A method for preparing a low-grade copper ore collector with frothability

Abstract

This invention relates to a method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore, belonging to the field of mineral flotation reagent preparation technology. The method includes the following steps: adding xanthate to distilled water or anhydrous ethanol to obtain a xanthate solution or xanthate-ethanol solution; adding a halogen element and sodium hydroxide to the obtained xanthate solution to obtain a haloxanthate solution; adding alkyl dithiophosphate to distilled water or anhydrous ethanol to obtain an alkyl dithiophosphate solution; adding the alkyl dithiophosphate solution to the haloxanthate solution and reacting; after the reaction, allowing the resulting liquid to stand to obtain a foaming collector for low-grade oxygen-sulfur mixed copper ore; allowing the resulting liquid to stand and separate into layers to obtain a purified foaming collector for low-grade oxygen-sulfur mixed copper ore. The beneficial effects of this invention are: improving the grade and recovery rate of copper concentrate from low-grade copper ore flotation using the prepared collector.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation reagent preparation technology, and specifically relates to a method for preparing a low-grade oxygen-sulfur mixed copper ore collector with foaming properties. Background Technology

[0002] With the continuous mining of copper resources, the grade of the selected ore is constantly decreasing, the mineral intergrowth relationship is becoming increasingly complex, and easily beneficiated sulfide copper ore resources are becoming increasingly depleted, with the remaining ore mostly being low-grade, fine-grained oxygen-sulfur mixed copper ores. Currently, the mainstream collectors in concentrators are butyl xanthate, butylammonium black, and conventional reagents such as Z-200. However, given the deteriorating ore properties, their collecting capacity, selectivity, and overall performance indicators are insufficient to meet production demands.

[0003] While there is a great deal of research on copper collectors, most studies focus on xanthates, black powders, sulfur and nitrogen compounds, and their simple modified products. There is a lack of research on reactive collectors that combine haloxanates and alkyl dithiophosphates. The mechanisms of action are mostly limited to traditional chelation mechanisms, resulting in a weak ability to recover both copper sulfide and copper oxide. Summary of the Invention

[0004] This invention provides a method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore, which addresses the technical problem of poor copper collection ability. The method involves adding an alkyl dithiophosphate solution to a haloxanate solution and reacting to generate a novel composite collector of alkyl dithiophosphate-xanate. This novel collector effectively recovers low-grade copper sulfide and copper oxide, reduces the collection of pyrite and other gangue minerals, and improves the grade and recovery rate of copper concentrate from low-grade copper ore flotation.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] A method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore includes the following steps:

[0007] Step 1: Add xanthate to distilled water or anhydrous ethanol, heat in a water bath, and stir to dissolve to obtain xanthate solution or xanthate ethanol solution;

[0008] Step 2: Add a halogen element and sodium hydroxide to the obtained xanthate solution to obtain a haloxanthate solution;

[0009] Step 3: Add alkyl dithiophosphate to distilled water or anhydrous ethanol, heat in a water bath, stir and dissolve to obtain alkyl dithiophosphate solution;

[0010] Step 4: Add alkyl dithiophosphate solution to haloxanate solution and react;

[0011] Step 5: After the reaction is complete, transfer the liquid obtained in step 4 to a separatory funnel and let it stand. Take the organic layer and wash it with distilled water more than 3 times to obtain a low-grade oxygen-sulfur mixed copper ore collector with foaming properties.

[0012] Step 6: Let the liquid obtained in Step 5 stand and separate into layers. Wash the organic layer with distilled water, dry it, and filter it to obtain a purified, foaming, low-grade oxygen-sulfur mixed copper ore collector.

[0013] Optionally, in step 1, the xanthate is any one of methyl xanthate, ethyl xanthate, propyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate, isopentyl xanthate, or neopentyl xanthate.

[0014] Optionally, in step 2, the halogen element is any one of Cl2, Br2, or I2, causing a substitution reaction between the xanthate and the halogen element to generate a reagent, as shown in the following reaction formula:

[0015] In this denominator, R is selected from C1-C5 alkyl groups and is any one of methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, propylene, butene, and pentyl, and X is any one of Cl, Br, and I.

