Dihydroxy thioisoflavone copper-arsenic separation inhibitor as well as preparation method and application thereof

Abstract

The invention relates to the field of mineral flotation, in particular to a dihydroxythioisoflavone copper-arsenic separation inhibitor and a preparation method and application thereof. The preparation method of the copper-arsenic separation inhibitor comprises the following steps: adding an 8-beta-D-glucopyranosyl-4 ', 7-dihydroxyisoflavone organic compound into a solvent, then adding a Lawson reagent, raising the temperature, and reacting to obtain a reaction solution; and cooling, filtering, purifying and crystallizing the reaction liquid to obtain the dihydroxythioisoflavone copper-arsenic separation inhibitor. The dihydroxy thioisoflavone copper-arsenic separation inhibitor prepared by the invention can selectively carry out oxidation inhibition on arsenic-containing minerals such as arsenopyrite, arsenhedrite and akaidite, reduces the content of arsenic in copper concentrate, is simple to apply on site, does not need to change the process flow on site, only needs to adjust the dosage of the medicament and add the medicament according to the amount, is simple to operate, and is suitable for industrial production. The index is stable.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation, specifically to a dihydroxythioisoflavone copper-arsenic separation inhibitor, its preparation method, and its application. Background Technology

[0002] The surface properties of chalcocite, arsenopyrite, arsenic chalcopyrite, covellite, and chalcopyrite are similar, and the collectors and depressants used in the flotation process have poor selectivity for each copper and arsenic mineral, leading to significant separation difficulties. Copper-arsenic flotation separation generally employs oxidation methods, which involve adding an oxidant to the solution to oxidize the arsenic-containing minerals, forming a hydrophilic oxide film on their surface. However, because arsenopyrite and arsenic chalcopyrite are more difficult to oxidize than chalcocite, traditional oxidation methods are no longer suitable for inhibiting arsenopyrite and arsenic chalcopyrite. Therefore, for complex ore bodies composed of copper and arsenic minerals, developing a depressant capable of selectively oxidizing and inhibiting arsenic-containing minerals provides a new depressant design approach for achieving copper-arsenic separation, which is of reference value for promoting technological progress in the industry. Summary of the Invention

[0003] To address the aforementioned issues, the purpose of this application is to provide a dihydroxythioisoflavone copper-arsenic separation inhibitor, its preparation method, and its application. This copper-arsenic separation inhibitor exhibits excellent inhibition effects on arsenic-containing minerals such as arsenopyrite, arsenic chalcopyrite, and arsenic thioclase, thereby improving the recovery rate of copper and the removal rate of arsenic.

[0004] To achieve the above objectives, this application provides a method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor, comprising the following steps:

[0005] S1. Add the organic compound 8-β-D-glucopyranose-4',7-dihydroxyisoflavone to the solvent, then add Lawson's reagent, raise the temperature, and react to obtain the reaction solution;

[0006] In the above reaction process, the increase in temperature causes Lawson's reagent to depolymerize, generating an unstable thiophosphorus ylide. The carbonyl oxygen of 8-β-D-glucopyranose-4',7-dihydroxyisoflavone acts as a nucleophile to attack the phosphorus of the thiophosphorus ylide, generating a thiophosphoric tetracyclic intermediate. Then, the ring is cleaved to generate a thiocarbonyl compound, namely the copper-arsenic separation inhibitor of dihydroxythioisoflavone.

[0007] S2. The reaction solution was cooled, filtered, purified, and crystallized to obtain the dihydroxythioisoflavone copper-arsenic separation inhibitor. The structure is as follows:

[0008]

[0009] Furthermore, the solvent is anhydrous toluene or tetrahydrofuran.

[0010] Furthermore, the temperature increase is raised to 80-120℃, and the reaction time is 0.5-1.5h.

[0011] Furthermore, the Lawson reagent has a molar ratio of 2-5:1-2 with 8-β-D-glucopyranose-4',7-dihydroxyisoflavone.

[0012] Furthermore, the cooling process involves cooling the temperature to 0-5°C.

[0013] Furthermore, the purification is carried out by elution using a silica gel column or a polyamide resin column, and the eluent used is at least one of petroleum ether and ethyl acetate.

