in distilled water or anhydrous ethanol to prepare alkyl dithiophosphate solution B. The alkyl dithiophosphates a and b can be the same or different salts. Alkyl dithiophosphate solution B is added to alkyl dithiophosphate halide solution, wherein the molar ratio of alkyl dithiophosphate halide to alkyl dithiophosphate is 1:1~1.1; after the reaction is completed, the resulting liquid is allowed to stand and separated, and the resulting organic phase is the foaming collector for low-grade copper sulfide ore.

2. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The alkyl dithiophosphate is selected from any one of methyl dithiophosphate, ethyl dithiophosphate, propyl dithiophosphate, butyl dithiophosphate, isobutyl dithiophosphate, pentyl dithiophosphate, isopentyl dithiophosphate, and neopentyl dithiophosphate.

3. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The process conditions for dissolving the alkyl dithiophosphate are: temperature 50~80℃, time 30~60min, and stirring speed 250r / min.

4. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The halogen element is selected from any one of Cl2, Br2, and I2.

5. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The reaction conditions between the alkyl dithiophosphate and the halogen element are a temperature of 120~180℃ and a time of 120~200min.

6. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The reaction conditions for the alkyl dithiophosphate and the alkyl dithiophosphate halide are a temperature of 25~50℃ and a time of 120~200min.

7. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The settling time for separation is 5-6 hours.

8. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The method also includes a purification step, specifically organic phase washing, drying, and filtration.

9. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The cleaning refers to rinsing with distilled water at least 3 times.

10. The method for preparing the foaming collector for low-grade copper sulfide ore according to claim 1, characterized in that, The drying temperature is 50~80℃ and the drying time is 12~14h.

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