[0016] Optionally, in step 2, the molar ratio of xanthate to sodium hydroxide of halogen elements is 1:1:0.2.

[0017] Optionally, in step 2, the reaction temperature is 120~180℃ and the reaction time is 120~200min.

[0018] Optionally, in step 1 or step 3, the water bath heating temperature is 50~80℃, the time is 30~60min, and the stirring speed is 250r / min.

[0019] Optionally, in step 4, the molar ratio of haloxanate to alkyl dithiophosphate is 1:1.04, and the reaction formula is as follows:

[0020] , where R, R / The alkyl group is selected from C1-C5, and is any one of methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, propylene, butene, and pentyl, X is any one of Cl, Br, and I, and Me is any one of Na or K.

[0021] Optionally, in step 4, the reaction temperature is 25~50℃ and the time is 120~200min.

[0022] Optionally, in step 5, the standing time is 5-6 hours, the drying temperature is 50-80℃, and the drying time is 12-14 hours.

[0023] The beneficial effects of this invention are:

[0024] 1. This invention involves adding elemental halogens and sodium hydroxide to a xanthate solution to obtain a haloxanthate solution. The haloxanthate solution, as a xanthate, plays a major role in mineral processing. As a preliminary foam flotation collector, the haloxanthate solution is beneficial for the initial collection of copper.

[0025] 2. This invention involves adding an alkyl dithiophosphate solution to a haloxanate solution and reacting to generate a novel composite collector of alkyl dithiophosphate-xanthate. This novel collector effectively recovers low-grade copper sulfide and copper oxide while minimizing the collection of pyrite and other gangue minerals, thus improving the grade and recovery rate of copper concentrate from low-grade copper ore flotation. The novel collector also possesses foaming properties, reducing the amount of foaming agent required. Since this product is a salt, it can be processed into powder through crystallization and granulation for easy production and use. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a flowchart of the preparation process of the present invention. Detailed Implementation

[0028] The embodiments of this application will now be described in detail with reference to the accompanying drawings.

[0029] Example 1

[0030] like Figure 1 As shown in the figure, this embodiment provides a method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore, characterized by comprising the following steps:

[0031] Step 1: Add xanthate to distilled water or anhydrous ethanol, heat in a water bath, and stir to dissolve to obtain xanthate solution or xanthate ethanol solution;

[0032] Step 2: Add a halogen element and sodium hydroxide to the obtained xanthate solution to obtain a haloxanthate solution;

[0033] Step 3: Add alkyl dithiophosphate to distilled water or anhydrous ethanol, heat in a water bath, stir and dissolve to obtain alkyl dithiophosphate solution;

[0034] Step 4: Add alkyl dithiophosphate solution to haloxanate solution and react;

[0035] Step 5: After the reaction is complete, transfer the liquid obtained in step 4 to a separatory funnel and let it stand. Take the organic layer and wash it with distilled water more than 3 times to obtain a low-grade oxygen-sulfur mixed copper ore collector with foaming properties.

[0036] Step 6: Let the liquid obtained in Step 5 stand and separate into layers. Wash the organic layer with distilled water, dry it, and filter it to obtain a purified, foaming, low-grade oxygen-sulfur mixed copper ore collector.

[0037] Specifically, in step 1, the xanthate is any one of methyl xanthate, ethyl xanthate, propyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate, isopentyl xanthate, or neopentyl xanthate.

[0038] In step 2, the halogen element is any one of Cl2, Br2, or I2, causing a substitution reaction between the xanthate and the halogen element to generate a reagent, as shown in the following reaction formula:

[0039] In this denominator, R is selected from C1-C5 alkyl groups and is any one of methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, propylene, butene, and pentyl, and X is any one of Cl, Br, and I.