[0014] This application provides a method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor, which yields the dihydroxythioisoflavone copper-arsenic separation inhibitor.

[0015] This application also provides the application of a dihydroxythioisoflavone copper-arsenic separation inhibitor in mineral flotation, comprising the following steps:

[0016] After grinding the raw ore to a particle size of -0.074 mm or higher (with 3000 g / t of calcium oxide added during grinding), 800 g / t of dihydroxythioisoflavone, 200 g / t of butyl xanthate as a collector, and 110 g / t of pine oil as a frother are added sequentially for roughing to obtain a rough concentrate. Then, 150 g / t of butyl xanthate is added for scavenging to obtain a scavenging concentrate. The rough concentrate and scavenging concentrate are mixed and then proceeded to the cleaning process. After adjusting the pulp pH to 11, 60 g / t of dihydroxythioisoflavone is added and the pulp is adjusted for 2 minutes for the first cleaning. Then, after adjusting the pulp pH to 10, 45 g / t of dihydroxythioisoflavone is added and the pulp is adjusted for 2 minutes for the second cleaning. Finally, after adjusting the pulp pH to 9, 25 g / t of dihydroxythioisoflavone is added and the pulp is adjusted for 2 minutes for the third cleaning. After three cleaning processes, a copper concentrate is obtained.

[0017] In summary, this application has the following beneficial effects:

[0018] The dihydroxythioisoflavone copper-arsenic separation inhibitor prepared in this application can selectively inhibit the oxidation of arsenic-containing minerals such as arsenopyrite, arsenic chalcopyrite, and thioarsenic chalcopyrite, thereby reducing the arsenic content in copper concentrate. Compared with traditional arsenic-containing mineral inhibitors, the copper concentrate obtained using the compound of this invention has a lower arsenic grade.

[0019] The dihydroxythioisoflavone copper-arsenic separation inhibitor prepared in this application is simple to apply in the field, requiring no changes to the on-site process. Only the dosage of the agent needs to be adjusted and added in the correct amount. The operation is simple and the indicators are stable. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying 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.

[0021] Figure 1 This is a process flow diagram for the application of this invention. Detailed Implementation

[0022] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] The reagents used in the specific embodiments of this application are of analytical grade. Additionally, Lawson reagent is from Saen Chemical Technology (Shanghai) Co., Ltd., catalog number: E080022; 8-β-D-glucopyranose-4',7-dihydroxyisoflavone is from Shanghai Yuanmu Biotechnology Co., Ltd., catalog number: Q1757.

[0024] Example 1

[0025] A method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor includes the following steps:

[0026] S1. Add 8-β-D-glucopyranose-4',7-dihydroxyisoflavone organic compound to anhydrous toluene at a mass-to-volume ratio of 1:50. Then, while stirring (100 rpm), add Lawson's reagent. The molar ratio of Lawson's reagent to 8-β-D-glucopyranose-4',7-dihydroxyisoflavone organic compound is 3:1. Raise the temperature to 100°C and react for 1 hour to obtain the reaction solution.

[0027] S2. The reaction solution was cooled at 4°C for 1 hour, then filtered through filter paper with a pore size of 2 μm. The solid particles were collected and dissolved in ethyl acetate at a mass-to-volume ratio of 1:5. The solution was then purified by elution using a silica gel column with petroleum ether and ethyl acetate as the eluent. The first elution ratio was 9:1, and the second elution ratio was 7:3. The solution of 8-β-D-glucopyranose-4',7-dihydroxythioisoflavone was obtained by elution with ethyl acetate. The solution was then evaporated and crystallized at 80°C to obtain the copper-arsenic separation inhibitor of dihydroxythioisoflavone.

[0028] Compare with Example 1

[0029] In this control example, ammonium sulfite was used as a copper-arsenic separation inhibitor.

[0030] Compare with Example 2

[0031] In this control example, sodium thiosulfate was used as a copper-arsenic separation inhibitor.

[0032] Performance testing

[0033] Functional tests were performed on the copper-arsenic separation inhibitors of Example 1 and Comparative Examples 1-2 of this application.