[0040] Xanthate, ROCSS - It is the xanthate ion, Me + Represents metal cations, such as: Na + or K + X2 is a halogen molecule (such as Cl2, Br2).

[0041] It is a haloxanate. These are salts formed by the reduction of halogens and their reaction with metal cations, such as NaCl and KBr.

[0042] In step 2, the molar ratio of xanthate to sodium hydroxide, a halogen element, is 1:1:0.2.

[0043] In step 2, the reaction temperature is 120~180℃ and the reaction time is 120~200min.

[0044] In step 1 or step 3, the water bath heating temperature is 50~80℃, the time is 30~60min, and the stirring speed is 250r / min.

[0045] In step 4, the molar ratio of haloxanate to alkyl dithiophosphate is 1:1.04, and the reaction formula is as follows:

[0046] , where R, R / The alkyl group is selected from C1-C5, and is any one of methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, propylene, butene, and pentyl, X is any one of Cl, Br, and I, and Me is any one of Na or K.

[0047] It is a haloxanate. It is an alkyl dithiophosphate. Me is an alkyl dithiophosphate group. + Represents a metal cation; It is an alkyl dithiophosphate-xanthate, a novel composite collector. Indicates xanthate group, These are salts formed by the reduction of halogens and their reaction with metal cations, such as NaCl and KBr.

[0048] In step 4, the reaction temperature is 25~50℃ and the time is 120~200min.

[0049] In step 5, the resting time is 5-6 hours, the drying temperature is 50-80℃, and the drying time is 12-14 hours.

[0050] Example 2

[0051] Based on Example 1, the specific steps for preparing a foaming low-grade oxygen-sulfur mixed copper ore collector are as follows:

[0052] 172.16 g of sodium butyl xanthate and 264.16 g of sodium dibutyl dithiophosphate were placed separately into 500 ml beakers, and 150 ml of distilled water was added. The mixture was heated in a water bath at 60 °C with magnetic stirring at 250 rpm for 40 min to dissolve the sodium butyl xanthate and sodium dibutyl dithiophosphate solutions. Then, 160 g of elemental bromine was added dropwise to the solutions at a rate of 2 drops / second, followed by 39.99 g of sodium hydroxide at a rate of 2 drops / second. The reaction temperature was maintained at 120 °C and the magnetic stirrer speed was 250 rpm. The reaction was carried out for 200 min under the condition of n to obtain a xanthate bromide solution. Then, a prepared sodium dibutyldithiophosphate solution was added to the xanthate bromide solution, and the reaction was carried out in a water bath at 50℃ with magnetic stirring at 250 r / min for 150 min. The product after the reaction was transferred to a separatory funnel and allowed to stand for 5 h. Then, the organic phase was taken and washed three times with distilled water. After filtration, the organic phase was dried at 50℃ for 13 h. The resulting organic layer was filtered to obtain a reagent with a purity of 66.32% and a yield of 70.31%.

[0053] A copper mine has a raw ore copper grade of 0.53%. Under conditions of 70% particle size (-0.074mm), one roughing, two cleaning, and one scavenging, the copper recovery rate reached 83.47% and the copper concentrate grade reached 20.85% after treatment with this reagent in the laboratory. However, after on-site treatment with sodium sulfide followed by sodium butyl xanthate, the copper recovery rate was 82.33% and the copper concentrate grade was 20.18%. Compared with the original reagent system, the frother dosage was reduced by 5g per ton of raw ore (the production condition frother dosage was 30g per ton of raw ore).

[0054] Among them, foaming agents are surfactants mainly used in mineral flotation processes. Their core function is to reduce the surface tension of water and form stable foam, thereby assisting useful minerals to float.

[0055] Example 3

[0056] Based on Example 1, the steps for preparing another foaming low-grade oxygen-sulfur mixed copper ore collector are as follows:

[0057] 128.14 g of sodium ethyl xanthate and 264.16 g of sodium dibutyldithiophosphate were placed separately into 500 ml beakers, and 150 ml of distilled water was added. The mixture was heated in a water bath at 60 °C with magnetic stirring at 250 rpm for 40 min to dissolve the sodium ethyl xanthate and sodium dibutyldithiophosphate solutions. Then, 160 g of elemental bromine was added dropwise to the solutions at a rate of 2 drops / second, followed by 39.99 g of sodium hydroxide at a rate of 2 drops / second. The reaction temperature was maintained at 120 °C and the magnetic stirrer speed was 250 rpm. The reaction was carried out for 200 min under the condition of n to obtain a xanthate bromide solution. Then, a prepared sodium dibutyldithiophosphate solution was added to the xanthate bromide solution, and the reaction was carried out in a water bath at 60℃ with magnetic stirring at 250 r / min for 150 min. The product after the reaction was transferred to a separatory funnel and allowed to stand for 5 h. Then, the organic phase was taken and washed three times with distilled water. After filtration, the organic phase was dried at 50℃ for 13 h. The obtained organic layer was filtered to obtain a reagent with a purity of 68.33% and a yield of 76.29%.

[0058] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope described in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore, characterized in that, Includes the following steps: Step 1: Add xanthate to distilled water or anhydrous ethanol, heat in a water bath, and stir to dissolve to obtain xanthate solution or xanthate ethanol solution; Step 2: Add a halogen element and sodium hydroxide to the obtained xanthate solution to obtain a haloxanthate solution; Step 3: Add alkyl dithiophosphate to distilled water or anhydrous ethanol, heat in a water bath, stir and dissolve to obtain alkyl dithiophosphate solution; Step 4: Add alkyl dithiophosphate solution to haloxanate solution and react; Step 5: After the reaction is complete, transfer the liquid obtained in step 4 to a separatory funnel and let it stand. Take the organic layer and wash it with distilled water more than 3 times to obtain a low-grade oxygen-sulfur mixed copper ore collector with foaming properties. Step 6: Let the liquid obtained in Step 5 stand and separate into layers. Wash the organic layer with distilled water, dry it, and filter it to obtain a purified, foaming, low-grade oxygen-sulfur mixed copper ore collector.

2. The method for preparing a foaming low-grade oxygen-sulfur mixed copper ore collector according to claim 1, characterized in that, In step 1, the xanthate is any one of methyl xanthate, ethyl xanthate, propyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate, isopentyl xanthate, or neopentyl xanthate.

3. The method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore according to claim 1, characterized in that, In step 2, the halogen element is any one of Cl2, Br2, or I2, causing a substitution reaction between the xanthate and the halogen element to generate a reagent, the reaction formula of which is as follows: In this denominator, R is selected from C1-C5 alkyl groups and is any one of methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, propylene, butene, and pentyl, and X is any one of Cl, Br, and I.

4. The method for preparing a foaming low-grade oxygen-sulfur mixed copper ore collector according to claim 1, characterized in that, In step 2, the molar ratio of the xanthate and the sodium hydroxide of the halogen element is 1:1:0.

2.

5. The method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore according to claim 1, characterized in that, In step 2, the reaction temperature is 120~180℃ and the reaction time is 120~200min.

6. The method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore according to claim 1, characterized in that, In step 1 or step 3, the water bath heating temperature is 50~80℃, the time is 30~60min, and the stirring speed is 250r / min.

7. The method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore according to claim 1, characterized in that, In step 4, the molar ratio of the haloxanate to the alkyl dithiophosphate is 1:1.04, and the reaction formula is as follows: , where R, R / The alkyl group is selected from C1-C5, and is any one of methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, propylene, butene, and pentyl, X is any one of Cl, Br, and I, and Me is any one of Na or K.

8. The method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore according to claim 1, characterized in that, In step 4, the reaction temperature is 25~50℃ and the time is 120~200min.

9. The method for preparing a foaming collector for low-grade oxygen-sulfur mixed copper ore according to claim 1, characterized in that, In step 5, the settling time is 5-6 hours, the drying temperature is 50-80℃, and the drying time is 12-14 hours.

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