[0034] Test of dihydroxythioisoflavone as a copper-arsenic separation inhibitor: Arsenic chalcopyrite (containing 0.3-0.5% copper, 0.012-0.020% arsenic, and 2-3% iron) was ground to a particle size of -0.074 mm or more (3000 g / t of calcium oxide was added during grinding). Then, 800 g / t of dihydroxythioisoflavone, 200 g / t of butyl xanthate as a collector, and 110 g / t of pine oil as a frother were added sequentially. After the reaction, roughing was carried out to obtain a rough concentrate. Then, 150 g / t of butyl xanthate was added and scavenging was carried out to obtain a scavenging concentrate. After mixing the roughing concentrate and scavenging concentrate, the mixture enters the cleaning process. After adjusting the pH of the pulp to 11, 60 g / t of dihydroxythioisoflavone is added and the pulp is adjusted for 2 minutes for the first cleaning. Then, after adjusting the pH of the pulp to 10, 45 g / t of dihydroxythioisoflavone is added and the pulp is adjusted for 2 minutes for the second cleaning. After adjusting the pH of the pulp to 9, 25 g / t of dihydroxythioisoflavone is added and the pulp is adjusted for 2 minutes for the third cleaning. After the three cleaning processes, copper concentrate is obtained, and the copper recovery rate and arsenic removal rate are measured.

[0035] Test of sodium sulfite as a copper-arsenic separation inhibitor: Sodium sulfite was used instead of the dihydroxythioisoflavones mentioned above, and the copper recovery rate and arsenic removal rate were measured respectively.

[0036] Test of sodium thiosulfate as a copper and arsenic separation inhibitor: Sodium thiosulfate was used instead of the dihydroxythioisoflavones mentioned above, and the copper recovery rate and arsenic removal rate were measured respectively. The test results are shown in Table 1:

[0037] Table 1

[0038] Copper recovery rate % Arsenic removal rate % Example 1 88.6 92.5 Compare with Example 1 65.9 70.1 Compare with Example 2 60.3 66.2

[0039] As shown in Table 1, under the same roughing process, Example 1, using dihydroxythioisoflavone as an arsenic-containing mineral inhibitor, can effectively improve the copper recovery rate and reduce the arsenic content. In Control Example 1 and Control Example 2, sodium sulfite and sodium thiosulfate were used as arsenic-containing mineral inhibitors, respectively. The results showed that the copper recovery rate was not high, indicating that the dihydroxythioisoflavone copper-arsenic separation inhibitor prepared in Example 1 of this application has a better copper recovery rate and arsenic removal rate.

[0040] The above description is merely an example and illustration of the concept of this application. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the inventive concept or exceed the scope defined in the claims, they should all fall within the protection scope of this application.

Claims

1. A method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor, characterized in that, Includes the following steps: S1. Add the organic compound 8-β-D-glucopyranose-4',7-dihydroxyisoflavone to the solvent, then add Lawson's reagent, raise the temperature, and react to obtain the reaction solution; S2. Cool, filter, purify, and crystallize the reaction solution to obtain the dihydroxythioisoflavone copper arsenic separation inhibitor.

2. The method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor according to claim 1, characterized in that, The solvent is anhydrous toluene or tetrahydrofuran.

3. The method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor according to claim 1, characterized in that, The temperature increase is to 80-120℃, and the reaction time is 0.5-1.5h.

4. The preparation method of the dihydroxythioisoflavone copper-arsenic separation inhibitor according to claim 1, characterized in that, The Lawson reagent has a molar ratio of 2-5:1-2 with 8-β-D-glucopyranose-4',7-dihydroxyisoflavone.

5. The method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor according to claim 1, characterized in that, The cooling process involves cooling the temperature to 0-5°C.

6. The method for preparing a dihydroxythioisoflavone copper-arsenic separation inhibitor according to claim 1, characterized in that, The purification process involves elution using a silica gel column or a polyamide resin column, with the eluent being at least one of petroleum ether and ethyl acetate.

7. A dihydroxythioisoflavone copper arsenic separation inhibitor prepared by a method for preparing a dihydroxythioisoflavone copper arsenic separation inhibitor as described in any one of claims 1-6.

8. The application of the dihydroxythioisoflavone copper arsenic separation inhibitor prepared by the method of any one of claims 1-7 in arsenic-containing copper minerals.

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